TW201632585A - Liquid crystal alignment agent and liquid crystal alignment film and liquid crystal display element formed from the liquid crystal alignment agent - Google Patents

Abstract

A liquid crystal alignment agent contains a polymer composition, a polysiloxane, and a solvent. The polymer composition is obtained by subjecting a mixture including a tetracarboxylic dianhydride component and a diamine component to a reaction. The diamine component includes first and second diamine compounds defined herein. The polysiloxane obtained by subjecting a polysiloxane compound containing an epoxy-based group and a carboxylic acid compound having a C4-C50 chain to a reaction. A liquid crystal display element made from the aforesaid liquid crystal alignment agent has reduced ion density.

Description

Liquid crystal alignment agent and liquid crystal matching formed by the liquid crystal alignment agent Film and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, and more particularly to a liquid crystal alignment agent for forming a liquid crystal alignment film having excellent ultraviolet light reliability. The present invention also relates to a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element comprising the liquid crystal alignment film.

In recent years, as the display quality requirements for liquid crystal displays have been increasing year by year, liquid crystal display elements have to be developed toward high performance, and then developed from TN and STN to liquid crystal displays of the IPS, VA, PSA and the like. Based on different display principles, the pretilt angles required for liquid crystals in various liquid crystal displays are also different. However, in order to have a better display quality, the common demand is a good liquid crystal alignment property, and therefore, the alignment property of the liquid crystal alignment agent becomes one of important research objects that affect the characteristics of the liquid crystal display element.

Japanese Patent Laid-Open No. 9-176651 shows a liquid crystal alignment film having a good pretilt stability. The liquid crystal alignment agent comprises a polymer and is composed of a cholesterol-containing A diamine compound of a steroid skeleton is obtained by polymerization of a tetracarboxylic dianhydride compound containing a cholesterol skeleton. The above liquid crystal alignment film can maintain a certain pretilt angle at a high temperature to achieve good liquid crystal alignment. However, the liquid crystal alignment agent still has a problem of low ultraviolet reliability and is not acceptable to the industry.

There is an increasing demand in the art for a liquid crystal alignment agent capable of forming a liquid crystal alignment film having superior ultraviolet reliability.

Accordingly, a first object of the present invention is to provide a liquid crystal alignment agent for forming a liquid crystal alignment film having superior ultraviolet reliability.

Thus, the liquid crystal alignment agent of the present invention comprises a polymer composition, a polyoxyalkylene oxide, and a solvent. The polymer composition is obtained by reacting a tetracarboxylic dianhydride component and a diamine component. The diamine component comprises a first diamine compound of formula (I):

Wherein R ¹² and R ¹⁴ are independently selected from -O-, -S-, , R ¹³ represents a C ₂ to C ₁₀ alkylene group, R ¹¹ is a monovalent organic group selected from the group consisting of a single bond, a methylene group, an extended ethyl group, and X represents a C ₁₇ to C ₄₀ having a cholesterol skeleton; a second diamine compound of formula (II):

Wherein R ¹⁵ is selected from -O-, , , , ,and And R ¹⁶ represents an organic group as shown in formula (II-1):

Wherein R ¹⁷ each independently represents hydrogen, fluorine or methyl; and R ¹⁸ , R ¹⁹ or R ²⁰ each independently represent a single bond, -O-, , , , , Or a C ₁ to C ₃ alkylene group; R ²¹ are each independently selected from and Wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl, and R ²² is selected from hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl, C ₁ Alkoxy group to C ₁₂ , -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents an integer of 1 or 2, and l, m and n are integers each independently representing 0 to 4, o, p and q Is an integer which independently represents 0 to 3, and the condition is o+p+q≧3, and r and s each independently represent 1 or 2; wherein the polyoxyalkylene is composed of an epoxy group-containing group The polyoxyalkylene compound of the group is reacted with a carboxylic acid compound having a side chain of C ₄ - C _{50 to} carry out a reaction.

A second object of the present invention is to provide a liquid crystal alignment film having superior ultraviolet reliability which is formed of the liquid crystal alignment agent.

Thus, the liquid crystal alignment film of the present invention is formed by the liquid crystal alignment agent as described above.

A third object of the present invention is to provide a liquid crystal display element comprising the liquid crystal alignment film and having better ultraviolet reliability.

Thus, the liquid crystal display element of the present invention comprises a liquid crystal alignment film as described above.

The effect of the present invention resides in that the diamine component comprising the first and second diamine compounds represented by the formula (I) and the formula (II) and the polyoxyalkylene compound containing the epoxy group are simultaneously used. The polyoxyalkylene obtained by reacting the carboxylic acid compound having a side chain of C ₄ - C ₅₀ causes the liquid crystal alignment film formed by the liquid crystal alignment agent to have better ultraviolet reliability.

11‧‧‧ first unit

111‧‧‧First substrate

112‧‧‧First conductive film

113‧‧‧First liquid crystal alignment film

12‧‧‧Second unit

121‧‧‧second substrate

122‧‧‧Second conductive film

123‧‧‧Second liquid crystal alignment film

13‧‧‧Liquid Crystal Unit

Other features and advantages of the present invention will be apparent from the description of the embodiments of the present invention. FIG. 1 is a partial schematic diagram illustrating an embodiment of a liquid crystal display element of the present invention.

Liquid crystal alignment agent

The liquid crystal alignment agent of the present invention comprises a polymer composition, a polyoxyalkylene oxide, and a solvent.

Polymer composition

The polymer composition is obtained by reacting a tetracarboxylic dianhydride component and a diamine component.

Tetracarboxylic dianhydride

The tetracarboxylic dianhydride component means that the component contains at least one tetracarboxylic dianhydride compound. The tetracarboxylic dianhydride compound is selected from the group consisting of an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, or has the formula (A-1) to (A). -6) a structural tetracarboxylic dianhydride compound, or a combination of the foregoing.

Wherein Y ⁷ represents a divalent group having an aromatic ring structure; n ¹ represents an integer of 1 to 2; and Y ⁷¹ and Y ⁷² may be the same or different and each represents hydrogen or an alkyl group, and

Y ⁸ represents a divalent group containing an aromatic ring structure; Y ⁸¹ and Y ⁸² may be the same or different and each represents hydrogen or an alkyl group.

The above tetracarboxylic dianhydride compound may be used singly or in combination of plural kinds.

The aliphatic tetracarboxylic dianhydride compound includes, but is not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and the like.

The alicyclic tetracarboxylic dianhydride compound includes, but is not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane IV Carboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloheptyl- 1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2.2.2]-oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, and the like.

The aromatic tetracarboxylic dianhydride compound includes, but is not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'-dimethyl Diphenyldecane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride], 1,2,3,4-furan tetracarboxylic dianhydride, 4,4' - bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-di Phenyltetracarboxylic dianhydride, bis(phthalic acid)benzenephosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl) Phthalic acid) dianhydride, bis(triphenylbenzenedioic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride , ethylene glycol-bis (dehydrated trimellitate), propylene glycol-bis (dehydrated trimellitate), 1,4-butane - bis (hydrogen trimellitate), 1,6-hexanediol-bis (anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2 - bis(4-hydroxyphenyl)propane-bis(hydroper trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3 ^a ,4,5,9 ^b - Hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione {(1,3,3 ^a) ,4,5,9 ^b -Hexahydro-5-(tetrahydro-2,5-dioxofuran-3-yl)naphtho[1,2-c]furan-1,3-dione)}, 1,3,3 ^a , 4,5,9 ^b -hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1, 3-diketone, 1,3,3 ^a , 4,5,9 ^b -hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho [1,2-c]-furan-1,3-dione, 1,3,3 ^a ,4,5,9 ^b -hexahydro-7-methyl-5-(tetrahydro-2,5-di Oxyloxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3 ^a ,4,5,9 ^b -hexahydro-7-ethyl -5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3 ^a , 4, 5,9 ^b -hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3- Diketone, 1,3,3 ^a , 4,5,9 ^b -hexahydro-8-ethyl-5-(tetrahydro-2,5-two side Oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3 ^a , 4,5,9 ^b -hexahydro-5,8-di Methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, and 5-(2,5 - Bis-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride.

Preferably, the tetracarboxylic dianhydride compound represented by formula (A-5) is selected from

Preferably, the tetracarboxylic dianhydride compound represented by formula (A-6) is

Preferred specific examples of the tetracarboxylic dianhydride compound include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- Naphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyl fluorene Tetracarboxylic dianhydride, or a combination of the foregoing.

Diamine component

The diamine component comprises a first diamine compound, a second diamine compound, and other diamine compounds different from the first and second diamine compounds.

