TW201912716A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal alignment agent and a method for manufacturing the liquid crystal alignment agent. The liquid crystal alignment agent includes a polymer (A) which is formed by reacting a first mixture including a tetracarboxylic dianhydride component (a) and a diamine component (a2). The polymer (A) is selected from a polyamide acid polymer, a polyimide polymer, a polyimide-based block copolymer or a combination thereof. The liquid crystal alignment agent of the invention has the advantages of low liquid crystal contact angle and high impedance. Furthermore, the invention also provides a liquid crystal alignment film made by the aforementioned liquid crystal alignment agent, a method for forming the liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The invention relates to a liquid crystal alignment agent and a manufacturing method thereof, a liquid crystal alignment film and a manufacturing method thereof, and a liquid crystal display element, and particularly to a liquid crystal alignment agent with a low liquid crystal contact angle and a high bulk impedance, a method for manufacturing the same, and the liquid crystal alignment Liquid crystal alignment film formed by an agent, a method for manufacturing the same, and a liquid crystal display element having the liquid crystal alignment film.

Generally, in liquid crystal display elements, various driving methods have been developed according to the structure of the electrodes or the physical properties of the liquid crystal molecules used. Currently known driving methods of liquid crystal display elements are, for example, TN type or STN type, VA type, lateral electric field effect display technology type (IPS type), and the like. In the above-mentioned liquid crystal display element, a liquid crystal alignment film is disposed to align liquid crystal molecules, and the material of the liquid crystal alignment film may be, for example, known polyimide acid or polyimide, polyester, polyorganosiloxane, and the like. material.

In recent years, in order to control the alignment of liquid crystal molecules of liquid crystal display elements, new technologies such as Polymer Sustained Alignment (PSA) have been proposed, such as Japanese Publication No. JP 2003-149647. The polymer stable alignment technology described therein A photopolymerizable component is added to the liquid crystal layer of the liquid crystal cell, and the liquid crystal molecules are tilted under a voltage applied state, and then the liquid crystal cell is irradiated with light, thereby polymerizing the photopolymerizable component, thereby controlling the alignment of the liquid crystal molecules.

However, when using polymer stabilized alignment technology to control the alignment of liquid crystal molecules, a relatively high amount of light is used, which causes defects such as the decomposition of liquid crystal molecules and the deterioration of the properties of the liquid crystal alignment film. Panel durability is degraded. On the other hand, if the amount of light irradiation is reduced, the reaction rate of liquid crystal molecules in the formed liquid crystal display element to a voltage change becomes slow. In order to make the liquid crystal alignment agent have the characteristics that a predetermined pretilt angle can be achieved with a small amount of light irradiation, and the liquid crystal molecules in the formed liquid crystal display element have a fast response speed to voltage, etc., Japanese Patent Publication No. 2011-118358 proposes Related technology in which a liquid crystal alignment agent containing a polyorganosiloxane such as a (meth) acrylfluorene group and a photopolymerizable component of polyimide acid or polyimide is disclosed, and the liquid crystal is The alignment agent forms a liquid crystal alignment film on the substrate. Next, the substrate is formed into a liquid crystal cell, and when a voltage is applied between the substrates, the liquid crystal cell is irradiated with light to produce a liquid crystal display element.

However, in the above method, because the liquid crystal contact angle of the liquid crystal alignment agent is too high, the liquid crystal cannot be uniformly covered on the liquid crystal alignment film. In addition, the bulk impedance of the above-mentioned liquid crystal alignment agent is still low, which cannot meet industrial requirements. Therefore, there is an urgent need to propose a liquid crystal alignment agent, which can improve the shortcomings of too high a liquid crystal contact angle and a low bulk impedance.

The present invention obtains a liquid crystal alignment agent by providing components such as a special polymer and polysiloxane. The liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have the advantages of low liquid crystal contact angle and high body impedance.

Therefore, the present invention provides a liquid crystal alignment agent, comprising: a polymer (A), which is prepared by reacting a first monomer mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2); Wherein, the polymer (A) is selected from the group consisting of a polyfluorinated acid polymer, a polyfluorinated imine polymer, a polyfluorinated block copolymer, or any combination thereof; polysiloxane (B ); And solvent (C); wherein the diamine component (a2) comprises at least one diamine compound (a2-1) represented by formula (I): Formula (I) In Formula (I), R _a is a single bond or a linear or branched alkyl group of C ₁ to C ₁₀ ; Y is —COO—, —OCO—, —NR _d CO— or —CONR _d -; R _b is a single bond, a straight-chain or branched-chain C ₁ to C ₁₀ alkyl group, the C or straight-chain or branched alkenyl group of ₁ to C _10; R _c is a linear or branched C ₁ to C ₁₀ of Alkyl, C ₁ to C ₁₀ linear or branched oxyalkyl, C ₁ to C ₁₀ ether, C ₁ to C ₁₀ keto, C ₂ to C ₁₀ ester, halogen or nitrile ; R _d is a hydrogen atom, or a linear or branched alkyl group of C ₁ to C ₁₀ ; Py is 2H-pyran, 4H-pyran, 3,4- Dihydropyran (3,4-dihydropyran), 3,6-dihydropyran (3,6-dihydropyran), cyclopenta [b] pyran (cyclopenta [b] pyran), cyclopentadiene Cyclopenta [c] pyran, 1H-benzopyran (1H-chrome), 2H-benzopyran (2H-chrome), 4H-benzopyran (4H-chrome), or 3,4-dihydro-2H-benzopyran (3,4-dihydro-2H-chrome); a1 is an integer from 0 to 5; and when R _c is plural, each R _{c is the} same or different.

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display device including the aforementioned liquid crystal alignment film.

The invention provides a liquid crystal alignment agent comprising: a polymer (A), which is prepared by reacting a first monomer mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2), Wherein, the polymer (A) is selected from the group consisting of a polyacrylic acid polymer, a polyimide polymer, a polyimide-based block copolymer, or any combination thereof; polysiloxane (B); And solvent (C); wherein the diamine component (a2) comprises at least one diamine compound (a2-1) represented by formula (I): Formula (I) In Formula (I), R _a is a single bond or a linear or branched alkyl group of C ₁ to C ₁₀ ; Y is —COO—, —OCO—, —NR _d CO— or —CONR _d -; R _b is a single bond, a straight-chain or branched-chain C ₁ to C ₁₀ alkyl group, the C or straight-chain or branched alkenyl group of ₁ to C _10; R _c is a linear or branched C ₁ to C ₁₀ of Alkyl, C ₁ to C ₁₀ linear or branched oxyalkyl, C ₁ to C ₁₀ ether, C ₁ to C ₁₀ keto, C ₂ to C ₁₀ ester, halogen or nitrile ; R _d is a hydrogen atom, or a linear or branched alkyl group of C ₁ to C ₁₀ ; Py is 2H-pyran, 4H-pyran, 3,4- Dihydropyran (3,4-dihydropyran), 3,6-dihydropyran (3,6-dihydropyran), cyclopenta [b] pyran (cyclopenta [b] pyran), cyclopentadiene Cyclopenta [c] pyran, 1H-benzopyran (1H-chrome), 2H-benzopyran (2H-chrome), 4H-benzopyran (4H-chrome), or 3,4-dihydro-2H-benzopyran (3,4-dihydro-2H-chrome); a1 is an integer from 0 to 5; and when R _c is plural, each R _{c is the} same or different.

In the present invention, the first monomer mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

Specifically, the polymer (A) is selected from the group consisting of a polyamidopolymer, a polyamidopolymer, a polyamidoblock copolymer, and any combination of the aforementioned polymers. Among them, the polyfluorene-based block copolymer includes a polyfluoride-based block copolymer, a polyfluoride-based imide block copolymer, a polyfluoride-based polyimide-block copolymer, or the above-mentioned polymerization. Combination of things. The polyfluorene acid polymer, the polyfluorene imine polymer, and the polyfluorine-based block copolymer in the polymer (A) may be composed of a tetracarboxylic dianhydride component (a1) and a diamine component ( a2) prepared by reacting the monomer mixture.

The tetracarboxylic dianhydride component (a1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and the formula (a1-1) to ( at least one of the tetracarboxylic dianhydride compounds represented by a1-6), or a combination thereof.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination thereof.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are 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-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclopeptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the foregoing compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethanetetracarboxylic dianhydride, 3,3', 4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'- Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisoprene Propyldiphthalic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (tris) Phenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (Triphenylphthalic acid) -4,4'- Phenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydromellitate), 1,4-butanediol-bis (anhydromellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- Bis (anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione {(1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene Benzo [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dione (Oxy-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo Yl-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl- 5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxo Tetrahydrofuranyl) aromatic tetracarboxylic dianhydride compounds such as 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination of the foregoing compounds.

The tetracarboxylic dianhydride compounds represented by the formula (a1-1) to the formula (a1-6) are shown below. (A1-1) (A1-2) (A1-3) (A1-4) (A1-5)

In formula (a1-5), A ¹ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ² and A ³ may be the same or different, and each may independently represent a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a1-5) include at least one of compounds represented by the formula (a1-5-1) to the formula (a1-5-3). Formula (a1-5-1) Formula (a1-5-2) Formula (a1-5-3) (A1-6)

In formula (a1-6), A ⁴ represents a divalent group containing an aromatic ring; A ⁵ and A ⁶ may be the same or different, and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (a1-6-1). Formula (I-6-1)

The tetracarboxylic dianhydride component (a1) may be selected from one of the tetracarboxylic dianhydride compounds alone or in combination.

Specific examples of the tetracarboxylic dianhydride component (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride), 1, 2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexane Alkanetetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylfluorenetetracarboxylic dianhydride, a compound represented by formula (a1-1), or a combination thereof.

Based on the total mole number of the diamine component (a2) is 100 moles, the use amount of the tetracarboxylic dianhydride component (a1) is preferably 80 moles to 120 moles, and more preferably 85 moles To 115 mol.

The diamine component (a2) according to the present invention includes at least one diamine compound (a2-1) represented by formula (I): Formula (I) In Formula (I), R _a is a single bond or a linear or branched alkyl group of C ₁ to C ₁₀ ; Y is —COO—, —OCO—, —NR _d CO— or —CONR _d -; R _b is a single bond, a straight-chain or branched-chain C ₁ to C ₁₀ alkyl group, the C or straight-chain or branched alkenyl group of ₁ to C _10; R _c is a linear or branched C ₁ to C ₁₀ of Alkyl, C ₁ to C ₁₀ linear or branched oxyalkyl, C ₁ to C ₁₀ ether, C ₁ to C ₁₀ keto, C ₂ to C ₁₀ ester, halogen or nitrile ; R _d is a hydrogen atom, or a linear or branched alkyl group of C ₁ to C ₁₀ ; Py is 2H-pyran, 4H-pyran, 3,4- Dihydropyran (3,4-dihydropyran), 3,6-dihydropyran (3,6-dihydropyran), cyclopenta [b] pyran (cyclopenta [b] pyran), cyclopentadiene Cyclopenta [c] pyran, 1H-benzopyran (1H-chrome), 2H-benzopyran (2H-chrome), 4H-benzopyran (4H-chrome), or 3,4-dihydro-2H-benzopyran (3,4-dihydro-2H-chrome); a1 is an integer from 0 to 5; and when R _c is plural, each R _{c is the} same or different.

