TW201814003A - Liquid crystal alignment agent and method of producing the same, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, comprising a polyer (A), polisiloxane (B) containing photo-reactive functional group and solvent (C). The present invention also provides a method of producing the liquid crystal alignment agent, comprising mixing the polyer (A), polisiloxane (B) containing photo-reactive functional group and solvent (C), in which the polyer (A) is obtained from reacting a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and the polisiloxane (B) containing photo-reactive functional group is obtained by reacting a polysiloxane (b1) including an epoxy group, an amino group compound (b2) and an unsaturated vinyl compound (b3). A liquid crystal alignment film and a liquid crystal display device formed by the liquid crystal alignment agent have a low liquid crystal contact angle.

Description

 Liquid crystal alignment agent and manufacturing method thereof, liquid crystal alignment film, and liquid crystal display element  

The present invention relates to a liquid crystal alignment agent, a method for producing the same, a liquid crystal alignment film, and a liquid crystal display device, and more particularly to a liquid crystal alignment agent having a low liquid crystal contact angle, a method for producing the same, and a liquid crystal alignment film formed of the liquid crystal alignment agent. And a liquid crystal display element comprising the above liquid crystal alignment film.

In general, as the liquid crystal display element, various driving methods have been developed depending on the electrode structure or the physical properties of the liquid crystal molecules used. For example, various currently known liquid crystal display elements such as TN type or STN type, VA type, and lateral electric field effect display technology type (IPS type). In the liquid crystal display element described above, a liquid crystal alignment film is disposed to align liquid crystal molecules. The material of the liquid crystal alignment film may be, for example, a known material such as polyimidic acid or polyamine, polyester, or polyorganosiloxane.

Further, in recent years, in order to control the alignment of liquid crystal molecules of liquid crystal display elements, a new technique such as Polymer Sustained Alignment (PSA) technology has been proposed, for example, Japanese Patent Publication No. JP 2003-149647. The polymer stabilizing alignment technique is to add a component having photopolymerization property to a liquid crystal layer of a liquid crystal cell, and to irradiate the liquid crystal cell with light while applying a voltage so that the liquid crystal molecules are inclined, thereby polymerizing the photopolymerizable component. This controls the alignment of the liquid crystal molecules.

However, in the case of controlling the alignment of the liquid crystal molecules by using the polymer stable alignment technique, it is necessary to use a relatively high amount of light irradiation, thereby causing defects such as decomposition of liquid crystal molecules, deterioration of properties of the liquid crystal alignment film, and the like, thereby causing uneven display of the liquid crystal display element. Sex, as well as panel durability. On the other hand, when the amount of the light irradiation is reduced, the liquid crystal molecules of the formed liquid crystal display element have a problem that the reaction speed with respect to the voltage change becomes slow. In view of the above problems, in order to obtain a liquid crystal display element which is capable of achieving a predetermined pretilt angle characteristic with a small amount of light irradiation amount and a liquid crystal molecule having a high reaction speed with respect to voltage, a liquid crystal display element for forming a coating film is proposed. The technology of the publication JP 2011-118358. The above prior publication discloses that a liquid crystal alignment film is formed on a substrate by using a liquid crystal alignment agent containing a polyorganosiloxane such as a (meth)acrylonitrile group and a photopolymerizable component of polyphosphoric acid or polyamidamine. . Next, the liquid crystal cell is formed on the substrate, and when a voltage is applied between the substrates, the liquid crystal cell is irradiated with light to obtain a liquid crystal display element.

However, the above method is still caused by the liquid crystal contact angle of the liquid crystal alignment agent being too high, so that the liquid crystal cannot be uniformly covered on the liquid crystal alignment film. Therefore, there is an urgent need to propose a liquid crystal alignment agent which can improve the disadvantage that the liquid crystal contact angle is too high.

One aspect of the present invention provides a liquid crystal alignment agent which may comprise a polymer (A), a photoreactive group-containing polyoxyalkylene (B), and a solvent (C).

Another aspect of the present invention provides a liquid crystal alignment film formed of the above liquid crystal alignment agent.

Still another aspect of the present invention is to provide a liquid crystal display element which can comprise a liquid crystal alignment film as described above.