First diamine compound

The first diamine compound is represented by the formula (I):

Wherein R ¹² and R ¹⁴ are independently selected from -O-, -S-, , R ¹³ represents a C ₂ to C ₁₀ alkylene group, R ¹¹ is a monovalent organic group selected from a single bond, a methylene group, an extended ethyl group, and X represents a C ₁₇ to C ₄₀ having a cholesterol skeleton.

The cholesterol skeleton refers to a cyclopentano-perhydrophenanthrene skeleton in which one or more carbon-carbon bonds in the skeleton may be double bonds.

The cholesterol skeleton includes, but is not limited to, the following formulas (X-1) to (X-4): Wherein, X ¹ can each be a structure of the following formula: + and * are independent representations of a binding key.

Specific examples of X include, but are not limited to, the following formula (X-1-1) to formula (X-4-1), Where * is a binding key.

The first diamine compound includes, but is not limited to, the following formula (I-1) to formula (I-29),

Second diamine compound

The second diamine compound represented by the formula (II): Wherein R ¹⁵ is selected from -O-, , , , ,and And R ¹⁶ represents an organic group as shown in formula (II-1):

Wherein R ¹⁷ is each independently selected from the group consisting of hydrogen, fluorine, and methyl; and R ¹⁸ , R ¹⁹ or R ²⁰ are each independently selected from the group consisting of a single bond, -O-, , , , , And C ₁ to C ₃ alkylene; R ²¹ are each independently selected from and Wherein R ²³ and R ²⁴ are each independently selected from hydrogen, fluoro or methyl, and R ²² is selected from hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl, C ₁ to C ₁₂ alkoxy group, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents a positive number from 1 to 2, and l, m and n are integers each independently representing 0 to 4, o, p And q are integers each independently representing 0 to 3, and the condition is o + p + q ≧ 3, and r and s each independently represent 1 or 2.

Specific examples of the diamine compound represented by the formula (II) may be, for example but not limited to, a diamine compound represented by the formula (II-2) to the formula (II-9): Wherein R ^{25 is} preferably an alkyl group selected from hydrogen, C ₁ to C ₁₂ , and a C ₁ to C ₁₂ alkoxy group.

Preferably, the diamine compound represented by the formula (II) is a diamine compound selected from the following formulas (II-10) to (II-14):

The above-mentioned diamine compounds may be used singly or in combination of plural kinds.

In the liquid crystal alignment agent of the present invention, when the diamine component for forming a polymer composition does not contain the first diamine compound represented by the formula (I) or the second diamine represented by the formula (II) In the case of a compound, the liquid crystal display element including the liquid crystal alignment film formed by the liquid crystal alignment agent has a problem that the ion density is excessively high after irradiation with ultraviolet rays.

Other diamine compounds

Specific examples of other diamine compounds different from the first and second diamine compounds represented by the formula (I) and the formula (II) may be, for example but not limited to, 1,2-diaminoethane [1, 2 -diaminoethane], 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 4,4'-diaminoheptane, 1,3-diamine Base-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7 -diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 2,11-di Aminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, 4,4'-diaminodicyclohexylmethane, 4,4 '-Diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine , tetrahydrodicyclopentadienylene diamine, tricyclic (6.2.1.0 ^2,7 )-undecene dimethyldiamine [tricyclic[6.2.1.0 ^{2 ,7} ]-undecylened Imethylene diamine], 4,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4' -diaminodiphenylanthracene, 4,4'-diaminobenzimidanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1, 5-Diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino-1-(4'-aminobenzene -1,3,3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 3,3'-diaminobenzophenone, 3, 4'-Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amine Benzophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl) Anthracene], 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline, 4,4'-( p-Phenyl isopropylidene) diphenylamine, 4 , 4'-(m-phenylene isopropylidene) bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenyl {5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminobenzene) Oxy)phenyl]-4-(4-ethylphenyl)cyclohexane {1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, and Diamine compounds shown in (VI-1) to (VI-25):

Where R ²⁶ represents -O-, , , , R ²⁷ represents a monovalent group selected from the group consisting of a steroid-containing group, a trifluoromethyl group, a fluorine group, a C ₂ -C ₃₀ alkyl group, and a derivative derived from pyridine [pyridine] or pyrimidine. a monovalent group containing a cyclic structure of a nitrogen atom such as [pyrimidine], triazine, piperidine, and piperazine, and a combination thereof

Where R ²⁸ represents -O-, , , , R ²⁹ and R ³⁰ each independently represent a divalent group selected from the group consisting of an aliphatic ring, an extended aromatic ring, and a heterocyclic group; and R ³¹ represents a C ₃ -C ₁₈ alkyl group, C. _{a 3-} C ₁₈ alkoxy group, a C ₁ -C ₅ fluoroalkyl group, a C ₁ -C ₅ fluoroalkoxy group, a cyano group, or a halogen atom;

Wherein Y ³ represents hydrogen, C ₁ -C ₅ fluorenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy or halogen, and Y ³ in each repeating unit may be the same or different; n ² is an integer from 1 to 3;

Where t is an integer from 2 to 12;

Where u is an integer from 1 to 5;

Wherein, Y ⁴ and Y ⁴² may be the same or different, and each independently represent a twelve monovalent organic group; and Y ⁴¹ represents a derived from pyridine, pyrimidine, triazine, piperidine, and piperazine ring nitrogen atom a divalent group of a structure;

Wherein Y ⁵ , Y ⁵¹ , Y ⁵² and Y ⁵³ are respectively the same or different and each independently represents a C ₁ -C ₁₂ hydrocarbon group, p ¹ represents an integer from 1 to 3, and q ¹ represents from 1 to 20 Integer

Wherein Y ⁶ represents -O- or a cyclohexane group, Y ⁶¹ represents -CH ₂ -, Y ⁶² represents a phenyl or cyclohexane group, and Y ⁶³ represents hydrogen or heptyl;

Specific examples of the other diamine compound described above may be used singly or in combination of plural kinds.

Preferably, a specific example of the diamine compound represented by the formula (VI-1) comprises 2,4-diaminophenyl ethyl formate, 3,5-diaminobenzene. 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3 ,5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diamine 1-hexadecoxy-2,4-diaminobenzene, 1-octadecoxy-2,4-diaminobenzene,

A preferred specific example of the diamine compound represented by the formula (VI-2) contains

(where v ¹ represents an integer from 3 to 12),

(where v ² represents an integer from 3 to 12),

(where v ³ represents an integer from 3 to 12), and

(where v ⁴ represents an integer from 3 to 12).

Preferably, specific examples of the diamine compound represented by the formula (VI-3) include: (1) when n is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene, 2, 5 -diamine toluene, etc.; (2) when n is 2:4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-di Aminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2, 2'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, and 4,4'-diamino-2,2'-bis(trifluoromethyl) linkage Benzene, etc.; (3) when n is 3: 1,4-bis(4'-aminophenyl)benzene or the like. More preferably, the diamine compound represented by the formula (VI-3) is selected from the group consisting of p-diamine benzene, 2,5-diamine toluene, 4,4'-diaminobiphenyl, 3,3'- Dimethoxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene, or a combination of the foregoing.

Preferably, a specific example of the diamine compound represented by the formula (VI-5) is 4,4'-diaminodiphenyl sulfide.

Preferably, a specific example of the diamine compound represented by the formula (VI-8) is selected from One of the aforementioned combinations.

Preferably, B ³⁹ of the diamine compound represented by the formulae (VI-17) to (VI-20) represents a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group; as in the formula (VI- B ⁴⁰ of the diamine compound shown in 21) to (VI-25) represents a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group.

Preferred specific examples of other diamine compounds suitable for use in the present invention include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethylbicyclo Hexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclic (6.2.1 .0 ^2,7 ) ^-undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,2-diaminoethane, 4,4'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, (VI-1-1), formula (VI-1-2), formula (VI-2-1), formula (VI-2-11), p-diamine benzene, m-diamine benzene, o-di Amine benzene, or a compound represented by the formula (VI-8-1).

Preferably, the first diamine compound represented by the formula (I) is used in an amount of 5 to 25 moles, more preferably 8 to 22 moles, based on the diamine component being 100 moles. The best is 10 to 20 moles.

Preferably, the second diamine compound represented by the formula (II) is used in an amount of 5 to 25 moles, preferably more preferably 100 moles based on the diamine component. It is 8 to 22 moles, more preferably 10 to 20 moles.

Preferably, the other diamine compound is used in an amount of from 50 to 90 moles, more preferably from 56 to 84 moles, still more preferably from 60 to 80 moles, based on the diamine component being 100 moles. .