The diamine component (a2-1) of the present invention can be obtained by synthesizing a dinitro compound represented by formula (I-1), and then reducing the nitro group to form an amine group. The reduction method of the dinitro compound is not particularly limited. For example, a catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, or platinum sulfide can be used in ethyl acetate and toluene. , Hydrogen, hydrazine, or hydrogen chloride is passed into a solvent such as tetrahydrofuran, dioxane, or alcohol to perform a reduction reaction. Formula (I-1) In formula (I-1), R _a is a single bond or a linear or branched alkyl group of C ₁ to C ₁₀ ; Y is -COO-, -OCO-, -NR _d CO- or -CONR _d -; R _b is a single bond, a straight-chain or branched-chain C ₁ to C ₁₀ alkyl group, the C or straight-chain or branched alkenyl group of ₁ to C _10; R _c is C ₁ to C ₁₀ of a straight-chain or branched alkyl, C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, C ₁ to C ₁₀ ether group of, C ₁ to C ₁₀ of the keto group, C ₂ to C ₁₀ ester group of, Halogen or nitrile; R _d is a hydrogen atom, or a linear or branched alkyl group of C ₁ to C ₁₀ ; Py is 2H-pyran, 4H-pyran, 3,4-dihydropyran (3,4-dihydropyran), 3,6-dihydropyran (3,6-dihydropyran), cyclopenta [b] pyran (cyclopenta [b] pyran), Cyclopentadiene [c] pyran, 1H-benzopyran (1H-chrome), 2H-benzopyran (2H-chrome), 4H-benzopyran (4H -chrome) or 3,4-dihydro-2H-benzopyran (3,4-dihydro-2H-chrome); a1 is an integer from 0 to 5; and when R _c is plural, each R _{c is the} same or different.

The method for synthesizing a dinitro compound varies depending on the kind of the binding group. When Y is -OCO-, for example, a dinitro compound can be obtained by a condensation reaction of dinitrobenzyl alcohol and 2H-Pyran-2-acetic acid. The condensation method is not particularly limited, and for example, a dinitrobenzyl alcohol and a carboxylic acid chloride represented by the following formula can be used to react in the presence of a base to obtain a dinitro compound. Alternatively, it can be obtained, for example, by reacting an alcohol and a carboxylic acid compound in the presence of another dehydrating condensation agent.

When Y is -NR _d CO-, for example, a dinitro compound can be obtained by a condensation reaction of dinitroaniline and 2H-pyran-2-acetic acid. The condensation method is not particularly limited. For example, a dinitroaniline and a carboxylic acid chloride represented by the following formula can be used to react in the presence of a base to obtain a dinitro compound. Alternatively, it can be obtained, for example, by reacting an amine and a carboxylic acid compound in the presence of another dehydrating condensation agent.

When Y is -COO-, for example, a dinitro compound can be obtained by a condensation reaction of dinitrobenzoic acid and 2H-Pyran-4-methanol. The condensation method is not particularly limited. For example, a dinitrobenzyl chloride and an alcohol represented by the following formula can be used to react in the presence of a base to obtain a dinitro compound. Alternatively, it can be obtained, for example, by reacting an alcohol and a carboxylic acid compound in the presence of another dehydrating condensation agent.

When Y is -CONR _d- , for example, it can be obtained by dinitrobenzoic acid and 3,4-dihydro-2H-pyran-6-methanamine. A dinitro compound is obtained by a condensation reaction. The condensation method is not particularly limited, and for example, a dinitrobenzoic acid chloride and an amine represented by the following formula can be used to react in the presence of a base to obtain a dinitro compound. Alternatively, it can be obtained, for example, by reacting an amine and a carboxylic acid compound in the presence of another dehydrating condensation agent.

The alcohol compound for synthesizing the dinitro compound may be represented by the following formula (I-2-1) to (I-2-103).

The amine compound for synthesizing the dinitro compound may be represented by the following formula (I-3-1) to (I-3-120).

The carboxylic acid compound for synthesizing the dinitro compound may be represented by the following formula (I-4-1) to (I-4-54).

In a specific example of the present invention, the total amount of the diamine component (a2) is 100 mol, and the amount of the diamine compound (a2-1) is 3 to 40 mol, preferably 5 to 35. Mohr, more preferably 5 to 30 moles. If the diamine component (a2) does not include the diamine compound (a2-1), the bulk impedance of the liquid crystal alignment agent is low, and the liquid crystal contact angle is high.

Preferably, the diamine component (a2) of the present invention may further include other diamine compounds (a2-2).

The other diamine compound (a2-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, and a diamine having the formula (a2-2-1) to the formula (a2-2-26). An amine compound, or a combination thereof.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , 4,4'-diaminoheptane, 1,3-diamino-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-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethyl Alkane, or a combination of the above.

Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.02,7] -undecyl Dimethydiamine, 4,4'-methylenebis (cyclohexylamine), or a combination of the foregoing.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzidineaniline, 4,4'-diaminostilbene stilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminediamine Phenyl ether, 3,3'-diaminochalcone, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indanes, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, hexahydro-4,7-methyl bridged indenyl 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-aminophenylphenyl) ) Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,10-bis ( 4-aminophenyl) anthracene [9,10-bis (4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) , 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) Propyl) 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-methylene-1,3-diamine Benzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diamino benzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- ( 4-ethylphenyl) cyclohexane {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, or a combination thereof.

The diamine compounds represented by the formula (a2-2-1) to the formula (a2-2-30) are shown below. Formula (a2-2-1)

In formula (a2-2-1), B ¹ represents , , , , ,or ; B ² represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluorine atom, a C ₂ to C ₃₀ alkyl group, or a derivative derived from A monovalent group of a nitrogen atom ring structure.

Specific examples of the compound represented by formula (a2-2-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl Ethyl formate, 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene Benzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), from the formula (a2-2-1- 1) At least one of the compounds represented by the formula (a2-2-1-6), or a combination of the aforementioned compounds. Formula (a2-2-1-1) Formula (a2-2-1-2) Formula (a2-2-1-3) Formula (a2-2-1-4) Formula (a2-2-1-5) Formula (a2-2-1-6) Formula (a2-2-2)

In formula (a2-2-2), and B ¹ in the formula (a2-2-1) B same as ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, a divalent aromatic or a divalent hetero ring Ring group; B ⁵ represents C ₃ to C ₁₈ alkyl, C ₃ to C ₁₈ alkoxy, C ₁ to C ₅ fluoroalkyl, C ₁ to C ₅ fluoroalkoxy, cyano or Halogen atom.

Specific examples of the compound represented by the formula (a2-2-2) include at least one of compounds represented by the formula (a2-2-2-1) to the formula (a2-2-2-13). Specifically, the compounds represented by the formula (a2-2-2-1) to the formula (a2-2-2-13) are shown below. Formula (a2-2-2-1) Formula (a2-2-2-2) Formula (a2-2-2-3) Formula (a2-2-2-4) Formula (a2-2-2-5) Formula (a2-2-2-6) Formula (a2-2-2-7) Formula (a2-2-2-8) Formula (a2-2-2-9) Formula (a2-2-2-10) Formula (a2-2-2-11) Formula (a2-2-2-12) Formula (a2-2-2-13)

In the formulae (a2-2-2-10) to (a2-2-2-13), s represents an integer of 3 to 12. Formula (a2-2-3)

In formula (a2-2-3), B ⁶ each independently represent a hydrogen atom, C ₁ to C ₅ of acyl, C ₁ to C ₅ alkyl group of, C ₁ to C ₅ alkoxy group or the halogen atom, and B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (a2-2-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; When u 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'-diaminobiphenyl, 3,3 '-Dichloro-4,4'-diaminobiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, etc .; or when u is 3 : 1,4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (a2-2-3) preferably include p-diaminebenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'- Dimethoxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination thereof. Formula (a2-2-4)

In the formula (a2-2-4), v represents an integer of 2 to 12. Formula (a2-2-5)

In the formula (a2-2-5), w represents an integer of 1 to 5. The compound represented by the formula (a2-2-5) is preferably 4,4'-diamino-diphenylsulfide. Formula (a2-2-6)

In formula (a2-2-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents a derivative derived from pyridine, pyrimidine, triazine, and piperidine Or a divalent group of a cyclic structure containing a nitrogen atom such as piperazine. Formula (a2-2-7)

In formula (a2-2-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a hydrocarbon group of C ₁ to C ₁₂ , and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ may be the same or different; X1 each independently represents an integer from 1 to 3; X2 represents an integer from 1 to 20. Formula (a2-2-8)

In formula (a2-2-8), B ¹⁴ represents an oxygen atom or a cyclohexyl group; B ¹⁵ represents a methylene group (methylene, -CH2-); B ¹⁶ represents a phenylene group or a cyclohexane group; B ¹⁷ represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (a2-2-8) include a compound represented by the formula (a2-2-8-1), a compound represented by the formula (a2-2-8-2), or a combination thereof. . Formula (a2-2-8-1) Formula (a2-2-8-2)

The compounds represented by the formula (a2-2-9) to the formula (a2-2-25) are shown below. Formula (a2-2-9) Formula (a2-2-10) Formula (a2-2-11) Formula (a2-2-12) Formula (a2-2-13) Formula (a2-2-14) Formula (a2-2-15) Formula (a2-2-16) (A2-2-17) Formula (a2-2-18) (A2-2-19) Formula (a2-2-20) Formula (a2-2-21) Formula (a2-2-22) Formula (a2-2-23) Formula (a2-2-24) Formula (a2-2-25)

In formulae (a2-2-17) to (a2-2-25), B ^{18 is} preferably a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group; B ^{19 is} preferably a A hydrogen atom, a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group. Formula (a2-2-26)

In formula (a2-2-26), B ²⁰ and B ²² each independently represent a single bond, -O-, -COO-, or -OCO-; B ²¹ is an alkylene group having 1 to 3 carbon atoms; B23 is a single Bond or alkylene having 1 to 3 carbons. d and g each independently represent 0 or 1; e represents an integer from 0 to 2; f represents an integer from 1 to 20; wherein d and e are not 0 at the same time.