Still another aspect of the present invention provides a method for producing a liquid crystal alignment agent comprising a mixed polymer (A), a photoreactive group-containing polyoxyalkylene (B), and a solvent (C), wherein the polymer ( A) is obtained by a reaction of a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and a photoreactive group-containing polyoxane (B) The epoxy group-containing polyoxyalkylene (b1), the amine compound (b2), and the ethylenically unsaturated compound (b3) are reacted.

Still another aspect of the present invention provides a liquid crystal alignment film which is formed using a liquid crystal alignment agent formed by the above-described method for producing a liquid crystal alignment agent.

Still another aspect of the present invention provides a liquid crystal display element comprising the above liquid crystal alignment film.

Liquid crystal alignment agent

First, the liquid crystal alignment agent of the present invention will be described. In one embodiment, the liquid crystal alignment agent may comprise a polymer (A), a photoreactive group-containing polyoxyalkylene (B), and a solvent (C), which are described below.

Polymer (A)

The polymer (A) is obtained by a reaction of a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

In detail, the polymer (A) includes poly-proline, polyimine, poly-proline-polyimide block copolymer or a combination of these polymers. Wherein the polyamidene block copolymer comprises a polyphthalic acid block copolymer, a polyamidiene block copolymer, a poly-proline-polyimine block copolymer or the above polymerization a combination of things. The polyaminic acid polymer, the polyamidimide polymer and the poly-proline-polyimine block copolymer may be a mixture of the tetracarboxylic dianhydride component (a1) and the diamine component (a2). The reaction was prepared.

Tetracarboxylic dianhydride component (a1)

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

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 of the above compounds.

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-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic 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 Cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or a combination of the above compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylate Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluorohetero Propyldiphthalic acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(three Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, double (triphenylphthalic acid)-4,4'- Phenyl methane dianhydride, ethylene glycol-bis (hydrogen trimellitate), propylene glycol-bis (hydrogen trimellitate), 1,4-butanediol-bis (hydrogen trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane- Bis(hydrogen trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-oxy-3-furanyl)-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-di-oxy-3-furanyl-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-six Hydrogen-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-cyanoyl)-naphtho[1,2-c]-furan-1,3-dione, 1, 3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphthalene And [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-two side Oxy-3-furanyl)-naphtho[ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxyl -3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5 -(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-di-oxyl An aromatic tetracarboxylic dianhydride compound such as tetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination of the above compounds.

The tetracarboxylic dianhydride compound represented by the formula (III-1) to the formula (III-6) is as follows.

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

In the formula (III-6), A ⁴ represents a divalent group containing an aromatic ring; and 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 (III-6) is preferably a compound represented by the formula (III-6-1).

The tetracarboxylic dianhydride compound (a1) can be used singly or in combination of two or more.

Specific examples of the tetracarboxylic dianhydride compound (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2, 3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexane Carboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4, 4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, a compound represented by the formula (III-1), or a combination of the above compounds.

The total mole number based on the diamine component (a2) is 100 moles, and the tetracarboxylic dianhydride component (a1) is preferably used in an amount ranging from 20 moles to 200 moles, more preferably 30 moles. 120 moles.

Diamine component (a2)

The diamine compound (a2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound represented by the formula (IV-1) to the formula (IV-30), 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-diaminodecane, 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-methyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)B Alkane, or a combination of the above compounds.

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, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.02,7]-edecene Alkylenediamine, 4,4'-methylenebis(cyclohexylamine), or a combination of the above compounds.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Bismuth, 4,4'-diaminobenzimidamide, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodi Phenyl ether, 3,3'-diaminochalcone, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethyl Hydroquinone, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene Diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4- (4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl) Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (4) -aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis ( 4-aminophenyl)anthracene, 2,7-diaminopurine, 9,9-bis(4-aminophenyl) , 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(meta-phenylene isophthalamide) Propyl)diphenylamine, 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-diamino 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 of the above compounds.

The diamine compound represented by the formula (IV-1) to the formula (IV-30) is shown below.

In the formula (IV-1), B ¹ represents ,or B ² represents a group having a guanidine (steroid) skeleton, a trifluoromethyl group, a fluorine atom, an alkyl group having 2 to 30 carbon atoms, or a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperazine. a monovalent group containing a cyclic structure of a nitrogen atom.