The polymer composition comprises a poly-proline polymer, a polyimine polymer, a polyamidene block copolymer, and combinations of the foregoing.

Polylysine polymer

A poly-proline polymer is prepared by subjecting a tetracarboxylic dianhydride component and a diamine component to a polycondensation reaction. The polycondensation reaction is carried out by performing a polycondensation reaction in a solvent at a temperature of from 0 ° C to 100 ° C for from 1 hour to 24 hours to form a reaction solution. Then, the above reaction solution is subjected to distillation under reduced pressure in an evaporator to obtain the polyaminic acid polymer. Alternatively, the above reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, which is then dried under reduced pressure to obtain the polyamic acid polymer.

Preferably, the tetracarboxylic dianhydride component is used in an amount ranging from 20 moles to 200 moles based on the total mole number of the diamine component of 100 moles; more preferably, the tetracarboxylic acid II The anhydride component is used in an amount ranging from 30 moles to 120 moles.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent. Further, the solvent used in the polycondensation reaction is not particularly limited as long as it is a soluble reactant and a product. Specific examples of the solvent include, but are not limited to, (1) an aprotic polar solvent: 1-methyl-2-pyrrolidone, nitrogen, nitrogen-dimethylacetamide, nitrogen, nitrogen. - dimethylformamide, dimethyl hydrazine, γ-butyrolactone, tetramethyl urinary Or hexamethylphosphoric acid triamide; (2) phenolic solvent: m-cresol, xylenol, phenol, halogenated phenol, and the like.

Preferably, the solvent used in the polycondensation reaction is used in an amount ranging from 200 parts by weight to 2,000 parts by weight based on 100 parts by weight of the total of the mixture of the tetracarboxylic dianhydride component and the diamine component; More preferably, the solvent used in the polycondensation reaction is used in an amount ranging from 300 parts by weight to 1,800 parts by weight.

In particular, in the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent as long as the polyamic acid polymer is not precipitated. The poor solvent may be used singly or in combination, and the poor solvent includes, but is not limited to, (1) an alcohol: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, three Ethylene glycol, etc.; (2) ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) esters: methyl acetate, ethyl acetate, butyl acetate, oxalic acid Diethyl ester, diethyl malonate, ethylene glycol ethyl ether acetate, etc.; (4) ethers: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol positive Ethyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.; (5) halogenated hydrocarbons: dichloromethane, 1, 2 - Dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; (6) Hydrocarbons: tetrahydrofuran, hexane, heptane, octane, benzene, toluene , xylene, etc.; or (7) a combination of the foregoing. Specific examples of the poor solvent may be used singly or in combination.

Preferably, the poor solvent is used in an amount ranging from 0 parts by weight to 60 parts by weight based on 100 parts by weight of the diamine component; more preferably, the poor solvent is used in an amount ranging from 0 parts by weight to 50 parts by weight. .

Polyimine polymer

The method for preparing the polyimine polymer comprises dissolving a mixture comprising a tetracarboxylic dianhydride component and a diamine component in a solvent, performing a polymerization reaction to form a poly-proline polymer, and the dehydrating agent and the contact In the presence of a medium, further heating and performing a dehydration ring-closure reaction, such that the proline functional group in the polyaminic acid polymer is converted into a quinone imine functional group (ie, ruthenium iodide) via a dehydration ring closure reaction to obtain a poly Yttrium imine polymer.

a tetracarboxylic dianhydride component and a diamine component used in the preparation of the polyamidene polymer, and the tetracarboxylic dianhydride component and the diamine used in the preparation of the polyamic acid polymer described above The components are the same.

The solvent used in the dehydration ring closure reaction may be the same as the solvent in the liquid crystal alignment agent, and therefore will not be described again. Preferably, the solvent used in the dehydration ring closure reaction is used in an amount ranging from 200 parts by weight to 2,000 parts by weight based on 100 parts by weight of the polyamidamide polymer; more preferably, it is used in a dehydration ring closure reaction. The solvent is used in an amount ranging from 300 parts by weight to 1,800 parts by weight.

Preferably, the dehydration ring closure reaction has an operating temperature in the range of from 40 ° C to 200 ° C, and more preferably from 40 ° C to 150 ° C. When the operating temperature of the dehydration ring-closure reaction is lower than 40 ° C, the reaction will be incomplete, resulting in a lower degree of oxime imidization of the poly-proline polymer. If the operating temperature of the dehydration ring-closure reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyimine polymer is low.

The polymer composition of the present invention for the liquid crystal alignment agent preferably has a ruthenium iodide ratio of from 30 to 90%, more preferably from 40 to 85%. More preferably 50 to 80%. When a polymer composition having a ruthenium iodide ratio as defined above and a liquid crystal alignment film formed of the liquid crystal alignment agent is used, the ion density after ultraviolet irradiation can be further reduced.

The dehydrating agent used in the dehydration ring closure reaction is, but not limited to, an acid anhydride compound such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like. The dehydrating agent is used in an amount ranging from 0.01 moles to 20 moles per mole of the polyamine polymer. The catalyst used in the dehydration ring closure reaction comprises a pyridine compound such as pyridine, trimethylpyridine, lutidine or the like; a tertiary amine compound such as triethylamine. For each mole of the dehydrating agent, the catalyst is used in an amount ranging from 0.5 moles to 10 moles.

Polyimide block copolymer

The polyamidiminated block copolymer includes, but is not limited to, a polyphthalic acid block copolymer, a polyamidiene block copolymer, a polyphthalic acid-polyimine block copolymer. Or a combination of the foregoing.

Preferably, the method for preparing the polyamidiminated block copolymer comprises the steps of: dissolving a starting material in a solvent and performing a polycondensation reaction, wherein the starting material comprises at least one of the above The polyamic acid polymer and/or at least one polyimine polymer as described above, and further may further comprise a tetracarboxylic dianhydride component and a diamine component.

The tetracarboxylic dianhydride component and the diamine component in the starting material are the same as the tetracarboxylic dianhydride component and the diamine component used in the preparation of the polyamic acid polymer described above, and the same is used for The solvent in the polycondensation reaction may be the same as the solvent in the liquid crystal alignment agent, and therefore will not be described again.

Preferably, the solvent used in the polycondensation reaction is used in an amount ranging from 200 parts by weight to 2,000 parts by weight based on 100 parts by weight of the starting material; more preferably, the solvent used in the polycondensation reaction The amount used ranges from 300 parts by weight to 1,800 parts by weight.

Preferably, the polycondensation reaction is operated at a temperature ranging from 0 ° C to 200 ° C; more preferably, the polycondensation reaction is operated at a temperature ranging from 0 ° C to 100 ° C.

Preferably, the starting material comprises, but is not limited to, (1) the terminal groups and structures of the first and second poly-proline polymers are different; (2) the ends of the first and second polyimine polymers The base and structure are different; (3) the poly-proline and polyimine polymers have different terminal groups and structures; (4) poly-proline polymer, tetracarboxylic dianhydride component and diamine component Wherein at least one of the tetracarboxylic dianhydride component and the diamine component is different from the tetracarboxylic dianhydride component and the diamine component structure used to form the polyamic acid polymer; (5) a polyimine polymer, a tetracarboxylic dianhydride component and a diamine component, wherein at least one of the tetracarboxylic dianhydride component and the diamine component and the tetracarboxylic acid used for forming the polyimine polymer The acid dianhydride component and the diamine component are structurally different; (6) a poly-proline polymer, a polyimine polymer, a tetracarboxylic dianhydride component, and a diamine component, wherein the tetracarboxylic acid At least one of the dianhydride component and the diamine component is different from the tetracarboxylic dianhydride component and the diamine component structure used for forming the polyphthalic acid polymer and the polyamidene polymer; (7) structural phase First and second a proline polymer, a tetracarboxylic dianhydride component, and a diamine component; (8) a first and a second polyimine polymer having a structural difference, a tetracarboxylic dianhydride component, and a diamine component (9) first and second polyaminic acid polymers having terminal groups which are anhydride groups and structurally different, and diamine components; (10) First and second polyamic acid polymers having an amine group and a different structure, and a tetracarboxylic dianhydride component; (11) first and second having an acid anhydride group and different structures a polyimine polymer, and a diamine component; (12) a first and a second polyimine polymer having an amine group and a different structure, and a tetracarboxylic dianhydride component.

Preferably, the polyaminic acid polymer, the polyamidiene polymer, and the polyamidene block copolymer may be molecular weight adjusted first, without affecting the efficacy of the present invention. End modified polymer. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. The method for producing the terminal modified polymer can be obtained by adding a monofunctional compound while carrying out a polycondensation reaction of the polyamic acid polymer.