In the formula (a2-2-26), the divalent group represented by "-B ^20- (B ²¹ -B ²² ) g-" is preferably an alkylene group having 1 to 3 carbon atoms, * -O- , * -COO- or * -O-C2H4-O- (where * represents a bond to a diaminophenyl group.). The group represented by "-C _f H _{2f + 1} " is preferably linear. The positions of two amine groups in the diaminophenyl group with respect to other groups are preferably the 2, 4-position or the 3, 5-position.

Specific examples of the compound represented by the formula (a2-2-26) include compounds represented by the following formula (a2-2-26-1) to (a2-2-26-4): Formula (a2-2-26-1) Formula (a2-2-26-2) Formula (a2-2-26-3) Formula (a2-2-26-4) Formula (a2-2-26-5)

This other diamine compound (a2-2) can be used individually or in combination of multiple types.

Specific examples of the other diamine compound (a2-2) preferably include, but are not limited to, 1,2-diaminoethane, 3,3'-diaminochalcone, and 4,4'-diamine Stilbene, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 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, 1-octadecyloxy-2,4-diaminobenzene, and the formula (a2-2-1 -1) a compound represented by the formula (a2-2-1-2), a compound represented by the formula (a2-2-1-4), a compound represented by the formula (a2-2-1-5) A compound, a compound represented by formula (a2-2-2-1), a compound represented by formula (a2-2-2-11), p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, A compound represented by the formula (a2-2-8-1), a compound represented by the formula (a2-2-26) to the formula (a2-2-30), or a combination thereof.

In a specific example of the present invention, based on the total usage of the diamine component (a2) is 100 moles, the usage of the other diamine compound (a2-2) is 60 to 97 moles, preferably 65 to 95 mol, more preferably 70 to 95 mol. Method for preparing polymer (A)

The polymer (A) may include at least one of polyamidic acid and polyamidoimine. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below. Method for preparing polyamic acid

The method for preparing the polyamidic acid is to first dissolve a first monomer mixture in a solvent, wherein the first monomer mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and The polycondensation reaction is performed at a temperature of from 100 ° C to 100 ° C. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes, but is not limited to (1) an aprotic polar solvent, such as: N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, Aprotic polar solvents such as N, N-dimethylformamide, dimethylmethylene sulfoxide, γ-butyrolactone, tetramethylurea or hexamethyl phosphate triamine; or (2) phenolic solvents, For example: m-cresol, xylenol, phenol or halogenated phenols. Based on the total amount of the first monomer mixture being 100 parts by weight, the amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight.

It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the total amount of the first monomer mixture being 100 parts by weight, the amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight. Method for preparing polyfluorene

The method for preparing polyimide is obtained by heating the polyamidic acid prepared by the method for preparing polyamidic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (that is, arsonimation) through a dehydration ring-closing reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (C) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.

In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles.

The fluorene imidization rate of the polymer (A) may be 30% to 80%, preferably 35% to 80%, and more preferably 35% to 75%. If the fluorenimidization ratio of the polymer (A) is within the above range, the liquid crystal contact angle of the liquid crystal alignment agent is low. Method for preparing polyfluorene imide block copolymer

The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.

The method for preparing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and carrying out a polycondensation reaction, wherein the starting material includes at least one polyamic acid and / or at least one polyfluorene Imine, and may further include a carboxylic anhydride component and a diamine component.

The carboxylic acid anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for preparing a polyamic acid, and are used for The solvent in the polycondensation reaction may be the same as the solvent (C) in the liquid crystal alignment agent described below, and details are not described herein again.

The used amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight based on the used amount of the starting material. The operating temperature of the polycondensation reaction is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 100 ° C.

The starting materials preferably include, but are not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two polyimines having different terminal groups and different structures; (3) ) Polyamines and polyimines having different terminal groups and structures; (4) Polyamines, carboxylic anhydride components, and diamine components, of which the carboxylic anhydride component and the diamine component are At least one of them is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyfluorinated acid; (5) the polyfluorene imine, the carboxylic acid anhydride component, and the diamine component, wherein At least one of the component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyimide; (6) the polyamidic acid, the polyimide, and the carboxylic acid anhydride component And a diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamic acid or polyimide; ( 7) Two kinds of polyfluorinated acid, carboxylic anhydride and diamine components with different structures; (8) Two kinds of polyfluorinated imine, carboxylic anhydride and diamine components with different structures; (9) Polyamines and diamines whose terminal groups are acid anhydride groups and have different structures; (10) Polyamines and carboxylic anhydrides whose terminal groups are amine groups and have different structures; (11) A kind of polyfluorene imine and diamine components whose terminal groups are acid anhydride groups and different structures; or (12) two kinds of polyfluorene imine and carboxylic acid anhydride components whose terminal groups are amine groups and different structures.

As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a polyfunctional compound while the polyamic acid is undergoing a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Monobasic anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) monoamine compounds such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a weight average molecular weight of 10,000 to 100,000; preferably 20,000 to 80,000; more preferably 30,000 to 70,000.

The liquid crystal alignment agent of the present invention includes a polysiloxane (B), and the polysiloxane (B) may include a polysiloxane (B-1) containing a photoreactive group.

The aforementioned photoreactive group-containing polysiloxane (B-1) is prepared by reacting a mixture, and the mixture may include an epoxy-containing polysiloxane (b1) and an ethylenically unsaturated compound (b2) The epoxy group-containing polysiloxane (b1) comprises a copolymer obtained by hydrolyzing and partially condensing a second monomer mixture.

The epoxy-containing polysiloxane (b1) includes at least one of a group represented by formula (III-1), a group represented by formula (III-2), and a group represented by formula (III-3) By: Formula (III-1) In Formula (III-1), B represents an oxygen atom or a single bond; c represents an integer from 1 to 3; d represents an integer from 0 to 6; and when d represents 0, B is a single bond ; Formula (III-2) In Formula (III-2), e represents an integer of 0 to 6; Formula (III-3) In Formula (III-3), D represents an alkylene group having 2 to 6 carbon atoms; and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The epoxy group-containing group preferably includes a group represented by the formula (III-1-1), a group represented by the formula (III-2-1), and a group represented by the formula (III-3-1) At least one of them. Formula (III-1-1) Formula (III-2-1) Formula (III-3-1)

The epoxy group-containing polysiloxane (b1) is a copolymer obtained by hydrolyzing and partially condensing a second monomer mixture. Wherein, the second monomer mixture includes a silane monomer (b1-1) as shown in formula (III-4): Si (R _f ) _p (OR _g ) _4-p formula (III-4) formula (III-4) -4) in, R _f is a hydrogen atom, C ₁ to C ₁₀ alkyl group, the C ₂ to C ₁₀ alkenyl group of, C ₆ to C ₁₅ aryl group, the alkyl group containing an epoxy group or the epoxy group-containing Alkoxy, and at least one R _f is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when p is plural, R _{f is} each the same or different; R _g is a hydrogen atom, C ₁ alkyl of ₆ to C, C ₁ to C ₆ acyl or a C aryl group of ₆ to C _15's; and when 4-p is plural, R _g are each the same or different; and p is an integer of 1-3.

In more detail, when R _f in the formula (III-4) represents an alkyl group of C ₁ to C ₁₀ , specifically, R _f is, for example, methyl, ethyl, n-propyl, isopropyl, n- Butyl, third butyl, n-hexyl or n-decyl. R _f may be an alkyl group having another substituent on the alkyl group. Specifically, R _{f is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.

When R _f in the formula (III-4) represents an alkenyl group of C ₂ to C ₁₀ , specifically, R _{f is,} for example, a vinyl group. R _f may be an alkenyl group having another substituent on the alkenyl group. Specifically, R _{f is,} for example, 3-propenyloxypropyl or 3-methacryloxypropyl.

When R _f in the formula (III-4) represents an aryl group of C ₆ to C ₁₅ , specifically, R _f is, for example, a phenyl group, a tolyl group, or a naphthyl group. R _f may be an aryl group having another substituent on the aryl group. Specifically, R _f is, for example, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl (1 -(o-hydroxyphenyl) ethyl), 2- (p-hydroxyphenyl) ethyl (2- (o-hydroxyphenyl) ethyl) or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl ( 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl).

When R _f in formula (III-4) represents an epoxy-containing alkyl group or an epoxy-containing alkoxy group, a specific example of R _f is the aforementioned epoxy-containing polysiloxane ( b1) contains epoxy groups, which will not be repeated here.

In addition, when R _{g of the} formula (III-4) represents a C ₁ to C ₆ alkyl group, specifically, R _g is, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl. When R _g in the formula (III-4) represents a fluorenyl group of C ₁ to C ₆ , specifically, R _{g is,} for example, an ethenyl group. When R _g in the formula (III-4) represents an aryl group of C ₆ to C ₁₅ , specifically, R _{g is,} for example, a phenyl group.

Specific examples of the silane monomer (b1-1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and 3- (N-allyl-N-glycidyl) amino group. Propyltrimethoxysilane, 3-glycidyletherpropyltrimethoxysilane, 3-glycidyletherpropyltriethoxysilane, 3-glycidyletherpropylmethyldimethoxysilane, 3-glycidyl ether propylmethyldiethoxysilane, 3-glycidyl ether propyldimethylmethoxysilane, 3-glycidyl ether propyldimethylethoxysilane, 2- Glycidyl ether ethyltrimethoxysilane, 2-glycidyl ether ethyltriethoxysilane, 2-glycidyl ether ethylmethyldimethoxysilane, 2-glycidyl ether ethylmethyl Didiethoxysilane, 2-glycidyl ether ethyl dimethylmethoxysilane, 2-glycidyl ether ethyl dimethyl ethoxysilane, 4-glycidyl ether butyl trimethoxy Silane, 4-glycidyl ether butyl triethoxy silane, 4-glycidyl ether butyl methyl dimethoxy silane, 4-glycidyl ether butyl methyl diethoxy silane, 4-glycidyl ether Butyl Methylmethoxysilane, 4-glycidyl ether butyl dimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-cyclo Oxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane ((3-ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxy Silane, ((3-ethyl-3-glycidyloxy) methoxy) propylmethyldimethoxysilane or ((3-ethyl-3-glycidyl) methoxy) propanedi Methylmethoxysilane, commercially available products such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC), or a combination of the aforementioned compounds.

Specific examples of the silane monomer (b1-1) represented by the formula (III-4) include 3-glycidyl ether propyltrimethoxysilane, 2-glycidyl ether ethyltrimethoxysilane, 4 -Glycidyl ether butyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane ((3-ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxy Silane, DMS-E01, DMS-E12, or a combination of these compounds.