Specific examples of the compound represented by the formula (IV-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenylethylate B 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- Diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (IV-1-1) to formula At least one of the compounds represented by (IV-1-6), or a combination of the above compounds.

The compound represented by the formula (IV-1-1) to the formula (IV-1-6) is shown below.

Of formula (IV-2) in, B ¹ same formula B (IV-1) is ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, or a cyano group or Halogen atom.

Specific examples of the compound represented by the formula (IV-2) include at least one of the compounds represented by the formula (IV-2-1) to the formula (IV-2-13). Specifically, the compound represented by the formula (IV-2-1) to the formula (IV-2-13) is as follows.

In the formula (IV-2-10) to the formula (IV-2-13), s represents an integer of from 3 to 12.

In the formula (IV-3), B ⁶ each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a 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 (IV-3) include when p is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diaminotoluene, etc.; 2 hours: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 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; or when u is 3: 1 , 4-bis(4'-aminophenyl)benzene, and the like.

Specific examples of the compound represented by the formula (IV-3) preferably include p-diamine benzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Alkoxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene or a combination of the above compounds.

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

In the formula (IV-5), w represents an integer of 1 to 5. The compound represented by the formula (IV-5) is preferably 4,4'-diamino-diphenyl sulfide.

In the formula (IV-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, piperidine or piperidine. a divalent group of a cyclic structure containing a nitrogen atom such as a azine.

In the formula (IV-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ may be the same or different; X1 Each represents an integer from 1 to 3; X2 represents an integer from 1 to 20.

In the formula (IV-8), B ¹⁴ represents an oxygen atom or group extending cyclohexane; B ¹⁵ represents a methylene group _{(methylene, -CH 2 -);} B 16 represents a phenylene group or cyclohexane extension; B ¹⁷ Represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (IV-8) include a compound represented by the formula (IV-8-1), a compound represented by the formula (IV-8-2) or a combination of the above compounds.

Formula (IV-8-2)

The compounds represented by the formula (IV-9) to the formula (IV-30) are shown below.

In the formulae (IV-17) to (IV-25), B ¹⁸ preferably represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; and B ¹⁹ preferably represents a hydrogen atom. An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The diamine compound (a2) can be used singly or in combination of two or more.

Specific examples of the diamine compound (a2) include, but are not limited to, 1,2-diaminoethane, 3,3'-diaminochalcone, and 4,4'-diaminostilbene stilbene. , 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentyl) Alkylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethyl Phenyl phenyl) cyclohexane, ethyl 2,4-diaminophenylcarboxylate, 1-octadecyloxy-2,4-diaminobenzene, a compound represented by formula (IV-1-1) a compound represented by the formula (IV-1-2), a compound represented by the formula (IV-1-4), a compound represented by the formula (IV-1-5), represented by the formula (IV-2-1) a compound, a compound represented by the formula (IV-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, a compound represented by the formula (IV-8-1), and a formula ( IV-26) to a compound represented by the formula (IV-30), or a combination of the above compounds.

Method for preparing polymer (A)

The polymer (A) may include at least one of polyamic acid and polyimine. Further, the polymer (A) may further include a polyimide-based block copolymer. The preparation methods of the above various polymers are further explained below.

Method for preparing polylysine

The method for preparing polylysine is to first dissolve the first mixture in a solvent, wherein the first mixture comprises a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and is at 0 ° C to 100 ° C. The polycondensation reaction is carried out at a temperature. After reacting for 1 hour to 24 hours, the reaction solution is subjected to distillation under reduced pressure with an evaporator to obtain polylysine. Alternatively, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. Next, the precipitate is dried by drying under reduced pressure to obtain polylysine.

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 is a soluble reactant and a 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, An aprotic polar solvent such as N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphoric acid triamide; or (2) a phenolic solvent, For example, a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the total amount of the first mixture.