Specific examples of the monofunctional compound include, but are not limited to, (1) monobasic acid anhydride: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecane Succinic anhydride, n-hexadecyl succinic anhydride, etc.; (2) monoamine compound: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, positive Indoleamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine , n-icosylamine, etc.; (3) monoisocyanate compound: phenyl isocyanate, naphthyl isocyanate, and the like.

The polymer composition of the present invention has a weight average molecular weight measured by gel permeation chromatography (GPC) ranging from 2,000 to 200,000, preferably from 3,000 to 100,000, more preferably from 4,000 to 50,000.

Polyoxane

The polyoxyalkylene is produced by reacting a polyoxyalkylene compound containing an epoxy group and a carboxylic acid compound having a side chain of C ₄ to C ₅₀ .

Preferably, the epoxy group-containing polyoxyalkylene compound is formed by polycondensation of a monodecane compound component comprising a first decane compound represented by formula (III): Si (R ³² ) _y (OR ³³ ) _4-y (III)

Wherein at least one R ³² is a functional group selected from the group consisting of the formula (B-1), the formula (B-2) or the formula (B-3), and the remaining R ³² is independently selected from a hydrogen atom, C ₁ An alkyl group of C ₁₀ , a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, and R ³³ are each independently selected from a hydrogen atom, a C ₁ to C ₆ alkyl group, and C ₁ to C ₆ acyl, and C ₆ to C ₁₅ aryl group, and Y represents and integer of 1 to 3;

Wherein A is selected from an oxygen atom or a single bond, h is an integer represented by 1 to 3, and i is an integer represented by 0 to 6, and the condition is that when i is 0, A represents a single bond,

Where j is an integer representing from 0 to 6,

Wherein B ¹ is an alkylene group representing C ₂ to C ₆ ; R ³⁴ represents a hydrogen atom or an alkyl group of C ₁ to C ₆ .

Preferably, in addition to the first decane compound represented by the formula (III) as described above, the decane compound further comprises the second decane compound represented by the formula (IV): Si(R ³⁵ ) _b ( OR ³⁶ ) _4-b (IV)

Wherein R ³⁵ is each independently selected from a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, and R ³⁶ is each independently selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, or a C ₆ to C ₁₅ aryl group, and b represents an integer of 0 to 3.

Preferably, the carboxylic acid compound has a C ₆ -C ₅₀ side chain.

When the liquid crystal alignment agent does not contain the polyoxyalkylene oxide, the liquid crystal display element containing the liquid crystal alignment film formed of the liquid crystal alignment agent has a poor voltage holding ratio after ultraviolet irradiation.

Preferably, the polysiloxane is used in an amount of from 3 to 30 parts by weight, more preferably from 4 to 25 parts by weight, still more preferably from 5 to 20 parts by weight, based on 100 parts by weight of the polymer composition.

First decane compound

The first silicon compound is alkoxy as shown in the formula ^{(III): Si (R 32} ) y (OR 33) 4-y (III)

Wherein at least one R ³² is a functional group selected from the group consisting of the formula (B-1), the formula (B-2) or the formula (B-3), and the remaining R ³² is independently selected from a hydrogen atom, C ₁ An alkyl group of C ₁₀ , a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, and R ³³ are each independently selected from a hydrogen atom, a C ₁ to C ₆ alkyl group, and C ₁ to C ₆ acyl, and C ₆ to C ₁₅ aryl group, and Y represents and integer of 1 to 3.

Specific examples of the first decane compound represented by the formula (III) include, but are not limited to, 3-(nitrogen, nitrogen-diglycidyl)aminopropyltrimethoxydecane [3-(N,N-diglycidyl). Aminopropyl trimethoxysilane], 3-(N-allyl-N-glycidyl)aminopropyl trimethoxysilane, 3-glycidyl ether Trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 3-glycidyl ether propyl methyl dimethoxy decane, 3-glycidyl ether propyl methyl diethoxy Decane, 3-glycidyl ether propyl dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, 2-shrink Glyceryl ether ethyl triethoxy decane, 2-glycidyl ether ethyl methyl dimethoxy decane, 2-glycidyl ether ethyl methyl diethoxy decane, 2-glycidyl ether Dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether butyl trimethoxy decane, 4-glycidyl ether butyl triethyl Oxydecane, 4-glycidyl ether butyl methyl dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4-glycidyl ether butyl dimethyl methoxy decane, 4- Glycidyl ether butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3) , 4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltri Ethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3- Epoxypropenyl)methoxy]propyltriethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy]propylmethyldimethoxydecane, and [(3- Ethyl-3-epoxypropenyl)methoxy]propane dimethyl methoxydecane, and the like. These compounds may be used singly or in combination of plural kinds.

In the above first decane compound represented by the formula (III), preferred is 3-glycidyl ether propyl trimethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, 4-glycidol. Ether butyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, [( 3-ethyl-3-epoxypropenyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy]propyltriethoxydecane, and One of the aforementioned combinations.

The first decane compound represented by the formula (III) is used in an amount of from 0.3 to 1.0 mol, preferably from 0.35 to 0.95 mol, more preferably from 0.4 to 0.9, based on 1 mol of the decane compound component. Moor.

Second decane compound

The second decane compound is as shown in formula (IV): Si(R ³⁵ ) _b (OR ³⁶ ) _4-b (IV)

Wherein R ³⁵ is each independently selected from a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, and R ³⁶ is each independently selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, or a C ₆ to C ₁₅ aryl group, and b represents an integer of 0 to 3.

When b is 0, the second decane compound represents a tetrafunctional decane compound. When b is 1, the second decane compound represents a trifunctional decane compound. When b is 2, the second decane compound represents a difunctional decane compound. when b is 3, and the second decane compound represents a monofunctional decane compound.

Specific examples of the second decane compound represented by the formula (IV) include, but are not limited to, (1) a tetrafunctional decane compound such as tetrachlorosilane, tetramethoxy decane, tetraethoxy decane, tetra-negative Propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, tetra- or 2-butoxybutane, etc.; (2) trifunctional decane compounds such as trichlorodecane, trimethoxy decane, triethoxy Decane, fluorotrichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane; methyltrichlorodecane; methyltrimethoxydecane, methyltriethoxydecane, 2-(trifluoromethyl)B Trichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane, methyloltrichlorodecane, hydroxymethyltrimethoxydecane , hydroxyethyltrimethoxydecane, decylmethyltrichlorodecane, 3-mercaptopropyltrichlorodecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, 3-mercaptopropyltrimethoxy Decane, 3-mercaptopropyltriethoxydecane, phenyltrichlorodecane, phenyltrimethoxydecane, phenyltriethoxydecane; (3) difunctional decane For example, methyl dichlorosilane, methyl dimethoxy decane, methyl diethoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl di Oxydecane, methyl [2-(perfluoro-n-octyl)ethyl]dichlorodecane, methyl [2-(perfluoro-n-octyl)ethyl]dimethoxydecane, 3-mercaptopropyl Dichlorodecane, 3-mercaptopropylmethyldimethoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, etc.; (4) monofunctional decane compounds, such as chlorodimethyl decane [ Chlorodimethylsilane], methoxydimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, chloromethyl diphenyl decane, methoxymethyl Diphenyl Decane and so on.

Specific examples of commercially available products of the second decane compound represented by the formula (IV) are, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21- manufactured by Shin-Etsu Chemical Co., Ltd. 5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X- 40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40- 9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, and KR9706; Glass Resin manufactured by Showa Denko; SH804, SH805 manufactured by Dow Corning Toray , SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, and SR2420; FZ3711 and FZ3722 manufactured by NUC; DMS-S12, DMS-S15, DMS-S21, DMS-S27 manufactured by JNC, DMS-S31, DMS-S32, DMS-S33, D MS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, and XMS-5025; methyl decanoate manufactured by Mitsubishi Chemical MS51 and methyl decanoate MS56; ethyl decanoate 28, ethyl citrate 40 and ethyl decanoate 48 manufactured by Colcoat; and GR100, GR650, GR908 and GR950 manufactured by Showa Denko.

Among the above second decane compounds represented by the formula (IV), preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, and phenyl. Trimethoxydecane, phenyltriethoxydecane, 3-mercaptopropylmethyldichlorodecane, 3-mercaptopropylmethyldimethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethyl Oxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, or a combination of the foregoing.

The second decane compound represented by the formula (IV) is used in an amount of from 0 to 0.7 mol, preferably from 0.05 to 0.65 mol, more preferably from 0.1 to 0.6, based on 1 mol of the decane compound component. Moor.