Based on the total amount of the monomers in the second monomer mixture being 1 mole, the silane monomer (b1-1) is used in an amount of 0.6 to 1 mole, preferably 0.65 to 1 mole. , More preferably 0.7 to 1 mole.

The second monomer mixture for reacting to form the epoxy-containing polysiloxane (b1) preferably further contains another silane monomer (b1-2) represented by formula (III-5): Si ( R _h ) _q (OR _i ) _4-q Formula (III-5) In formula (III-5), R _h is a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, C ₆ to C ₁₅ aryl group or alkyl group containing acid anhydride group; when q is plural, R _h are each the same or different; R _i is hydrogen atom, C ₁ to C ₆ alkyl group, C ₁ to C ₆ A fluorenyl group or an aryl group of C ₆ to C ₁₅ ; when 4-q is plural, each of R _i is the same or different; and p is an integer of 1 to 3.

When R _h in formula (III-5) represents 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, specific examples and preferred examples thereof include the aforementioned R _f As shown, it will not be repeated here.

When _Rh in the formula (III-5) represents an alkyl group containing an acid anhydride group, the alkyl group is preferably a C ₁ to C ₁₀ alkyl group. Specifically, the acid-anhydride-containing alkyl group is, for example, ethylsuccinic anhydride represented by formula (III-5-1), propylsuccinic anhydride represented by formula (III-5-2), or formula ( III-5-3). It is worth mentioning that the acid anhydride group is a group formed by dicarboxylic acid by intramolecular dehydration. The dicarboxylic acid is, for example, succinic acid or glutaric acid. Formula (III-5-1) Formula (III-5-2) Formula (III-5-3)

When R _i in formula (III-5) represents 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, specific examples and preferred examples thereof include the aforementioned R _g As shown, it will not be repeated here.

The other silane monomer (b1-2) represented by the formula (III-5) may be used alone or in combination, and the other silane monomer (b1-2) represented by the formula (III-5) contains one having a silicon atom. Compound. The compound having one silicon atom includes a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, and a silane having one hydrolyzable group. Compound, or a combination thereof.

Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane , Tetra-second butoxysilane, or a combination thereof.

Specific examples of the silane compound having three hydrolyzable groups include methyltrimethoxysilane (MTMS for short), methyltriethoxysilane, methyltriisopropoxysilane, methyltriisosilane Methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl Tri-n-butoxysilane (n-propyltrimethoxysilane), n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane (n -butyltrimethoxysilane), n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane decyltrimethoxysilane), vinyltrimethoxysilane, vinyltriethoxysilane, 3-propenyloxypropyl 3-acryoyloxypropyltrimethoxysilane, 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylacryloyloxypropyltrimethoxysilane (3-methylacryloyloxypropyltrimethoxysilane) methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxybenzene (1- (p-hydroxyphenyl) ethyltrimethoxysilane), 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5 -(P-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane), trifluoromethyltrimethoxysilane, trifluoromethyltrimethoxysilane Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane methoxysilane), 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (triphenoxysilyl) propylsuccinic anhydride ( 3-triphenoxysilyl propyl succinic anhydride), a commercially available product manufactured by Shin-Etsu Chemical Co., Ltd .: 3- (trimethoxysilyl propyl succinic anhydride) (trade name X-12-967), Commercial products manufactured by WACKER: 3- (triethoxysilyl) propyl succinic anhydride (trade name: GF-20), 3- (trimethoxysilyl) (3- (trimethoxysilyl) propyl glutaric anhydride (TMSG), 3- (triethoxysilyl) propyl glutaric anhydride), 3- (trimethoxysilyl) 3- (triphenoxysilyl) propyl glutaric anhydride) or a combination thereof.

Specific examples of the silane compound having two hydrolyzable groups include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane , Di-n-butyldimethoxysilane, or a combination thereof.

Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butylethoxysilane, or A combination of the above compounds.

The other silane monomer (b1-2) of the structure represented by the formula (III-5) is preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, thiomethyltrimethoxysilane, thiomethyltriethoxy Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, or a combination of these compounds.

Based on the total amount of monomers in the second monomer mixture being 1 mole, the silane monomer (b1-2) is used in an amount of 0 mole to 0.7 mole, preferably 0 to 0.6 mole. , More preferably 0 to 0.5 mole.

The second monomer mixture may further include a commercially available silane monomer, and specific examples thereof include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, and X-21. -5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX , X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X -40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40 -9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L , KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (made by Shin-Etsu Chemical); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840 , SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31 , DMS-S32, DMS-S33, DMS-S35, DMS-S38, D MS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (made by JNC); MS51, MS56 (made by Mitsubishi Chemical); and GR100, GR650, Some condensates of GR908 and GR950 (manufactured by Showa Denko). Method for preparing epoxy group-containing polysiloxane (b1)

The polycondensation reaction of the epoxy group-containing polysiloxane compound can be formed by a general method. For example, an organic solvent, water, or a catalyst is optionally further added to the second monomer mixture, and then an oil bath is used. The heating is performed at 50 ° C to 150 ° C, and the heating time is preferably 0.5 hours to 120 hours. During heating, the mixed solution may be stirred or placed under reflux conditions.

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

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, cyclohexanone, and 2-butanone , 2-hexanone and other ketone solvents; ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and other esters Solvents; Ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane (dioxane); 1-hexanol, 4-methyl 2-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. Alcohol solvents; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, trimethylamine hexamethyl phosphate, 1,3-dimethyl Amidamine-based solvents such as 2-imidazolidinone, or a combination of the above organic solvents.

These organic solvents may be used alone or in combination.

Based on the molar amount of the second monomer mixture being 1 mol, the amount of the organic solvent used is preferably 10 g to 1200 g, and more preferably 30 g to 1000 g.

Based on the second monomer mixture being 1 mole, the amount of water used is preferably from 20 grams to 1000 grams.

The catalyst is not particularly limited. Preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, triethylamine Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and other tertiary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above.

The amount of catalyst used varies depending on the reaction conditions such as type, temperature, etc., and can be appropriately set. For example, based on 1 mole of the second monomer mixture, the amount of the catalyst added is 5 to 50 grams, preferably 8 g to 45 g, more preferably 10 g to 40 g.

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction liquid is preferably washed with water. When performing this washing | cleaning, it is preferable to wash | clean with water containing a small amount of salt, for example, about 0.2 weight% of ammonium nitrate aqueous solution etc. The washing can be performed until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the organic solvent is removed to obtain an epoxy group-containing Polysiloxane (b1).

The ethylenically unsaturated compound (b2) of the present invention may include a structure such as the formula (II): Formula (II) In formula (II), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of hydrogen atoms of a functional group of R ₁ is Substituted or unsubstituted; R ₂ is a methylene group or a linear or branched alkylene group from C ₂ to C ₁₀ and a part of the hydrogen atom of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond, Methylene, or a linear or branched alkylene group from C ₂ to C ₁₀ , and a part of hydrogen atoms of R ₃ functional group is substituted or unsubstituted; R ₄ is hydrogen atom or methyl group; L is -OCO- , -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; and when a is plural, a plurality of R ₂ and L are each For the same or different.

Specifically, examples of the compound of the above formula (II) may include acrylic acid, methacrylic acid, 2-propenyloxyethyl-2-hydroxyethyl phthalic acid, 4- (2-methyl-acrylic acid) Benzoic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylhexylhydrophthalic acid, methacrylic acid Dicarboxylic acid, phthalic acid monohydroxyethyl acrylate. One or more of the above examples can be used. Examples of commercially available products of the above compounds are acrylic acid and methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Lightester HO-MS, Lightester HO-HH, HOA-MPL, HOA-MS, HOA-HH (Kyoeisha) Chemical Co., Ltd.), M-5400 (East Asia Synthesis Co., Ltd.).

Examples of the compound of the above formula (II) may also include compounds of the following formula (II-1) to (II-16). Formula (II-1) Formula (II-2) Formula (II-3) Formula (II-4) Formula (II-5) Formula (II-6) Formula (II-7) Formula (II-8) Formula (II-9) Formula (II-10) Formula (II-11) Formula (II-12) Formula (II-13) Formula (II-14) Formula (II-15) Formula (II-16)

In the formulae (II-10) to (II-16), R ⁴ represents a hydrogen atom or a methyl group, t1 is an integer of 1 to 10, and t2 + t3 is an integer of 1 to 10.

In the synthesis of the photoreactive group-containing polysiloxane (B-1), when the ethylenically unsaturated compound (b2) is used, the bulk resistance of the liquid crystal alignment agent is high.

Based on the total amount of monomers in the second monomer mixture being 1 mol, the amount of the ethylenically unsaturated compound (b2) used is 0.1 mol to 0.5 mol, preferably 0.15 mol to 0.45 mol, but More preferably 0.12 to 0.4 mol. If the use amount of the ethylenically unsaturated compound (b2) is within the above range, the liquid crystal contact angle of the liquid crystal alignment agent is low.

In the present invention, the obtained mixture of the photoreactive group-containing polysiloxane (B-1) may further include a side chain compound (b3), and the side chain compound (b3) includes a formula (IV) Structure: E ^1- L ^0- L ^1- Z Formula (IV) In formula (IV), E ¹ is a C ₁ to C ₃₀ alkyl group, substituted with a C ₁ to C ₂₀ alkyl group or an alkoxy group, or Unsubstituted C ₃ to C ₁₀ cycloalkyl, or C ₁₇ to C ₅₁ hydrocarbon group containing a steroid skeleton, part of the hydrogen atom of the alkyl group and alkoxy group of E ¹ is substituted or unsubstituted; L ⁰ Is a single bond, ^{* 1} -O-, ^{* 1} -COO- or ^{* 1} -OCO-, where ^{* 1} is the junction with E ¹ ; L ¹ is a single bond, C ₁ to C ₂₀ Phenyl, biphenyl, cyclohexyl, dicyclohexyl or a group represented by the following formula (IV-1) or (IV-2): Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; ^{* 2} is a bond with Z; and Z is a monovalent organic group that reacts with an epoxy group to form a bonding group.

The linear or branched C ₁ to C ₃₀ alkyl group described by E ^{1 in} the above formula (IV) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl , N-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethyl Butyl, 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 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethyl Butyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2- Methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl , N-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-decyl, Eighteen bases, n-nineteen bases, etc.