It is worth noting that in the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent, wherein the poor solvent does not cause precipitation of the polyamic acid. The poor solvent may be used singly or in combination of two or more, and includes, but is not limited to, (1) an alcohol such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, or 1,4-butane. An alcohol such as an alcohol or triethylene glycol; (2) a ketone such as a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or (3) an ester such as: An ester of 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 diethylene glycol An ether such as an ether; (5) a halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichloro a halogenated hydrocarbon such as benzene; or (6) a hydrocarbon such as a hydrocarbon such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. The amount of the poor solvent to be used is preferably from 0 part by weight to 60 parts by weight, and more preferably from 0 part by weight to 50 parts by weight, based on 100 parts by weight of the diamine component (a2).

Method for preparing polyimine

The method for preparing the polyimine is obtained by heating the polylysine prepared by the above method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During heating, the proline functional group in the polylysine can be converted to a quinone imine functional group (ie, hydrazide) via a dehydration ring closure reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (C) in the liquid crystal alignment agent, and therefore will not be further described herein. The amount of the solvent used in the dehydration ring-closure reaction is preferably from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the polylysine.

In order to obtain a preferred degree of ruthenium iodide, the operating temperature of the dehydration ring closure reaction is preferably from 40 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the reaction of ruthenium imidization is incomplete, and the degree of ruthenium iodide of poly-proline is lowered. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyimine 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 or trifluoroacetic anhydride. The dehydrating agent is used in an amount of from 0.01 mol to 20 mol based on 1 mol of the polyglycolic acid. The catalyst used in the dehydration ring closure reaction may be selected from (1) a pyridine compound such as a pyridine compound such as pyridine, trimethylpyridine or lutidine; and (2) a tertiary amine compound, for example: A tertiary amine compound such as triethylamine. The amount of the dehydrating agent used is 1 mole, and the catalyst can be used in an amount of 0.5 mole to 10 moles.

The ruthenium amination rate of the polymer (A) may be from 30% to 80%, preferably from 35% to 80%, and more preferably from 35% to 75%. When the ruthenium imidation ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the liquid crystal display element has a low liquid crystal contact angle.

Method for preparing polyamidene block copolymer

The polyamidene block copolymer is selected from the group consisting of polyphthalic acid block copolymers, polyamidiene block copolymers, polyamido acid-polyimine block copolymers or the above polymerizations. Any combination of objects.

The method for preparing the polyimine-based block copolymer is preferably first dissolving the starting material in a solvent and performing a polycondensation reaction, wherein the starting material comprises at least one poly-proline and/or at least one polyfluorene. The imine, and may further comprise a carboxylic anhydride component and a diamine component.

The carboxylic 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 the polyamic acid, and 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 will not be further described herein.

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

Preferably, the starting material comprises, but is not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two kinds of polyamidiamines having different terminal groups and different structures; a poly-proline and a polyamidiamine having different terminal groups and different structures; (4) a poly-proline, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride component and the diamine component At least one of the structure is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid; (5) a polyimine, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride group At least one of the diamine component and the carboxylic anhydride component used in forming the polyimine are different from the structure of the diamine component; (6) poly-proline, polyimine, and carboxylic anhydride components And a diamine component, wherein at least one of the carboxylic anhydride component and the diamine component is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid or the polyimine; 7) two structurally different polylysine, carboxylic anhydride component and diamine component; (8) two structurally different polyimine, carboxylic anhydride component and diamine component; (9) Two terminal groups are anhydride groups and structures a different polyamic acid and a diamine component; (10) two polyamines having a terminal group which is an amine group and having a different structure, and a carboxylic anhydride component; (11) the two terminal groups are an acid anhydride group and a structural phase a different polyimine and a diamine component; or (12) a polyimine and a carboxylic anhydride component in which the terminal groups are amine groups and have different structures.

The polyglycolic acid, the polyimine, and the polyimide-based block copolymer are preferably terminal-modified polymers which are molecularly adjusted first, within a range not affecting the efficacy of the present invention. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. The manner of preparing the terminal-modified polymer can be obtained by adding a monofunctional compound while carrying out a polycondensation reaction of poly-proline.

Specific examples of the monofunctional compound include, but are not limited to, (1) a monobasic acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, ortho-fourth a monobasic anhydride such as an alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) a monoamine compound such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, A monoamine compound such as n-octadecylamine or n-icosylamine; or (3) a monoisocyanate compound such as a monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate.