Method for preparing polyoxyalkylene containing epoxy groups

A general method can be used for the condensation reaction of preparing the epoxy group-containing polyoxyalkylene. For example, an organic solvent, water or a catalyst is further added to the above decane compound or a mixture thereof, followed by heating at 50 ° C to 150 ° C by an oil bath or the like, preferably for 0.5 to 120 hours. While heating, the mixture may be stirred or placed under reflux.

The above organic solvent is not particularly limited and may be the same as or different from the solvent contained in the liquid crystal alignment agent of the present invention.

The organic solvent is selected from the group consisting of a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Specific examples of the hydrocarbon compound include toluene and xylene; and specific examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. Specific examples of the aforementioned ester compound include ethyl acetate, n-butyl acetate, isoamyl acetate, and propylene Alcohol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate; specific examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxins Specific examples of the aforementioned alcohol compound include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol single n-Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether. The organic solvent may be used singly or in combination of two or more.

Preferably, the organic solvent is used in an amount of 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total of the decane compound.

Preferably, the water is used in an amount of from 0.5 to 100 moles, more preferably from 1 to 30 moles, based on 1 mole of hydrolyzable groups contained in the decane compound.

The catalyst can be, for example but not limited to, an acid, an alkali metal compound, an organic base, a titanium compound, or a zirconium compound.

The acid can be, for example but not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic anhydride, or a combination of the foregoing.

The alkali metal compound may be, for example but not limited to, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide or the like.

The organic base may be, for example but not limited to, one to two organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-di a tertiary organic amine such as methylaminopyridine or diazabicycloundecene; and a fourth organic amine such as tetramethylammonium hydroxide.

The amount of the catalyst used varies depending on the reaction conditions such as the type and temperature, and should be appropriately set. For example, the catalyst is preferably used in an amount of from 0.01 to 5 moles, more preferably from 0.03 to 3 moles, still more preferably from 0.05 to 1 mole, based on the total of the decane compound being 1 mole.

After the reaction is terminated, it is preferred to wash the organic solvent layer separated from the reaction solution with water. More preferably, the reaction solution is washed with water containing a small amount of salt to facilitate washing. For example: washing with an aqueous solution containing approximately 0.2% by weight of ammonium nitrate. The washing is carried out until the aqueous layer after washing becomes neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed to obtain the polyoxyalkylene.

The polyoxyalkylene of the present invention has a weight average molecular weight measured by gel permeation chromatography (GPC) ranging from 500 to 100,000, preferably from 800 to 50,000, more preferably from 1,000 to 20,000.

Carboxylic acid compound

The carboxylic acid compound has a side chain of C ₄ to C ₅₀ . Preferably, the carboxylic acid compound has a side chain of from C ₆ to C ₅₀ .

Specific examples of the compound having a carboxylic acid side chain of C ₄ to C ₅₀ comprising of but not limited to a carboxylic acid derivative having a steroid skeleton, a compound represented by the formula (V), or a combination of one of the foregoing.

B ² -L ⁰ -L ¹ -Z (V)

Specific examples of the carboxylic acid derivative having an anthracene skeleton include, but are not limited to, a benzoic acid derivative having an anthracene skeleton, a succinic acid derivative having an anthracene skeleton, a compound represented by the formula (IV), or a combination of the foregoing.

In formula (IV), n ³ is an integer from 0 to 18, X ² by the Formula (X ² -1), Formula (X ² -2) or Formula (X ² -3) a group represented by:

Specific examples of the carboxylic acid derivative having an anthracene skeleton include, but are not limited to, cholestanyloxy benzoic acid, cholestenyloxy benzoic acid, lanostanyl benzoic acid (lanostanyloxy) Benzoic acid), cholestanyloxy carbonyl benzoic acid, cholestenyloxy carbonyl benzoic acid, lanostanyloxy carbonyl benzoic acid, Succinic acid-5ξ-cholestane-3-yl ester (5ξ-cholestane-3-yl succinate), amber Acid-5ξ-cholestene-3-yl succinate, succinic acid-5ξ-lanostane-3-yl vinegar (5ξ-lanostane-3-yl succinate), by formula ( A compound represented by IV-1), a compound represented by the formula (IV-2), or a combination of the above compounds.

B ² -L ⁰ -L ¹ -Z (V)

In the formula (V), B ² represents a linear alkyl group or a branched alkyl group of C ₄ to C ₅₀ . A part or all of the hydrogen atom of the above alkyl group may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group.

Specific examples of the linear alkyl or branched alkyl group in which B ² represents C ₄ to C ₅₀ include, but are not limited to, n-butyl group, second butyl group, tert-butyl group, n-pentyl group, and 3-methyl group. Base, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2 - dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl 4,4-Dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl , 2,3-dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl , 2,3,3-trimethylbutyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5- Methyl heptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-decyl, n-decyl, n. Alkyl, n-dodecane , N-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, or n-nonadecyl group.

Preferably, in the formula (V), B ² represents a C ₆ to C ₅₀ linear alkyl group or a branched alkyl group, or a C ₆ to C ₅₀ linear chloroalkyl group or a branched chloroalkyl group.

L ⁰ represents a single bond or * -O-, wherein "*" represents a bonding position B ^2.

L ¹ represents a single bond, a phenylene group, a stretched biphenyl group, a cyclohexylene group, a dicyclohexyl group, or a group represented by the formula (L ¹ -1) or the formula (L ¹ -2): Wherein * represents the position bonded to Z, and Z represents a carboxylic acid group.

When L ¹ is a single bond, L ⁰ is a single bond.

Preferably, the compound represented by the formula (V) is selected from the compounds represented by the formula (V-1) to the formula (V-5): H _2W+1 C _w -COOH (V-1), F _2u+1 C _u -C _v H _2v -COOH (V-3),

Wherein u represents an integer from 1 to 5, v represents an integer from 1 to 18, u+v≧4, w represents an integer from 4 to 20, p represents 0 or 1, and r represents an integer from 0 to 18, u+r≧ 4, and s and t each represent an integer of 0 to 2.

Specific examples of the formulae (V-1) to (V-5) include, but are not limited to, valeric acid, caproic acid, n-heptanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, N-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-octadecylbenzoic acid, 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4- Octadecyloxybenzoic acid, 4-(4-pentyl-cyclohexyl)benzoic acid, 4-(4-hexyl-cyclohexyl)benzoic acid, 4-(4-heptyl-cyclohexyl)benzoic acid, 4 '-pentyl-two Cyclohexyl-4-carboxylic acid, 4'-hexyl-dicyclohexyl-4-carboxylic acid, 4'-heptyl-dicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid (4'-pentyl-biphenyl-4-carboxylic acid), 4'-hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4-(4-pentyl-di Cyclohexyl-4-yl)benzoic acid, 4-(4-hexyl-dicyclohexyl-4-yl)benzoic acid, 4-(4-heptyl-dicyclohexyl-4-yl)benzoic acid, V-6) to at least one of the compounds represented by the formula (V-8), or a combination of the foregoing.

F ₃ CC ₃ H ₆ -COOH (V-6),

Preferably, specific examples of the carboxylic acid compound having a C ₄ to C ₅₀ side chain include, but are not limited to, cholestyloxybenzoic acid, cholestyloxycarbonylbenzoic acid, represented by the formula (IV-1) Compound, valeric acid, caproic acid, n-heptanoic acid, n-octanoic acid, n-hexadecanoic acid, stearic acid, n-hexylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexyloxybenzoic acid, 4-ten Octaoxybenzoic acid, 4-(4-pentyl-cyclohexyl)benzoic acid, 4'-pentyl-dicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4-(4-hexyl-dicyclohexyl-4-yl)benzoic acid, a compound represented by the formula (V-6), a compound represented by the formula (V-7), or a combination of the foregoing.

Preferably, the molar equivalent amount of the carboxylic acid compound having a C ₄ to C ₅₀ side chain and the first decane compound represented by the formula (III) is in the range of 0.2 to 1.2, and more preferably 0.3 to 1.1. More preferably, it is 0.4 to 1.0.

When the liquid crystal alignment agent contains the carboxylic acid compound having a C ₆ to C ₅₀ side chain, the liquid crystal display element containing the liquid crystal alignment film formed of the liquid crystal alignment agent has a preferable voltage holding ratio after ultraviolet irradiation.

Method for preparing the polyoxyalkylene

The polyoxyalkylene is produced by reacting the epoxy group-containing polyoxyalkylene compound and the carboxylic acid compound having a C ₄ to C ₅₀ side chain in a solvent and in the presence of a catalyst. Got it.

The solvent is not particularly limited and may be the same as or different from the solvent for preparing the epoxy group-containing polyoxyalkylene compound. Preferably, specific examples of the solvent are 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination of the foregoing.