The C ₃ to C ₁₀ cycloalkyl group described by E ^{1 in} the above formula (IV) may be, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl Wait. These cycloalkyl groups described above may be substituted with or without C ₁ to C ₂₀ alkoxy groups. For specific examples of the C ₁ to C ₂₀ alkoxy group, reference may be made to the specific examples given in the description of the C ₁ to C ₃₀ alkyl group described above. For specific examples of the C ₁ to C ₂₀ alkoxy group, reference may be made to the specific examples of the alkyl group mentioned in the description of the C ₁ to C ₃₀ alkyl group, and the group obtained by bonding with an oxygen atom. The alkyl group and the alkoxy group described in E ¹ may have at least a part of hydrogen atoms substituted, and examples of the group for replacing a hydrogen atom include a nitrile group, a fluorine atom, and a trifluoromethyl group.

The hydrocarbon group of C ₁₇ to C ₅₁ containing a steroid skeleton as described in E ^{1 in} the above formula (IV) may be, for example, a group represented by the following formulae (S-1) to (S-3), wherein ^{* 5} represents a bond between the above group and L ⁰ of formula (IV). Formula (S-1) Formula (S-2) Formula (S-3)

Preferably, E ¹ may be selected from C ₁ to C ₂₀ alkyl groups, C ₁ to C ₂₀ fluoroalkyl groups, groups of the above formula (S-1), and groups of the above formula (S-3) A group of people. Z is preferably a carboxyl group. The alkylene group of C ₁ to C ₂₀ described in L ^{1 in} the above formula (IV) may be, for example, removing one hydrogen atom from each of the groups mentioned in the aforementioned alkyl group of C ₁ to C ₃₀ And the resulting group.

The compound represented by the above formula (IV) is preferably a compound represented by the following formulae (IV-1) to (IV-8). Formula (IV-1) Formula (IV-2) Formula (IV-3) Formula (IV-4) Formula (IV-5) Formula (IV-6) Formula (IV-7) Formula (IV-8)

In formulae (IV-1) to (IV-8), u is an integer from 1 to 5, v is an integer from 1 to 18, w is an integer from 1 to 20, k is an integer from 1 to 5, and p is 0 or 1. q is an integer from 1 to 18, r is an integer from 0 to 18, and j is an integer from 1 to 18. s and t are each independently an integer of 0 to 2. However, s and t are not 0 at the same time.

Preferably, v in the above formula (IV-1) is an integer of 1 to 18, but an integer of 1 to 12 is more preferable. W of the above formula (IV-2) is preferably an integer of 5 to 20, and more preferably 10 to 18. W of the above formula (IV-3) may be an integer of 1 to 17, but an integer of 3 to 12 is more preferable. W of the above formula (IV-4) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable. W of the above formula (IV-8) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable. In the above formulae (IV-5) and (IV-6), r is preferably an integer of 0 to 15, but an integer of 0 to 8 is more preferable. In the above formula (IV-6), q may be an integer of 1 to 12, but an integer of 1 to 5 is more preferable. J in the above formula (IV-8) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable.

Among the above compounds, at least one of the above formulae (IV-2) to (IV-5), (IV-7), and (IV-8) is preferable. Specifically, the following formulae (IV-1 ') to (IV-8') are preferred. Formula (IV-1 ') Formula (IV-2 ') Formula (IV-3 ') Formula (IV-4 ') Formula (IV-5 ') Formula (IV-6 ') Formula (IV-7 ') Formula (IV-8 ')

Based on the total amount of monomers in the second monomer mixture being 1 mole, the amount of the side chain compound (b3) used is 0.05 to 0.3 moles, preferably 0.08 to 0.3 moles. 0.08 mole to 0.27 mole is more preferred. If the amount of the side chain compound (b3) is within the above range, the liquid crystal contact angle of the liquid crystal alignment agent is low.

Based on the use amount of the polymer (A) is 100 parts by weight, the use amount of the photoreactive group-containing polysiloxane (B-1) is 3 to 60 parts by weight, preferably 5 to 60 parts by weight It is more preferably 5 parts by weight to 55 parts by weight. Preparation method of photoreactive group-containing polysiloxane (B-1)

The photoreactive group-containing polysiloxane (B-1) used in the present invention can be obtained by mixing the epoxy-group-containing polysiloxane (b1) with an ethylenically unsaturated compound (b2) and a side chain compound (b3). ), Reaction synthesis in the presence of a catalyst.

As the catalyst, an organic salt or a known compound such as a hardening accelerator that can accelerate the reaction between the epoxy compound and the acid anhydride can be used.

Examples of the organic salt include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, and tri-n-butylamine. Tertiary organic amines such as amines, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and tertiary organic amines such as tetramethylammonium hydroxide. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, or tetramethylammonium hydroxide, etc. are preferred. Grade organic amine.

Specific examples of the hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptylimidazole, 2-n-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyano (Ethyl) -2-5-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2 -Phenyl-4,5-bis [(2'-cyanoethoxy) methyl] imidazole, l- (2-cyanoethyl-2-n-undecylimidazolium trimellitate , 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitic acid Salt, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine, 2,4-diamino-6- (2'-n-deca Monoalkylimidazole) ethyl-S-triazine, 2,4-diamino-6- [2'- -4'-methylimidazolyl- (1 ')] ethyl-S-triazine, trimeric isocyanate adduct of 2-methylimidazole, triphenyl isocyanate addition of 2-phenylimidazole Imidazole compounds such as trimeric isocyanate adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine; diphenyl Organophosphorus compounds such as phosphine, triphenylphosphine, and triphenyl phosphite; benzyl triphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, Ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium acetate- O, O-diethylphosphodithiosulfate (tetra-n-butyl phosphonium-O, O-diethyl phosphorodithionate), tetra-n-butylphosphonium benzotriazole, tetra-n-butylphosphonium benzotriazolate, tetra Tertiary phosphonium salts such as n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, etc .; 1,8-diazabicyclo [5.4.0] Diazabicyclic olefins such as monoene-7 or its organic acid salts; zinc octoate, tin octoate, acetamidine Organometallic compounds such as aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc. Grade ammonium salts; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; dicyandiamide or the addition of amines and epoxy resins Latent hardening accelerators with high melting point dispersion, such as amine addition molding accelerators such as products; microcapsules that cover the surface of the hardening accelerators such as imidazole compounds, organic phosphorus compounds, or quaternary phosphonium salts with polymers Latent Hardening Accelerator; Amine Salt Latent Hardening Accelerator; Lactoacid, Bronsted Acid Salt, and other high-temperature dissociation-type thermal cationic polymerization latent hardening accelerator, etc. Wait.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

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

The synthesis reaction of the photoreactive group-containing polysiloxane (B-1) can be carried out in the presence of an organic solvent, if necessary. The organic solvent is not particularly limited, and may be the same as or different from the organic solvent used in the preparation of the epoxy-containing polysiloxane (b1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. the same. Specific examples of the organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

The weight-average molecular weight of the photoreactive group-containing polysiloxane (B-1) of the present invention is 2,000 to 20,000; preferably 3,000 to 18,000; more preferably 5,000 to 15,000.

The liquid crystal alignment agent of the present invention includes a polysiloxane (B), and the polysiloxane (B) may include a polysiloxane (B-2) without a photoreactive group. This photoreactive group-containing polysiloxane (B-2) can also be used together with the photoreactive group-containing polysiloxane (B-1).

The aforementioned polysiloxane (B-2) without a photoreactive group is an epoxy group-containing polysiloxane (b4), and the epoxy group-containing polysiloxane (b4) contains a Copolymer obtained by hydrolyzing and partially condensing the third monomer mixture. Wherein, the third monomer mixture may include the aforementioned silane monomer (b1-1) and / or other silane monomer (b1-2), and the preparation method thereof is the same as that of the aforementioned polysiloxane containing photoreactive group. (B-1), I will not repeat them here.

In the present invention, the third monomer mixture may further include a side chain compound (b3), wherein the side chain compound (b3) is the same as described above, and is not repeated here.

Based on the total amount of monomers in the third monomer mixture being 1 mole, the amount of the side chain compound (b3) used is 0.05 to 0.3 moles, preferably 0.08 to 0.3 moles. 0.08 mole to 0.27 mole is more preferred. If the amount of the side chain compound (b3) is within the above range, the liquid crystal contact angle of the liquid crystal alignment agent is low.

Based on 100 parts by weight of the polymer (A), the polysiloxane (B-2) without photoreactive groups is used in an amount of 3 to 60 parts by weight, and preferably 5 parts by weight To 60 parts by weight, and more preferably 5 to 55 parts by weight.

The weight-average molecular weight of the non-photoreactive group-containing polysiloxane (B-2) of the present invention is 2,000 to 20,000; preferably 3,000 to 18,000; more preferably 5,000 to 15,000.

Based on the used amount of the polymer (A) being 100 parts by weight, the used amount of the polysiloxane (B) is 3 to 60 parts by weight, preferably 5 to 60 parts by weight, and then 5 parts by weight It is more preferably from 55 to 55 parts by weight.

When the liquid crystal alignment agent of the present invention does not include polysiloxane (B), the bulk impedance of the liquid crystal alignment agent is low and the liquid crystal contact angle is too high.

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it dissolves the polymer (A), the polysiloxane (B) and other arbitrary components and does not react therewith, it is preferably The same solvents as those used in the synthesis of the polyamic acid may be used together with the lean solvents used in the synthesis of the polyamino acid.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl 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, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N, N-dimethylformamide or N, N-dimethyl acetamide. The solvent (C) may be used alone or in combination.

Based on 100 parts by weight of the polymer (A), 800 to 3000 parts by weight of the solvent (C) is used, preferably 1,000 to 3000 parts by weight, and more preferably 1000 to 2800 parts by weight.

To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (D), wherein the additive (D) includes a compound having at least two epoxy groups, a silane compound having a functional group, Or a combination.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- M-xylylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, or a combination of the above compounds.

The compound having at least two epoxy groups may be used alone or in combination.

The use amount of the compound having at least two epoxy groups may be 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight based on the use amount of the polymer (A).

Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Silyl, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene Triamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilyl- 3,6-Diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Ethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxysilane Silane, or combinations of the above compounds.

The silane compound having a functional group may be used alone or in combination.

Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the silane compound having a functional group may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

The use amount of the additive (D) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight based on the total use amount of the polymer (A). Manufacturing method of liquid crystal alignment agent

The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example, the polymer (A) and the polysiloxane (B) prepared in the above manner are first mixed uniformly to form a mixture. Next, the solvent (C) is added under the condition of a temperature of 0 ° C. to 200 ° C., and the additive (D) is optionally added. Finally, the stirring is continued with a stirring device until dissolved. In addition, it is preferable to add the solvent (C) at a temperature of 20 ° C to 60 ° C.