Photoreactive group-containing polyoxyalkylene (B)

The photoreactive polyoxyalkylene (B) is obtained by reacting a second mixture, wherein the second mixture may include an epoxy group-containing polyoxyalkylene (b1) and an amine compound (b2). The photoreactive polyoxyalkylene (B) comprises a structure as shown in the formula (I-1):

In the formula (I-1), E ¹ is an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an alkoxy group substituted or unsubstituted, and a cycloalkane having 3 to 10 carbon atoms. a base, or a hydrocarbon group having a carbon number of 17 to 51 containing a steroid skeleton, an alkyl group of E ¹ and at least a part of hydrogen atoms of the alkoxy group being substituted or unsubstituted; L ⁰ is a single bond, * ¹ -O- , * ¹ -COO- or * ¹ -OCO-, wherein * ¹ represents a bond with E ¹ ; the L ¹ is a single bond, an alkyl group having a carbon number of 1 to 20, a phenyl group, a phenyl group (biphenylene group), cyclohexylene group, bicyclohexylene or a group represented by the following formula (I-1-1) or formula (I-1-2):

Wherein * ² represents a group of the formula (I-1-1) or the formula (I-1-2) bonded to the nitrogen atom of the formula (I-1); when L ¹ is a single bond, L ⁰ It is a single button, and * ³ represents the bond.

In one embodiment, the second mixture further comprises an ethylenically unsaturated compound (b3). In the above embodiment, the photoreactive group-containing polyoxyalkylene (B) obtained by the reaction of the second mixture may comprise a structure as shown in the formula (I-2):

In the formula (I-2), R ₁ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a phenyl group, a cyclohexylene group, and a hydrogen atom of a part of the R ₁ functional group is substituted. Or unsubstituted; R ₂ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, and a part of the hydrogen atom of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond, sub a methyl group having a linear or branched alkylene group having 2 to 10 carbon atoms, a hydrogen atom of one of the R ₃ functional groups being substituted or unsubstituted; R ₄ being a hydrogen atom or a methyl group; and 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; R ₂ and L may each be the same or different; and, * ⁴ represents a bond Junction.

Specific examples and synthesis methods of the epoxy group-containing polyoxyalkylene oxide (b1), the amine compound (b2), and the ethylenically unsaturated compound (b3) will be described below.

Epoxy-containing polyoxyalkylene (b1)

The epoxy group contained in the epoxy group-containing polyoxyalkylene (b1) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group or a propylene oxide. Oxetanyl group.

The epoxy group-containing group contained in the epoxy group-containing polyoxyalkylene (b1) includes a group represented by the formula (II-1), a group represented by the formula (II-2), and a formula (II-). 3) At least one of the indicated bases.

Specifically, the group represented by the formula (II-1) is as follows.

In the formula (II-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond.

Further, the group represented by the formula (II-2) is as follows.

In the formula (II-2), e represents an integer of 0 to 6.

The group represented by the formula (II-3) is as follows.

In the formula (II-3), D represents an alkylene group having a carbon number of 2 to 6; 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 (II-1-1), a group represented by the formula (II-2-2), and a group represented by the formula (II-3-1). At least one of them.

Decane monomer (b1-1)

The epoxy group-containing polyoxyalkylene (b1) of the present invention comprises a copolymer obtained by subjecting a third mixture to hydrolysis and partial condensation, and the third mixture comprises a decane represented by the formula (II-4) Body (b1-1); Si(R ^a ) _p (OR ^b ) _4-p (II-4)

In the formula (II-4), R ^a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an epoxy group. Or an alkoxy group containing an epoxy group, at least one R ^a is an alkyl group having an epoxy group or an alkoxy group having an epoxy group; and R ^b each independently represents a hydrogen atom and has a carbon number of 1 to 6. An alkyl group, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; p represents an integer of 1 to 3; when p represents 2 or 3, a plurality of R ^a may be the same or different; When p represents 1 or 2, a plurality of R ^b may be the same or different.