The catalyst is not particularly limited and may be the same as or different from the catalyst for preparing the epoxy group-containing polyoxyalkylene compound, and a curing accelerator may also be used.

The hardening accelerator is a compound which can promote the reaction of the epoxy group-containing polyoxyalkylene compound and the carboxylic acid compound having a C ₄ -C ₅₀ side chain. Specific examples of the hardening accelerator include, but are not limited to, tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, triethanolamine; Imidazole compounds such as 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole , 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2 -ethyl-4-methyloxazol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2- Cyanoethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecyl 1-(2-cyanoethyl)-2-n-undecanyl imidazolium trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium benzoate, 1- (2-cyanoethyl)-2-ethyl-4-methylimidazolium benzoate, 2,4-diamino-6-[2'-methylimidazolyl-(1')] Ethyl-s-triazine, 2,4- Diamino-6-(2'-n-undecylimidazolyl)ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl -(1')]ethyl-s-triazine, isocyanuric acid addition of 2-methylimidazole, isocyanuric acid addition of 2-phenylimidazole, 2,4-diamino- An isocyanuric acid adduct of 6-[2'-methylimidazolyl-(1')]ethyl-s-triazine; an organophosphorus compound such as diphenylphosphine, triphenylphosphine, triphenylphosphite a quaternary phosphonium salt such as benzyl triphenyl phosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, positive Butyl triphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphonium disulfide Sulfate, tetra-n-butylphosphonium benzotriazole salt, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, etc.; Bicyclic olefins such as 1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octoate, tin octoate, aluminum acetonate complex (alumi) Nium acetylacetone complex); quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride; boron compounds such as boron trifluoride, boric acid a phenyl ester; a metal halide such as zinc chloride or tin chloride; a high melting point dispersion type latent hardening accelerator such as dicyanodiamine or an amine addition accelerator of an amine and an epoxy resin; The microcapsule-type latent curing accelerator is formed, for example, by coating a surface of a hardening accelerator such as the above-described imidazole compound, organophosphorus compound, or quaternary phosphonium salt with a polymer; an amine salt type latent curing accelerator; a pyrolysis type thermal cation; A polymeric latent hardening accelerator such as Lewis acid salt or Bronsted acid salt.

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

Based on the amount of the carboxylic acid compound having a C ₄ to C ₅₀ side chain of the 100 parts by weight, the amount of catalyst is not more than 100 parts by weight, preferably 0.01 to 100 parts by weight, more preferably 0.1 to 20 wt. Share.

The reaction temperature is preferably in the range of 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably in the range of 0.1 to 50 hours and more preferably 0.5 to 20 hours.

Solvent

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as the polymer composition and the polyoxyalkylene oxide can be dispersed or dissolved. The solvent includes, but is not limited to, nitrogen-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone , ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol Propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, nitrogen, nitrogen-dimethylformamide, or nitrogen, N-N-dimethylethanamide. The solvent used in the liquid crystal alignment agent may be used singly or in combination of plural kinds.

Preferably, the solvent is used in an amount ranging from 1,000 parts by weight to 2,000 parts by weight based on 100 parts by weight of the polymer composition; more preferably, the solvent is used in an amount ranging from 1,200 parts by weight to 2,000 parts by weight.

additive

The liquid crystal alignment agent further contains an additive, and the additive is a compound having at least two epoxy groups in one molecule or a decane compound containing a functional group, and the like, within a range not impairing the efficacy of the present invention. The additives may be used singly or in combination of plural kinds.

Specific examples of the functional group-containing decane compound include, but are not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-Aminopropyltriethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyl Methyl dimethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, nitrogen-ethoxycarbonyl-3-aminopropyl trimethoxy decane, Nitrogen-ethoxycarbonyl-3-aminopropyltriethoxydecane, nitrogen-triethoxydecylpropyltriamine, nitrogen-trimethoxydecylpropyltriamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecyl-3,6 - Dimercaptoacetate, 9-triethoxydecyl-3,6-dimercaptoacetate, nitrogen-benzyl-3-aminopropyltrimethoxydecane, nitrogen-benzyl 3-aminopropyltriethoxydecane, nitrogen-phenyl-3-aminopropyltrimethoxydecane, nitrogen- Phenyl-3-aminopropyltriethoxydecane, nitrogen-bis(oxyethylene)-3-aminopropyltrimethoxydecane, nitrogen-bis(ethylene oxide)-3-aminopropyltriethyl Oxydecane, etc.

The functional group-containing decane compound is used in an amount ranging from 0 parts by weight to 10 parts by weight based on 100 parts by weight of the polymer composition; preferably, the functional group-containing decane compound is used in an amount ranging It is from 0.5 part by weight to 10 parts by weight.

Specific examples of the compound having at least two epoxy groups in the molecule include, but are not limited to, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, and three Propylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl Ether, 2,2-dibromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, nitrogen, nitrogen, nitrogen ', nitrogen' -tetraethoxypropyl-m-xylylenediamine, 1,3-bis(nitrogen, nitrogen-diepoxypropylaminomethyl)cyclohexane, nitrogen, nitrogen, nitrogen ', nitrogen'-tetracyclic Oxypropyl-4,4'-diaminodiphenylmethane, nitrogen, nitrogen-glycidyl-p-glycidoxyaniline, 3-(nitrogen, nitrogen-diepoxypropyl)amino Propyltrimethoxydecane] and the like.

The compound having at least two epoxy groups in the molecule may be used in an amount of from 0 to 40 parts by weight, and preferably from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the polymer composition.

Preferably, the additive is used in an amount of from 0.5 to 50 parts by weight, more preferably from 1 to 45 parts by weight, based on 100 parts by weight of the polymer composition.

The method for producing the liquid crystal alignment agent of the present invention is not particularly limited You can use the general blending method. For example, the liquid crystal alignment agent of the present invention firstly mixes a polyamic acid polymer, a polyamidene polymer, or a selective polyamidene block copolymer to form a polymer composition, and then forms a polymer composition. And adding the polymer to the polyoxoxane, the solvent at a temperature of 0 ° C to 200 ° C, preferably 20 to 60 ° C, and optionally adding the additive, and continuously stirring until dissolved .

Liquid crystal alignment film

The liquid crystal alignment film of the present invention is formed by a liquid crystal alignment agent as described above.

The liquid crystal alignment film is formed by coating the liquid crystal alignment agent on a substrate by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. On the surface, a precoat layer is formed, which is then obtained by subjecting the precoat layer to a pre-bake treatment, a post-bake treatment, and an alignment treatment.

The preheating treatment aims to volatilize the solvent in the precoat layer. Preferably, the preheating treatment has an operating temperature in the range of 30 ° C to 120 ° C, more preferably 40 ° C to 110 ° C, still more preferably 50 ° C to 100 ° C.

The post-heat treatment step is aimed at further subjecting the polymer in the precoat layer to a dehydration ring-closing (deuteration) reaction. Preferably, the post-heat treatment has an operating temperature in the range of from 150 ° C to 300 ° C, more preferably from 180 ° C to 280 ° C, still more preferably from 200 ° C to 250 ° C.

There is no special restriction on the alignment treatment, and nylon and human can be used. The fabric made of fibers such as silk and cotton is wound around the drum and rubbed in a certain direction for alignment. The above alignment processing is well known to those skilled in the art, and therefore will not be described again.

Liquid crystal display element

As shown in FIG. 1, a preferred embodiment of the liquid crystal display device of the present invention includes a first unit 11, a second unit 12 spaced apart from the first unit, and a first unit 11 and a first unit The liquid crystal cell 13 between the two cells 12.

The first unit 11 includes a first substrate 111, a first conductive film 112 formed on the surface of the first substrate 111, and a first surface formed on the first conductive film 112 and opposite to the first substrate 111. Liquid crystal alignment film 113.

The second unit 12 includes a second substrate 121, a second conductive film 122 formed on the surface of the second substrate 121, and a second surface formed on the surface of the second conductive film 122 and opposite to the second substrate 121. Liquid crystal alignment film 123.

The first substrate 111 and the second substrate 121 suitable for use in the present invention are selected from a transparent material or the like, such as an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass for a liquid crystal display device. , polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and the like. The material of the first conductive film 112 and the second conductive film 122 is selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like.

The first liquid crystal alignment film 113 and the second liquid crystal alignment film 123 are respectively the liquid crystal alignment film described above, and the function thereof is to shape the liquid crystal cell 13 Into a pretilt angle. The liquid crystal cell 13 can be driven by an electric field generated by the cooperation of the first conductive film 112 and the second conductive film 122.