At 25 ° C, the viscosity of the liquid crystal alignment agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps. Liquid crystal alignment film and method for manufacturing liquid crystal display element

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display device including the aforementioned liquid crystal alignment film.

The liquid crystal alignment film of the present invention is formed by using the liquid crystal alignment agent prepared as described above. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited, and it may be a vertical alignment type.

The liquid crystal alignment film and the method for manufacturing a liquid crystal display element of the present invention may include: coating the liquid crystal alignment agent of the present invention on a pair of conductive films of a substrate having a conductive film, and then heating the substrate to form a coating film. The first step; the second step of arranging the pair of substrates with the coating film formed thereon to construct a liquid crystal cell; and arranging the pair of substrates with a conductive film with light when the voltage is applied to the liquid crystal cell The third step. First step: formation of coating film

In this step, two substrates provided with a patterned transparent conductive film are used as a pair, and the liquid crystal alignment agent of the present invention is coated on the surface of the substrate on which the transparent conductive film is formed, preferably a lithography The liquid crystal alignment agent is applied by a printing method, a spin coating printing method, a roll coating method, or an inkjet method. The substrate referred to here may be, for example, glass such as float glass, soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, poly (alicyclic olefin) And other plastic transparent substrates. The transparent conductive film provided on the surface of the substrate can be a NESA film (registered trademark of American PPG Corporation) formed of tin oxide (SnO ₂ ), or an indium oxide and tin oxide (In ₂ O ₃ -SnO ₂ ) ITO film. The patterned transparent conductive film can be formed by, for example, first forming an unpatterned transparent conductive film, then photo-etching a pattern forming method, and using a mask having a predetermined pattern when the transparent conductive film is formed. Reached. When applying the liquid crystal alignment agent, in order to provide good adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is formed may be previously coated with a functional silane compound and a functional titanium compound. Wait before processing.

After the liquid crystal alignment agent is applied, in order to prevent the applied liquid crystal alignment agent from dripping, it is preferable to perform prebake. The pre-baking temperature may be 30 ° C to 200 ° C, preferably 40 ° C to 150 ° C, and more preferably 40 ° C to 100 ° C. The pre-baking time may be from 0.25 to 10 minutes, preferably from 0.5 to 5 minutes. After that, the solvent is completely removed, and the substrate is subjected to a step of sintering (post-baking) in order to form the necessary polymer and the structure of the amino acid to be thermally imidized. The post-baking temperature may be 80 ° C to 300 ° C, preferably 120 ° C to 250 ° C. The post-baking time may be 5 minutes to 200 minutes, preferably 10 minutes to 100 minutes. Therefore, the thickness of the formed film can be 0.001 μm to 1 μm, and preferably 0.005 μm to 0.5 μm.

The heating step after the liquid crystal alignment agent is applied can remove the organic solvent, thereby forming a coating film of the liquid crystal alignment film. At this time, the polymer contained in the liquid crystal alignment agent of the present invention includes a polyfluorene acid or a fluorene imine polymer having a fluorene imine structure and a fluorin acid structure. Thereafter, the formed coating film is further heated, and the polymer undergoes a dehydration ring-closing reaction to form a fluorinated coating film. The coating film formed by the above method can be directly used as a liquid crystal alignment film, but a predetermined rubbing treatment can also be performed. The second step: the construction of liquid crystal cells

In this step, two substrates on which the above-mentioned liquid crystal alignment film is formed are provided, and a liquid crystal layer containing a liquid crystal compound and a photopolymerizable compound is disposed between the two substrates disposed oppositely to form a liquid crystal cell. Examples of the method for manufacturing the liquid crystal cell include the following two methods.

The first method is a conventional method (vacuum injection method). First, two substrates are arranged opposite to each other so that a gap (cell gap; Cell Gap) is formed between the oppositely arranged liquid crystal alignment films. The two substrates are bonded together with an adhesive, and a liquid crystal compound and a photopolymerizable compound are injected and filled in a cell gap defined by the substrate surface and the adhesive, and then the injection holes are sealed to obtain a liquid crystal. Cell.

The second method is called One Drop Filling (ODF). For example, a UV-curable adhesive is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed. Next, after a mixture of a liquid crystal compound and a photopolymerizable compound is dropped at a predetermined position of the liquid crystal alignment film, the liquid crystal alignment film and the liquid crystal alignment film of the other substrate are disposed opposite to each other, and the two substrates are bonded together so that the liquid crystal is on the substrate. Diffuses over the entire surface, and then irradiates the entire substrate with ultraviolet light to harden the adhesive to produce liquid crystal cells. Regardless of which method is used, after the liquid crystal cell is formed, the substrate is heated to a temperature at which the liquid crystal compound used is converted to an isotropic temperature, and then slowly cooled to room temperature to remove the flow alignment during liquid crystal filling.

As the above-mentioned adhesive, an epoxy resin as a hardener and a spacer can be used, which contains alumina balls. The liquid crystal compound is preferably a nematic liquid crystal having negative dielectric anisotropy. For example, dicyanophenyl liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azo oxide liquid crystal, and biphenyl liquid crystal can be used. , Phenylcyclohexyl liquid crystal, terphenyl liquid crystal and the like. In addition, in order to make the response speed of the liquid crystal display device of the PSA mode faster, it is preferable to use an alkenyl liquid crystal in combination, which is a monofunctional liquid crystal compound having one alkenyl or fluoroalkenyl group. The alkenyl liquid crystal may be a conventional alkenyl liquid crystal, for example, a compound represented by the following formula (L1-1) to formula (L1-9).

As the photopolymerizable compound, a compound having a functional group capable of performing a radical polymerization reaction, such as an acryl group, a methacryl group, or a vinyl group, can be used. Among these, from the viewpoint of reactivity, a compound having a functional group of at least two of an acrylamide group and a methacryl group is preferably used. In addition, from the viewpoint of maintaining the alignment stability of the liquid crystal molecules, the photopolymerizable compound is a liquid crystal skeleton, and a compound having at least two of a cyclohexane ring and a benzene ring is preferably used. As the photopolymerizable compound, a conventional photopolymerizable compound can be used. The photopolymerizable compound is preferably used in an amount of 0.1% to 0.5% by weight based on the entire weight of the liquid crystal compound. The thickness of the liquid crystal layer is preferably 1 μm to 5 μm. Third step: exposure step

After the liquid crystal cell is constructed, a voltage is applied between the conductive films of the pair of substrates, and at the same time, light is irradiated. The voltage applied here can be, for example, 5V to 50V DC or AC. In addition, the irradiated light may be, for example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm, but ultraviolet light including light having a wavelength of 300 nm to 400 nm is more preferable. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. In addition, a light source can be used in combination with a filter, a diffraction grating, and the like to obtain the above-mentioned ultraviolet light in the preferred wavelength range.

The irradiation amount of light may be 1,000 J / m ² or more and less than 100,000 J / m ² , and preferably 1000 J / m ² to 50,000 J / m ² . For example, it is known that when manufacturing a liquid crystal display element in the PSA mode, a light irradiation amount of 100,000 J / m ² is required. However, the liquid crystal display element of the present invention can use an irradiation light amount of less than 100,000 J / m ² or even less than 50,000 J / m ² To obtain a liquid crystal display element having a predetermined pretilt angle characteristic, and reduce the manufacturing cost of the liquid crystal display element. Furthermore, it is possible to suppress deterioration of electrical properties and deterioration of reactivity of liquid crystal molecules due to strong light irradiation.

Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell, so that the liquid crystal display element of the present invention can be manufactured. The above polarizing plate can be exemplified by a polarizing film of polyvinyl alcohol extending alignment and absorbing iodine liquid, called "H film", and a polarizing film formed by sandwiching the above polarizing film with a cellulose acetate protective film. board.

The liquid crystal display element of the present invention can be applied to various devices, such as: watches, portable game consoles, word processors, notebook computers, navigation systems, video cameras, PDAs, digital cameras, mobile phones, smart phones, and various screens. , LCD TV, electronic signage and other display devices.

The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples. Preparation of diamine compound (a2-1) <Synthesis Example a2-1-1>

In a 500 ml three-necked flask, 25.0 g (0.13 mol) of 1,3-dinitrobenzyl alcohol, 3,4-dihydro-2H-pyran-2-propionic acid chloride (3,4-dihydro- 2H-Pyran-2-propanoic chloride) 15.6 g (0.1 mol) and 300 ml of tetrahydrofuran. Next, 9.0 ml of pyridine was added dropwise, and the mixture was stirred at room temperature for 25 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Then, anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and the solvent was removed by a cycloconcentrator after filtration. The residue was dissolved in tetrahydrofuran / hexane = 1/3 (volume ratio, the same below) and recrystallized to obtain 30.3 g (0.94 mol) of a milky white solid (yield 94%). The reaction formula of the above reaction is as follows.

Then, a 500 ml four-necked flask was charged with 25 g of a dinitro compound, 2.5 g of platinum / carbon (mass ratio: 1/10, the same applies hereinafter), and 240 g of methanol, and stirred in a hydrogen atmosphere for 43 hours. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol and recrystallized to obtain 17.4 g of the diamine compound a2-1-1 (light orange solid, yield 85%). The reaction formula of the above reaction is as follows. <Synthesis example a2-1-2>

A 500 ml four-necked flask was charged with 0.1 mol of 3,5-dinitrobenzidine chloride, 0.1 mol of 2H-Pyran-4-methanol, and 200 ml of tetrahydrofuran. Next, 9.7 ml of pyridine was added dropwise, and the mixture was stirred at room temperature for 16 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was purified by silica gel column chromatography (mobile phase: hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 29.1 g (0.095 mol) of a dinitro compound (yield 95%), as shown in the following formula: (I-5-1). Formula (I-5-1)

A 500 ml four-necked flask was charged with 25 g of a dinitro compound, 2.5 g of platinum / carbon, and 300 ml of methanol, and stirred under a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol / hexane = 1/1 and recrystallized to obtain 9.2 g of a diamine compound a2-1-2 (light brown solid, yield 46%), as shown in the following formula (I-5-2 ). Formula (I-5-2) <Synthesis example a2-1-3>

A 500 ml three-necked flask was charged with 0.1 mol of 3,5-dinitroaniline, 12 ml of pyridine, and 300 ml of tetrahydrofuran, and then 2H-1-benzopyran-4-acetic acid chloride (2H-1) was added dropwise. -Benzopyran-4-acetic chloride) 0.1 ml, and stirred at room temperature for 18 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was dissolved in tetrahydrofuran / hexane = 1/3 and recrystallized to obtain 29.8 g (0.095 mol) of a dinitro compound (yield 84%), as shown in the following formula (I-5-3). Formula (I-5-3)