In more detail, when R ^a in the formula (II-4) represents an alkyl group having ^a carbon number of 1 to 10, specifically, R ^a is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, or the like. N-butyl, tert-butyl, n-hexyl or n-decyl. Further, R ^a may also be an alkyl group having another substituent on the alkyl group, and specifically, R ^{a is,} for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-aminopropyl group, or a 3- Mercaptopropyl or 3-isocyanate propyl.

When R ^a in the formula (II-4) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R ^{a is,} for example, a vinyl group. Further, R ^a may be an alkenyl group having another substituent on the alkenyl group, and specifically, R ^{a is,} for example, 3-propenyloxypropyl group or 3-methylpropenyloxypropyl group.

When R ^a in the formula (II-4) represents an aryl group having ^a carbon number of 6 to 15, specifically, R ^a is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, R ^a may also be an aryl group having an aryl group having another substituent, and specifically, R ^a is, for example, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl (1) -(o-hydroxyphenyl)ethyl), 2-(o-hydroxyphenyl)ethyl or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl ( 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

Further, when R ^a in the formula (II-4) represents an epoxy group-containing alkyl group or an epoxy group-containing alkoxy group, ^a specific example of R ^a is the aforementioned epoxy group-containing polyfluorene oxide ( The epoxy group contained in b1) will not be described here.

Further, when R ^{b of the} formula (II-4) represents an alkyl group having a carbon number of 1 to 6, specifically, R ^b is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. When R ^b in the formula (II-4) represents a fluorenyl group having 1 to 6 carbon atoms, specifically, R ^{b is,} for example, an acetamidine group. When R ^b in the formula (II-4) represents an aryl group having 6 to 15 carbon atoms, specifically, R ^{b is,} for example, a phenyl group.

Specific examples of the decane monomer (b1-1) include 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N-glycidyl)amino group Propyltrimethoxydecane, 3-glycidyl ether propyl trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 3-glycidyl ether propyl methyl dimethoxy decane, 3-glycidyl ether propyl methyl diethoxy decane, 3-glycidyl ether propyl dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxy decane, 2- Glycidyl ether ethyl trimethoxy decane, 2-glycidyl ether ethyl triethoxy decane, 2-glycidyl ether ethyl methyl dimethoxy decane, 2-glycidyl ether ethyl Diethoxy decane, 2-glycidyl ether ethyl dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether butyl trimethoxy Decane, 4-glycidyl ether butyl triethoxy decane, 4-glycidyl ether butyl methyl dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4-glycidyl ether Butyl Methyl methoxy decane, 4-glycidyl ether butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-ring Oxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltriethoxy Decane, ((3-ethyl-3-epoxypropenyl)methoxy)propylmethyldimethoxydecane or ((3-ethyl-3-epoxypropenyl)methoxy)propane II Methyl methoxy decane, a commercial product such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC) or a combination of the above compounds.

Specific examples of the decane monomer (b1-1) represented by the formula (II-4) preferably include 3-glycidyl ether propyl trimethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, and 4 - glycidyl ether butyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltriethoxy Decane, DMS-E01, DMS-E12 or a combination of the above compounds.

The decane monomer (b1-1) is used in an amount of from 0.6 mol to 1 mol, preferably from 0.65 to 1 mol, based on the total amount of monomers in the third mixture of 1 mol. Good for 0.70 to 1 mol.

Other decane monomers (b1-2)

The third mixture for reacting to form the epoxy group-containing polyoxyalkylene (b1) preferably further comprises another decane monomer (b1-2) represented by the formula (II-5): Si (R ^c ) _q (OR ^d ) _4-q (II-5)

In the formula (II-5), R ^c each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms or an acid anhydride group. Alkyl; R ^d each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; q represents an integer of 0 to 3; When q represents 2 or 3, a plurality of R ^c may be the same or different; when q represents 0 to 2, a plurality of R ^d may be the same or different.

When R ^c in the formula (II-5) represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, specific examples thereof and preferably, for example, The foregoing R ^{a is} shown here, and will not be described again.

When R ^c in the formula (II-5) represents an alkyl group having an acid anhydride group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the acid group-containing alkyl group is, for example, ethyl succinic anhydride represented by the formula (II-5-1), propyl succinic anhydride represented by the formula (II-5-2) or a formula ( The propyl glutaric anhydride shown in II-5-3). It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of a dicarboxylic acid such as succinic acid or glutaric acid.