The liquid crystal used in the liquid crystal cell 13 includes, but is not limited to, diaminobenzene liquid crystals, pyridazine liquid crystals, shiff base liquid crystals, and azoxy groups. Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl, biphenylcyclohexane liquid crystal a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, etc., and optionally, such as cholesteryl chloride, Cholesterol-type liquid crystals such as cholesterol cholesteryl carbonate and cholesterol ester carbonate, or chiral products (trade name "C-15" and "CB-15" (made by Merck) Or a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate. The foregoing liquid crystals may be used singly or in combination of two or more.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

Example [Preparation of polymer composition] [Preparation of poly-proline compounds] Synthesis Example 1

A nitrogen inlet, a stirrer, a condenser and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced, and the first diamine compound of the formula (I-11) (4.44 g, 0.0075 mol) was added (b). -1-1), a second diamine compound of formula (II-10) (1.16 g, 0.0025 mol) (b-2-1), p-diamine benzene (4.32 g, 0.04 mol) (b- 3-1), and nitrogen-methyl-2-pyrrolidone (80 g) were stirred at room temperature until dissolved. Further, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (11.2 g, 0.05 mol) (a1-1) and nitrogen-methyl-2-pyrrolidone (20 g) were added and reacted at room temperature for 2 hours. . After the reaction was completed, the reaction liquid was poured into (1500 ml) of water to precipitate a polymer. The polymer obtained by filtration was repeatedly washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer composition. (A-1-1).

Synthesis Examples 2 to 5 and Synthesis Comparative Examples 1 to 3 and 6

Synthesis Examples 2 to 5 and Synthesis Comparative Examples 1 to 3 and 6 were prepared in the same manner as in Synthesis Example 1 to prepare the polymer compositions (A-1-2) to (A-1-5), (A-3) The difference between -1) and (A-3-3) and (A-3-6) is that the type and amount of the tetracarboxylic dianhydride compound and the diamine compound are changed as shown in Tables 1 and 2.

[Preparation of Polyimine Compounds] Synthesis Example 6

A nitrogen inlet, a stirrer, a condenser and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen was introduced, and the first diamine compound of the formula (I-11) (4.44 g, 0.0075 mol) was added (a2). -1-1), a second diamine compound of formula (II-5) (1.16 g, 0.0025 mol) (a2-2-1), p-diamine benzene (4.32 g, 0.04 mol) (a2- 3-1), and nitrogen-methyl-2-pyrrolidone (80 (g), stir at room temperature until dissolved. Further, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (11.2 g, 0.05 mol) (a1-1) and nitrogen-methyl-2-pyrrolidone (20 g) were added and reacted at room temperature for 6 hours. . Then, nitrogen-methyl-2-pyrrolidone (97 g), acetic anhydride (2.55 g) and pyridine (19.75 g) were added to the reaction solution. The mixture was heated to 60 ° C and stirred for 2 hours to carry out hydrazine imidation. After the reaction was completed, the reaction liquid was poured into (1500 ml) water to precipitate a polymer, and the polymer obtained by filtration was repeatedly washed with methanol and filtered three times, and placed. In a vacuum oven, after drying at a temperature of 60 ° C, a polyiminoimine polymer (A-2-1) is obtained.

Synthesis Examples 7 to 13 and Synthesis Comparative Examples 4 and 5

Synthesis Examples 7 to 13 and Synthesis Comparative Examples 4 and 5 were prepared in the same manner as in Synthesis Example 6 (A-2-2) to (A-2-8), (A-3-4). The difference between (A-3-5) and the type of tetracarboxylic dianhydride compound, diamine compound, catalyst and dehydrating agent and their amounts are shown in Tables 1 and 2.

[Preparation of polyoxyalkylene] Synthesis Example 14

In a 500 ml three-necked flask, 2-glycidyloxyethyl trimethoxysilane (GETMS, 0.50 mol), dimethyldimethoxysilane (dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, Abbreviated as DMDMS, 0.10 mol), methyltrimethoxysilane (MTMS, 0.40 mol), a compound represented by formula (V-6) in the specification (abbreviated as FPA, 0.1 mole), and propylene glycol monoethyl Propylene glycol Monoethylether, referred to as PGME, 6g). An aqueous solution of triethylamine (TEA) (20 g of triethylamine/200 g of pure water) was added over 30 minutes while stirring at room temperature. Next, the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 90 ° C in 30 minutes. When the internal temperature of the solution reached 75 ° C, heating and stirring were continued for polycondensation for 6 hours. After the completion of the polycondensation, the organic layer was taken out from the flask and washed with an aqueous solution of ammonium nitrate (2 wt%) to prepare the polyoxane (B-1).

The first and second decane compounds, the solvent, and the catalyst, and the amounts thereof, and the reaction conditions used in the preparation of the synthesis examples are summarized in Table 3.

Synthesis Examples 15 to 19 and Synthesis Comparative Examples 7 and 8

Synthesis Examples 15 to 19 and Synthesis Comparative Examples 7 and 8 were prepared in the same manner as in Synthesis Example 14 to prepare the polysiloxanes (B-2) to (B-6) and (B'-1) and (B'. -2), the difference is: change the type of decane compound, solvent and catalyst and their dosage, as shown in Table 3.

[Preparation of Liquid Crystal Aligning Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element] Example 1

100 parts by weight of the polymer composition of Synthesis Example 1, 5 parts by weight of polyfluorene oxide of Synthesis Example 14, 1200 parts by weight of nitrogen-methyl-2-pyrrolidone, and 600 parts by weight of ethylene glycol n-butyl group were weighed. The ether was stirred and mixed at room temperature to form a liquid crystal alignment agent.

The liquid crystal alignment agent was applied to two glass substrates each having a conductive film made of ITO (indium-tin-oxide) by a printing machine (Model S15-036, manufactured by Nippon Photo Printing Co., Ltd.). A precoat layer was formed, and then prebaked on a hot plate at a temperature of 100 ° C for 5 minutes, and baked in a circulating oven at a temperature of 220 ° C for 30 minutes. The alignment treatment is performed on the surface of the conductive film. The two glass substrates can be respectively coated with a liquid crystal alignment film by the aforementioned process.

Then, the two glass substrates having the liquid crystal alignment film prepared as described above are coated with a thermocompression adhesive on one of the substrates, and a spacer of 4 μm is sprinkled on the other substrate, and the two glass sheets are aligned in the vertical direction. Further, a pressure of 10 kg was applied by a hot press, and hot pressing was performed at a temperature of 150 °C. Then, liquid crystal injection is performed by a liquid crystal injection machine (manufactured by Shimadzu Corporation, model ALIS-100X-CH), and the liquid crystal injection port is sealed with ultraviolet light (UV) hardening glue, hardened by ultraviolet light, and dried in an oven. A liquid crystal display element can be obtained by performing liquid crystal tempering treatment at a temperature of 60 ° C for 30 minutes. The liquid crystal alignment agent and the liquid crystal display element were evaluated for each test item, and the results are shown in Table 4.

Examples 2 to 15 and Comparative Examples 1 to 10

Examples 2 to 15 and Comparative Examples 1 to 10 were prepared in the same manner as in Example 1 to prepare the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element, except that the polymer composition and the polyoxyalkylene were changed. The types of solvents and additives and their use are shown in Table 4. These liquid crystal alignment agents and the liquid crystal display elements were evaluated for each test item, and the results are shown in Tables 4 and 5.

[evaluation project]

1, hydrazine imidization rate:

The imidization rate refers to the proline function in the polyimine polymer. Based on the total number of bases and the number of quinone rings, the ratio of the number of quinone rings is calculated as a percentage.

The detection method is that the polymers of Synthesis Examples 1 to 13 and the synthetic comparative examples 1 to 6 are dried under reduced pressure, and then dissolved in a suitable deuteration solvent, for example, deuterated dimethyl hydrazine. The results of ¹ H-NMR (hydrogen atomic magnetic resonance) were measured from room temperature (for example, 25 ° C) using tetramethyl decane as a reference material, and the sulfhydrylation ratio (%) was determined by the following formula.

醯 imidization rate (%) = [1-Δ ¹ / (△ ² × α)] × 100

Wherein Δ ¹ : the peak area of the chemical shift of the proton of the NH group at around 10 ppm; Δ ² : the peak area of other protons; and α: the polymer of the polymer component The proportion of one proton of the NH group in the polyproline precursor relative to the number of other protons.