In a 1 L four-necked flask, 25 g of a dinitro compound, 2.5 g of platinum / carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were added, and stirred in a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol / hexane = 1/1 and recrystallized to obtain 18.3 g of a diamine compound a2-1-3 (light brown solid, yield 88%), as shown in the following formula (I-5-4 ). Formula (I-5-4) <Synthesis Example a2-1-4>

A 500 ml four-necked flask was charged with 0.1 mol of 3,5-dinitrobenzidine chloride, 0.1 mol of 2H-Pyran-6-methanamine, and 200 ml of tetrahydrofuran. Then, 9.5 ml of pyridine was added dropwise, and stirred at room temperature for 16 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was purified by silica gel column chromatography (mobile phase: hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 28.4 g (0.093 mol) of a dinitro compound (yield 93%), as shown in the following formula: (I-5-5). Formula (I-5-5)

In a 1 L four-necked flask, 25 g of a dinitro compound, 2.5 g of platinum / carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were added, and stirred in a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol / hexane = 1/1 and recrystallized to obtain 9.6 g of a diamine compound a2-1-4 (light brown solid, yield 48%), as shown in the following formula (I-5-6 ). Formula (I-5-6) <Synthesis Example a2-1-5>

In a 500 ml four-necked flask, add 0.1 mol of cyclopentadiene [c] pyran-1-acetic acid and 170 ml of dichloromethane, and cool from room temperature to 0 ° C. Next, 5.9 ml of chloramphenicol and 0.5 g of DMF were added, and the mixture was stirred at room temperature for 2 hours. After stirring, add 0.1 mol of 3,5-dinitrophenol and 6 ml of pyridine, and stir at room temperature for 16 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Then, ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtering through celite, the solvent was removed by a cycloconcentrator. The residue was washed with isopropanol to obtain 29 g of a dinitro compound (yield: 85%), as shown in the following formula (I-5-7). Formula (I-5-7)

A 500 ml four-necked flask was charged with 25 g of a dinitro compound, 2.5 g of platinum / carbon, and 200 g of tetrahydrofuran, and stirred for 21 hours under a hydrogen atmosphere. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol and recrystallized to obtain 14.4 g of a diamine compound a2-1-5 (light brown solid, yield 70%), as shown in the following formula (I-5-8). Formula (I-5-8) <Synthesis example a2-1-6>

In a 500 ml four-necked flask, add 0.1 mol of 3,5-dinitrobenzidine chloride, 6-methoxy-2H-1-benzopyran-3-methylamine (6-methoxy-2H-1 -Benzopyran-3-methanamine) 0.1 mol and 200 ml of tetrahydrofuran, and then 9.5 ml of pyridine was added dropwise, followed by stirring at room temperature for 16 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was purified by silica gel column chromatography (mobile phase: hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 36.19 g (0.094 mol) of a dinitro compound (yield 94%), as shown in the following formula: (I-5-9). Formula (I-5-9)

In a 1 L four-necked flask, 25 g of a dinitro compound, 2.5 g of platinum / carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were added, and stirred in a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol and recrystallized to obtain 9.7 g of a diamine compound a2-1-6 (light brown solid, yield 46%), as shown in the following formula (I-5-10). Formula (I-5-10) <Synthesis example a2-1-7>

A 500 ml three-necked flask was charged with 0.1 mol of 3,5-dinitroaniline, 12 ml of pyridine, and 300 ml of tetrahydrofuran, and then 3- (2H-1-benzopyran-3-yl) -2 was added dropwise. -0.1 ml of 3- (2H-1-benzopyran-3-yl) -2-propenoic chloride and stirred at room temperature for 18 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was dissolved in tetrahydrofuran / hexane = 1/3 and recrystallized to obtain 30.1 g of a dinitro compound (yield 82%), as shown in the following formula (I-5-11). Formula (I-5-11)

In a 1 L four-necked flask, 25 g of a dinitro compound, 2.5 g of platinum / carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were added, and stirred in a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol and recrystallized to obtain 18.0 g of a diamine compound a2-1-7 (light brown solid, yield 86%), as shown in the following formula (I-5-12). Formula (I-5-12) <Synthesis example a2-1-8>

In a 500 ml four-necked flask, add 0.1 mol of 3,5-dinitrobenzidine chloride, 6-fluoro-4-methyl-2H-1-benzopyran-3-methylamine (6-fluoro- 4-methyl-2H-1-Benzopyran-3-methanamine) 0.1 mol and 250 ml of tetrahydrofuran, 10 ml of pyridine was added dropwise, and the mixture was stirred at room temperature for 16 hours. After the reaction was completed, 50 ml of pure water was added and stirred for 1 hour. Ethyl acetate was added to extract the organic layer, and the organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated common salt solution. Anhydrous magnesium sulfate was added to dehydrate and dry the organic layer, and after filtration, the solvent was removed by a cycloconcentrator. The residue was purified by silica gel column chromatography (mobile phase: hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 35.6 g (0.092 mol) of a dinitro compound (yield 92%), as shown in the following formula: (I-5-13). Formula (I-5-13)

In a 1 L four-necked flask, 30 g of a dinitro compound, 3.0 g of platinum / carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were added, and stirred in a hydrogen atmosphere and room temperature. After the reaction was completed, it was filtered through celite, and the solvent was removed by a cycloconcentrator. The residue was dissolved in isopropanol and recrystallized to obtain 12.7 g of a diamine compound a2-1-8 (light brown solid, yield 50%), as shown in the following formula (I-5-14). Preparation of Formula (I-5-14) Polymer (A) <Synthesis Example A-1-1>

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, 0.0015 mol of the diamine compound a2-1-1 of the aforementioned Synthesis Example, 0.0435 mol of p-diamine benzene (abbreviated as a2-2-1), and 0.005 mol of the table were added. A2-2-4 and 80 g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, abbreviated as NMP) shown in 1 are stirred at room temperature until dissolved. Next, 0.05 mol of 2,3,5-tricarboxycyclopentylacetic dianhydride (abbreviated as a1-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 0.035 mole of acetic anhydride, and 0.05 mole of pyridine were added, the temperature was raised to 115 ° C., and stirring was continued for 3 hours to carry out the imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1). <Synthesis Examples A-1-2 to A-1-12 and Comparative Synthesis Examples A-3-1 to A-3-2>

Synthesis Examples A-1-2 to A-1-12 and Comparative Synthesis Examples A-3-1 to A-3-2 The polymer was prepared in the same procedure as in Synthesis Example A-1-1, except for the differences The reason is that the types of tetracarboxylic dianhydride compounds or diamine compounds and their usage amounts, the usage amounts of acetic anhydride and pyridine, and the reaction temperatures are shown in Tables 1 and 2. <Synthesis example A-2-1>

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, 0.005 moles of a2-1-1 of the aforementioned Synthesis Example, 0.04 moles of p-diaminebenzene (abbreviated as a2-2-1), and 0.005 moles are shown in Table 1. A2-2-5 and 80 g of N-methyl-2-pyrrolidone NMP, and stir at room temperature until dissolved. Next, 0.05 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a1-2) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1). <Synthesis example A-2-2 and comparative synthesis examples A-3-3 to A-3-4>

Synthesis Example A-2-2 and Comparative Synthesis Examples A-3-3 to A-3-4 were prepared by the same procedure as Synthesis Example A-2-1, except that the tetracarboxylic acid was changed The types and amounts of dianhydride compounds or diamine compounds are shown in Tables 1 and 2. Table 1: Table 2: In Tables 1 and 2 Preparation of photoreactive group-containing polysiloxane (B-1) <Synthesis Example B-1-1>

A 500 ml three-necked flask was equipped with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 1.00 mol of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as ECETS) and 600 g of propylene glycol monomethyl ether (hereinafter referred to as PGME), and triethylamine (hereinafter referred to as TEA) aqueous solution (20 g TEA / 200 g H ₂ O) was added within 30 minutes while stirring at room temperature. Next, the three-necked 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. within 30 minutes. When the internal temperature of the solution reached 75 ° C., the mixture was continuously heated and stirred for 6 hours . After the reaction is completed, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution to obtain a solution of an epoxy-containing polysiloxane compound.

Next, 0.50 mole of ethylenically unsaturated compound b2-1 and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO) were added to a solution of an epoxy-containing polysiloxane compound. Then, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the oil bath was heated to 115 ° C. within 30 minutes. When the internal temperature of the solution reached 100 ° C., heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain a polysiloxane (B-1-1) containing a photoreactive group. <Synthesis example B-1-2 to synthesis example B-1-10>

Synthesis Examples B-1-2 to B-1-10 were prepared by the same procedure as Synthesis Example B-1-1, and this photoreactive group-containing polysiloxane (B-1) was prepared, and the difference was that : Change the type of reactant of polysiloxane (B-1) containing photoreactive group and its use amount, the type of catalyst and solvent and its use amount, reaction temperature and polycondensation time (see Table 3-1 , As shown in Table 3-2). Preparation of polysiloxane (B-2) without photoreactive group <Synthesis Examples B-2-1 to B-2-7>

Synthesis Examples B-2-1 to B-2-7 were prepared by the same procedure as in Synthesis Example B-1-1 of the above-mentioned photoreactive group-containing polysiloxane (B-1). Polysiloxane (B-2), and the difference lies in that: the type of the reactant of polysiloxane (B-2) which does not contain a photoreactive group and its amount, catalyst and solvent are changed And its use amount, reaction temperature and polycondensation time (as shown in Table 4-1 and Table 4-2). Table 3-1: Table 3-2: Table 4-1: Table 4-2: In Table 3-1, Table 3-2, Table 4-1 and Table 4-2 Preparation of liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element <Example 1>

Weigh 100 parts by weight of polymer (A-1-1), 3 parts by weight of photoreactive group-containing polysiloxane (B-1-1), and 1200 parts by weight of N-methyl-2-pyrrolidone (Abbreviated as C-1) and 300 parts by weight of ethylene glycol n-butyl ether (abbreviated as C-2), and continuously stirred with a stirring device at room temperature until dissolved, the liquid crystal alignment agent of Example 1 can be formed. This liquid crystal alignment agent was evaluated for each detection item, and the obtained results are shown in Table 5-1. <Examples 2 to 24 and Comparative Examples 1 to 5>

Examples 2 to 24 and Comparative Examples 1 to 5 were used to prepare the liquid crystal alignment agent in the same steps as in Example 1. The difference was that the types and amounts of polymer composition, solvent, and additives were changed, as shown in the table. 4 and 5. These liquid crystal alignment agents were evaluated for each detection item, and the results obtained are shown in Table 5-1, Table 5-2, and Table 6. Table 5-1: Table 5-2: Table 6: In Table 5-1, Table 5-2 and Table 6: Evaluation method <body impedance>