When R ^d in the formula (II-5) represents an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, specific examples thereof and preferably, for example, The foregoing R ^{b is} shown here, and details are not described herein again.

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

Specific examples of the decane compound having 4 hydrolyzable groups include tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane. , four second butoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having three hydrolyzable groups include methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltriisopropoxysilane, and Methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl "ethyltri-n-butoxysilane", n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxydecane (n -butyltrimethoxysilane), n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxydecane Decyltrimethoxysilane), vinyltrimethoxysilane, vinyltriethoxysilane, 3-propenyloxypropane 3-acryoyloxypropyltrimethoxysilane, 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylpropenyloxypropyltriethoxydecane (3) -methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyl) Phenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy- 5-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltri Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane (3-aminopropyltr) Imethoxysilane), 3-aminopropyltriethoxysilane, 3-mereaptopropyltrimethoxysilane, 3-(triphenyloxyindenyl)propyl succinic anhydride 3-triphenoxysilyl propyl succinic anhydride), commercially available from Shin-Etsu Chemical Co., Ltd.: 3-trimethoxysilyl propyl succinic anhydride (trade name X-12-967), Commercial product manufactured by WACKER: 3-(triethoxysilyl)propyl succinic anhydride (trade name: GF-20), 3-(trimethoxyfluorene) 3-(trimethoxysilyl)propyl glutaric anhydride (TMSG), 3-(triethoxysilyl)propyl glutaric anhydride, 3-(three) 3-(triphenoxysilyl) propyl glutaric anhydride or a combination of the above compounds.

Specific examples of the decane compound having two hydrolyzable groups include methyl dimethoxydecane, methyl diethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, and methyl group. [2-(Perfluoro-n-octyl)ethyl]dimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, diphenyldimethoxydecane, dimethyldiethoxydecane Di-n-butyldimethoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having one hydrolyzable group include methoxydimethyl decane, methoxy trimethyl decane, methoxymethyl diphenyl decane, tri-n-butyl ethoxy decane, or A combination of the above compounds.

The other decane monomer (b1-2) of the structure represented by the formula (II-5) is preferably tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, Phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxy A decyl alkane, dimethyl dimethoxy decane, dimethyl diethoxy decane, or a combination of the above compounds.

The decane monomer (b1-2) is used in an amount of from 0 moles to 0.7 moles, preferably from 0 to 0.6 moles, based on the total amount of monomers in the third mixture being 1 mole. Good for 0 to 0.5 moles.

The third mixture may further contain a commercially available decane 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 (manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400 , SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning); FZ3711, FZ3722 (manufactured by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS -S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42 DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by JNC); MS51, MS56 (manufactured by Mitsubishi Chemical Corporation); and GR100, GR650, GR908, GR950 ( A partial condensate such as Showa Electric Co., Ltd.).

Method for preparing epoxy group-containing polyoxane (b1)

The polycondensation reaction of the epoxy group-containing polyoxyalkylene compound can be carried out by a general method, for example, by adding an organic solvent, water or selectively further adding a catalyst to the above decane compound or a mixture thereof, followed by using an oil bath or the like. Heating is carried out at 50 ° C to 150 ° C, preferably for a period of from 0.5 hours to 120 hours. While heating, the mixture may be stirred or placed under reflux.

The above organic solvent is not particularly limited and may be the same as or different from the solvent (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-amyl ketone, diethyl ketone, cyclohexanone, and 2-butanone. a ketone solvent such as 2-hexanone; an ester of ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc. Solvent; ether solvent such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol 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 solvent; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, trimethylamine hexamethylphosphate, 1,3-dimethyl A guanamine solvent such as 2-imidazolidinone or a combination of the above organic solvents.

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

The organic solvent is preferably used in an amount of 10 parts by weight to 1200 parts by weight, more preferably 30 parts by weight to 1,000 parts by weight based on 100 parts by weight of all of the decane compound.

The water-based group is preferably used in an amount of from 0.5 mol to 2 mol based on 1 mol of the hydrolyzable group of all the decane compounds.

The catalyst is not particularly limited, and 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, piperididine, pyrrolidine, pyrrole, etc.; triethylamine, three Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc.; An amine or the like, or a combination of the above compounds.