2, UV reliability:

Ion density:

The ion density of the liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 to 10 was measured with an electric measuring machine (manufactured by TOYO Corporation, Model 6254) under the conditions of applying a voltage of 1.7 volts and a triangular wave of 0.01 Hz. In the current-voltage waveform, the ion density (measured as ID1) can be measured by calculating the peak area in the range of 0 to 1 volt; the liquid crystal display element is then irradiated with ultraviolet light of 4200 mJ/cm ² (the ultraviolet light irradiation model is KN- SH48K1; Light Energy Industrial Co., Ltd.) After irradiation, the ion density after irradiation with ultraviolet light was measured under the same test conditions (calculated as ID2). Finally, the UV reliability of the obtained ion density (calculated as ID ^UV ) is calculated according to the following formula:

The evaluation criteria are as follows:

◎: ID ^UV <5%

○: 5% ≦ ID ^UV <10%

△: 10% ≦ ID ^UV <20%

╳: ID ^UV ≧ 20%

Voltage retention rate:

The voltage holding ratios of the liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 to 10 were respectively measured with an electric measuring machine (manufactured by TOYO Corporation, model Modcl 6254) under the application time of 4 volts for a period of 2 milliseconds. After the span of 1667 milliseconds was applied, the voltage holding ratio (measured as VHR1) after 1667 milliseconds of application cancellation was measured; then the liquid crystal display element was irradiated with ultraviolet light of 4200 mJ/cm ² (the ultraviolet light irradiation model was KN-SH48K1). After the irradiation, the voltage holding ratio after irradiation with ultraviolet light (calculated as VHR2) was measured under the same test conditions. Finally, calculate the UV reliability of the voltage holding ratio (calculated as VHR ^UV ) according to the following formula:

The evaluation criteria are as follows:

◎: VHR ^UV <5%

○: 5% ≦VHR ^UV <10%

△: 10% ≦VHR ^UV <20%

╳: VHR ^UV ≧ 20%

As shown in Table 4, in Examples 1 to 15, a combination of the first and second diamine compounds as shown in the formulas (I) and (II) is used for preparing the polymer composition, and the polyfluorene The oxane is obtained by reacting a polyoxyalkylene compound containing an epoxy group and a carboxylic acid compound having a side chain of C ₄ to C ₅₀ . The liquid crystal alignment agent has better ultraviolet reliability, and when the liquid crystal alignment film is formed on a liquid crystal display element, since the liquid crystal alignment agent contains a polymer composition and a polyoxyalkylene, the liquid crystal display element is in ultraviolet light. It has a lower ion density and a better voltage holding ratio after irradiation.

As shown in Table 5, the liquid crystal display elements formed by Comparative Examples 1 to 6 had a higher ion density and a lower voltage holding ratio after ultraviolet irradiation. Particularly in Comparative Examples 1 and 4, the polymer compositions were prepared without using the first diamine compound represented by the formula (I). In Comparative Example 2, the polymer composition was not prepared using the second diamine compound represented by the formula (II). In Comparative Examples 3, 5 and 6, the polymer compositions were prepared without using the first and second diamine compounds as shown in the formulae (I) and (II).

In Comparative Examples 7 to 10, the polyoxyalkylene described in the present invention was not used in the preparation of the liquid crystal alignment agent. A liquid crystal display element containing a liquid crystal alignment film produced using the liquid crystal alignment agent has a poor voltage holding ratio after ultraviolet irradiation.

Further, when the sulfonium imidization ratio of the polymer composition is 30% to 90%, when the liquid crystal alignment film formed of the liquid crystal alignment agent is applied to a liquid crystal display element, the liquid crystal display element has a higher after ultraviolet irradiation Low ion density. Further, when a polysiloxane having a polyoxyalkylene compound containing an epoxy group and a carboxylic acid compound having a side chain of C ₆ to C ₅₀ is used, a liquid crystal display containing the liquid crystal alignment film is used. The component has a better voltage holding ratio after ultraviolet irradiation.

In summary, in the present invention, the liquid crystal alignment film has a preferable ultraviolet ray reliability and is obtained by reacting the first and second diamine compounds represented by the formulas (I) and (II). Polymer composition, and liquid crystal alignment of polyoxyalkylene obtained by reacting a polyoxyalkylene compound containing an epoxy group and a carboxylic acid compound having a C ₄ to C ₅₀ side chain The agent is formed. Further, since the liquid crystal display element including the liquid crystal alignment film has a low ion density and a preferable voltage holding ratio after irradiation with ultraviolet rays, the object of the present invention can be surely achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

11‧‧‧ first unit

111‧‧‧First substrate

112‧‧‧First conductive film

113‧‧‧First liquid crystal alignment film

12‧‧‧Second unit

121‧‧‧second substrate

122‧‧‧Second conductive film

123‧‧‧Second liquid crystal alignment film

13‧‧‧Liquid Crystal Unit

Claims (9)

A liquid crystal alignment agent comprising: a polymer composition obtained by reacting a tetracarboxylic dianhydride component and a diamine component; a polyoxyalkylene oxide; and a solvent; wherein the diamine component The first diamine compound represented by the formula (I) is included: Wherein R ¹² and R ¹⁴ are independently selected from -O-, -S-, , R ¹³ represents a C ₂ to C ₁₀ alkylene group, R ¹¹ is a monovalent organic group selected from the group consisting of a single bond, a methylene group, an extended ethyl group, and X represents a C ₁₇ to C ₄₀ having a cholesterol skeleton; a second diamine compound of formula (II): Wherein R ¹⁵ is selected from -O-, , , , R ¹⁶ represents an organic group as shown in the formula (II-1): Wherein R ¹⁷ is independently hydrogen, fluoro or methyl; and R ¹⁸ , R ¹⁹ or R ²⁰ each independently represents a single bond, -O-, , , , , Or a C ₁ to C ₃ alkylene group; R ²¹ is independently selected from and Wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl, and R ²² is selected from the group consisting of hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl, C ₁ to Alkoxy group of C ₁₂ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; k represents an integer of 1 or 2, and l, m and n are integers each independently representing 0 to 4, and o, p and q are Each independently represents an integer from 0 to 3, and the condition is o+p+q≧3, and r and s each independently represent 1 or 2; wherein the polyoxyalkylene is composed of an epoxy group-containing group The polyoxyalkylene compound is obtained by reacting a carboxylic acid compound having a side chain of C ₄ to C ₅₀ . The liquid crystal alignment agent according to claim 1, wherein the epoxy group-containing polyoxyalkylene compound is formed by polycondensation of a monodecane compound component, wherein the decane compound component comprises a formula (III) The first decane compound shown: Si(R ³² ) _y (OR ³³ ) _4-y (III) wherein at least one of R ³² is selected from the group consisting of formula (B-1), formula (B-2) or formula ( a functional group of B-3), the remaining R ³² being independently selected from a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, R ³³ is an aryl group each independently selected from a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, or a C ₆ to C ₁₅ aryl group, and Y represents an integer of 1 to 3; Wherein A is selected from an oxygen atom or a single bond, h is an integer representing from 1 to 3, and i is an integer representing from 0 to 6, and the condition is that when i is 0, A represents a single bond, Where j is an integer representing from 0 to 6, Wherein B ¹ is an alkylene group representing C ₂ to C ₆ ; R ³⁴ represents a hydrogen atom or an alkyl group of C ₁ to C ₆ . The liquid crystal alignment agent according to claim 2, wherein the decane compound further comprises a second decane compound represented by the formula (IV): Si(R ³⁵ ) _b (OR ³⁶ ) _4-b (IV) wherein R ³⁵ is independently selected from a hydrogen atom, C ₁ to C ₁₀ alkyl group, the C ₂ to C ₁₀ alkenyl groups, and aryl groups and C ₆ to C ₁₅ a, R ³⁶ are each independently selected from a hydrogen atom, C ₁ to C ₆ alkyl, and C ₁ to C ₆ acyl or C ₆ to C ₁₅ aryl group, and and b represents an integer of 0 to 3. The requested item of the liquid crystal alignment agent, wherein the carboxylic acid compound having a C ₆ to C ₅₀ of the side chain. The liquid crystal alignment agent according to claim 1, wherein the first diamine compound represented by the formula (I) is used in an amount ranging from 5 to 25 mols, based on the total amount of the decane compound component being 100 mol. And the second diamine compound represented by the formula (II) is used in an amount ranging from 5 to 25 mols. The liquid crystal alignment agent according to claim 1, wherein the polymer composition has a oxime imidization ratio ranging from 30 to 90%. The liquid crystal alignment agent according to claim 1, wherein the polysiloxane is used in an amount of from 3 to 30 parts by weight based on 100 parts by weight of the polymer composition, and the solvent is used in an amount of from 500 to 3,000 parts by weight. A liquid crystal alignment film is provided by any one of claims 1 to 7 The liquid crystal alignment agent is formed. A liquid crystal display element comprising the liquid crystal alignment film of claim 8.