The prepared liquid crystal alignment agent was dropped into an aluminum dish with a diameter of 32 mm and baked on a hot plate to obtain a film having a film thickness of about 0.01 mm. Continue to measure the resistance value of the film with a resistance meter (AGILENT 4339b High resistance meter), clamp the positive and negative electrodes of the instrument to both ends of the aluminum plate containing the film, and record the measured resistance value at a voltage of 50 volts. Its evaluation standard As follows: ◎: resistance value ≧ 5.0 × 10 ¹² ○: 1.0 × 10 ¹² ≦ resistance value <5.0 × 10 ¹² ╳: resistance value <1.0 × 10 ¹² <liquid crystal contact angle>

The above-mentioned liquid crystal alignment agent was applied on a transparent electrode surface of a glass substrate provided with an electrode structure on an ITO surface by a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), and heated at 80 ° C. for 1 minute on a hot plate Pre-baked) to remove solvent. After that, it was heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 800Å. 7 μl of MLC-2038 liquid crystal (manufactured by Merck) was dropped on the substrate and left for 30 seconds, and then a contact angle measuring device (DropMaster 700) manufactured by Kyowa Interface Chemical Co., Ltd. was used to measure the contact angle by the θ / 2 method The measurement standards are as follows: ◎: liquid crystal contact angle ≦ 13 ° ○: 13 °> liquid crystal contact angle ≧ 15 ° ╳: liquid crystal contact angle> 15 °.

The above embodiments are only for explaining the principle of the present invention and its effects, but not for limiting the present invention. Modifications and changes made by those skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.

Claims (19)

A liquid crystal alignment agent comprises: a polymer (A), which is prepared by reacting a first monomer mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2), wherein the polymer (A) is selected from the group consisting of a polyamidopolymer, a polyamidopolymer, a polyamidoblock copolymer, or any combination of the aforementioned polymers; a polysiloxane (B); and a solvent (C ); Wherein the diamine component (a2) comprises at least one diamine compound (a2-1) represented by formula (I): Formula (I) In Formula (I), R _a is a single bond or a linear or branched alkyl group of C ₁ to C ₁₀ ; Y is —COO—, —OCO—, —NR _d CO— or —CONR _d -; R _b is a single bond, a straight-chain or branched-chain C ₁ to C ₁₀ alkyl group, the C or straight-chain or branched alkenyl group of ₁ to C _10; R _c is a linear or branched C ₁ to C ₁₀ of Alkyl, C ₁ to C ₁₀ linear or branched oxyalkyl, C ₁ to C ₁₀ ether, C ₁ to C ₁₀ keto, C ₂ to C ₁₀ ester, halogen or nitrile ; R _d is a hydrogen atom, or a linear or branched alkyl group of C ₁ to C ₁₀ ; Py is 2H-pyran (4H-pyran), 3,4- Dihydropyran (3,4-dihydropyran), 3,6-dihydropyran (3,6-dihydropyran), cyclopenta [b] pyran (cyclopenta [b] pyran), cyclopentadiene Cyclopenta [c] pyran, 1H-benzopyran (1H-chrome), 2H-benzopyran (2H-chrome), 4H-benzopyran (4H-chrome), or 3,4-dihydro-2H-benzopyran (3,4-dihydro-2H-chrome); a1 is an integer from 0 to 5; and when R _c is plural, each R _{c is the} same or different. The liquid crystal alignment agent according to claim 1, wherein the sulfonium imidization rate of the polymer (A) is 30% to 80%. The liquid crystal alignment agent according to claim 1, wherein the amount of the polysiloxane (B) is 3 to 60 parts by weight based on 100 parts by weight of the polymer (A), and the solvent ( C) is used in an amount of 800 parts by weight to 3000 parts by weight. The liquid crystal alignment agent according to claim 1, wherein the total amount of the diamine component (a2) is 100 mol, and the diamine compound (a2-1) represented by the formula (I) The amount used is 3 to 40 moles. The liquid crystal alignment agent according to claim 1, wherein the polysiloxane (B) includes a photoreactive group-containing polysiloxane (B-1), and the photoreactive group-containing polysiloxane The alkane (B-1) is prepared by reacting a mixture including an epoxy-group-containing polysiloxane (b1) and an ethylenically unsaturated compound (b2), and the epoxy-group-containing polysiloxane (b1) comprises a copolymer obtained by subjecting a second monomer mixture to hydrolysis and partial condensation. The liquid crystal alignment agent according to claim 5, wherein the amount of the photoreactive group-containing polysiloxane (B-1) is 3 parts by weight based on 100 parts by weight of the polymer (A). To 60 parts by weight. The liquid crystal alignment agent according to claim 5, wherein the epoxy group-containing polysiloxane (b1) includes a group represented by the formula (III-1) and a group represented by the formula (III-2) And at least one of the radicals represented by formula (III-3): Formula (III-1) In Formula (III-1), B represents an oxygen atom or a single bond; c represents an integer from 1 to 3; d represents an integer from 0 to 6; and when d represents 0, B is a single bond ; Formula (III-2) In Formula (III-2), e represents an integer of 0 to 6; Formula (III-3) In Formula (III-3), D represents an alkylene group having 2 to 6 carbon atoms; and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The liquid crystal alignment agent according to claim 5, wherein the second monomer mixture includes a silane monomer (b1-1) represented by formula (III-4): Si (R _f ) _p (OR _g ) _4-p in the formula (III-4) of formula (III-4), R _f is a hydrogen atom, C ₁ to C ₁₀ alkyl group of, C ₂ to C ₁₀ alkenyl group of, C ₆ to C ₁₅ aryl group of , An alkyl group containing an epoxy group or an alkoxy group containing an epoxy group, and at least one R _f is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when p is plural, each of R _f are the same or different; R _g is a hydrogen atom, C ₁ to C ₆ alkyl group of, C ₁ to C ₆ acyl or of C ₆ to C ₁₅ aryl group of; when 4-p is plural, R _g are each The same or different; and p is an integer from 1 to 3. The liquid crystal alignment agent according to claim 8, wherein the amount of the silane monomer (b1-1) used is 0.6 mol based on the total amount of monomers in the second monomer mixture. To 1 mole. The liquid crystal alignment agent according to claim 5, wherein the ethylenically unsaturated compound (b2) includes a structure as shown in formula (II): Formula (II) In formula (II), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of hydrogen atoms of a functional group of R ₁ is Substituted or unsubstituted; R ₂ is a methylene group or a linear or branched alkylene group from C ₂ to C ₁₀ and a part of the hydrogen atom of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond, Methylene, or a linear or branched alkylene group from C ₂ to C ₁₀ , and a part of hydrogen atoms of R ₃ functional group is substituted or unsubstituted; R ₄ is hydrogen atom or methyl group; L is -OCO- , -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; and when a is plural, a plurality of R ₂ and L are each For the same or different. The liquid crystal alignment agent according to claim 5, wherein the amount of the ethylenically unsaturated compound (b2) is 0.1 mol based on the total amount of monomers in the second monomer mixture. To 0.5 Mor. The liquid crystal alignment agent according to claim 5, wherein the mixture to obtain the photoreactive group-containing polysiloxane (B-1) further includes a side chain compound (b3), and the side chain Compound (b3) contains a structure as shown in Formula (IV): E ¹ -L ⁰ -L ¹ -Z Formula (IV) In Formula (IV), E ¹ is an alkyl group of C ₁ to C ₃₀ , and C ₁ to C ₂₀ alkyl or alkoxy substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl, or C ₁₇ to C ₅₁ hydrocarbon group containing a steroid skeleton, part of the alkyl and alkoxy groups of E ^{1 are} hydrogen Atoms are substituted or unsubstituted; L ⁰ is a single bond, ^{* 1} -O-, ^{* 1} -COO- or ^{* 1} -OCO-, where ^{* 1} is the junction with E ¹ ; L ¹ is a single bond, C ₁ to C ₂₀ alkylene, phenylene, phenylene, cyclohexyl, dicyclohexyl or a group represented by the following formula (IV-1) or (IV-2): Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; ^{* 2} is a bond with Z; and Z is a monovalent organic group that reacts with an epoxy group to form a bonding group. The liquid crystal alignment agent according to claim 12, wherein the amount of the side chain compound (b3) used is 0.05 mol to 0.3 based on the total amount of monomers in the second monomer mixture. Mor. The liquid crystal alignment agent according to claim 1, wherein the polysiloxane (B) includes a polysiloxane (B-2) without a photoreactive group, and the polysiloxane (B-2) without a photoreactive group. The siloxane (B-2) is an epoxy-containing polysiloxane (b4), and the epoxy-containing polysiloxane (b4) includes a third monomer mixture Copolymer obtained by condensation. The liquid crystal alignment agent according to claim 14, wherein based on 100 parts by weight of the polymer (A), the used amount of the polysiloxane (B-2) without a photoreactive group is 3 weight Parts to 60 parts by weight. The liquid crystal alignment agent according to claim 14, wherein the epoxy group-containing polysiloxane (b4) includes a group represented by the formula (III-1) and a group represented by the formula (III-2) And at least one of the radicals represented by formula (III-3): Formula (III-1) In Formula (III-1), B represents an oxygen atom or a single bond; c represents an integer from 1 to 3; d represents an integer from 0 to 6; and when d represents 0, B is a single bond ; Formula (III-2) In Formula (III-2), e represents an integer of 0 to 6; Formula (III-3) In Formula (III-3), D represents an alkylene group having 2 to 6 carbon atoms; and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The liquid crystal alignment agent according to claim 14, wherein the third monomer mixture includes a silane monomer (b1-1) represented by formula (III-4): Si (R _f ) _p (OR _g ) _4-p in the formula (III-4) of formula (III-4), R _f is a hydrogen atom, C ₁ to C ₁₀ alkyl group of, C ₂ to C ₁₀ alkenyl group of, C ₆ to C ₁₅ aryl group of , An alkyl group containing an epoxy group or an alkoxy group containing an epoxy group, and at least one R _f is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when p is plural, each of R _f are the same or different; R _g is a hydrogen atom, C ₁ to C ₆ alkyl group of, C ₁ to C ₆ acyl or of C ₆ to C ₁₅ aryl group of; when 4-p is plural, R _g are each The same or different; and p is an integer from 1 to 3. A liquid crystal alignment film is formed by the liquid crystal alignment agent according to any one of claims 1 to 17. A liquid crystal display element includes the liquid crystal alignment film according to claim 18.