The amount of the catalyst to be used varies depending on the reaction conditions such as the type and temperature, and can be appropriately set, for example, 1 mol based on all the decane compound, and the amount of the catalyst added is 0.01 mol to 5 m, preferably 0.03 moles to 3 moles, more preferably 0.05 moles to 1 mole.

From the viewpoint of stability, after completion of the polycondensation reaction, it is preferred to wash the organic solvent layer fractionated from the reaction liquid with water. In the case of performing the cleaning, it is preferred to use a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like. The cleaning can be carried out until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with an anhydrous agent such as anhydrous calcium sulfate or molecular sieves, and then the organic solvent is removed to obtain an epoxy group-containing. Polyoxane (b1).

When the photoreactive group-containing polyoxyalkylene (B) does not use an epoxy group-containing polyoxyalkylene (b1) or the polyoxyalkylene (b1) used does not contain an epoxy group, the liquid crystal alignment agent The liquid crystal contact angle is too high.

Amino compound (b2)

The amine-based compound (b2) of the present invention contains a structure represented by the formula (I-1'): E ¹ -L ⁰ -L ¹ -NH ₂ Formula (I-1')

In the formula (I-1'), E ¹ is an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an alkoxy group or an unsubstituted carbon ring having 3 to 10 carbon atoms. An alkyl group, or a hydrocarbon group having a carbon number of 17 to 51 containing a steroid skeleton, wherein at least a part of the hydrogen atoms of the alkyl group and the alkoxy group of E ¹ are substituted or unsubstituted; L ⁰ is a single bond, * ¹ -O -, * ¹ -COO- or * ¹ -OCO-, wherein * ¹ represents a bond with E ¹ ; L ¹ is a single bond, an alkyl group having a carbon number of 1 to 20, a phenyl group, a phenyl group a cyclohexyl group, a dicyclohexylene group or a group represented by the following formula (I-1-1) or formula (I-1-2):

Wherein * ² represents a group in which the group represented by the formula (I-1-1) or the formula (I-1-2) is bonded to a nitrogen atom; and when L ¹ is a single bond, L ⁰ is a single bond.

The linear or branched carbon group having a carbon number of 1 to 30, as defined by E ¹ in the above formula (I-1) and formula (I-1'), may be, for example, methyl or ethyl. Base, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl Base, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethyl Butyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethyl Butyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3 , 4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1 ,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl , 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-B Hexyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodecyl, n-tridedecyl, n-tetradecyl, n-pentadecayl, n-hexadecanyl, n- Hexyl group, n-octadecyl group, n-n-19 group, and the like.

Of (I-1) and formula ^(I-1 ') E 1 of the formula indicated number of carbon atoms a cycloalkyl group of 3 to 10, for example, may be a cyclopentyl, cyclohexyl, cycloheptyl, Cyclooctyl, cyclodecyl, cyclodecyl and the like. These cycloalkyl groups may be substituted with or without an alkyl group or alkoxy group having a carbon number of 1 to 20. Specific examples of the alkyl group having 1 to 20 carbon atoms can be referred to the specific examples of the above description of the alkyl group having 1 to 30 carbon atoms. Specific examples of the alkoxy group having 1 to 20 carbon atoms may be referred to the alkyl group of the specific example shown in the above description of the alkyl group having 1 to 30 carbon atoms, and a group bonded to an oxygen atom. The alkyl group and the alkoxy group described in E ¹ may have at least a part of a hydrogen atom substituted, and a group for substituting a hydrogen atom may, for example, be a nitrile group, a fluorine atom, a trifluoromethyl group or the like.

The hydrocarbon group having a carbon number of 17 to 51, which is represented by the above formula (I-1) and E ¹ in the formula (I-1'), may be, for example, the following formula (S-1) to (formula). S-3) of the group represented by wherein * ⁵ represents a group of the above formula (I-1) and formula (I-1 ') of the L-bonded at ^0.

Preferably, E ¹ may be selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a group of the above formula (S-1), and a group of the above formula (S-3). The group consists of one group. The number of carbon atoms in L ¹ of the formula (I-1) and formula (I-1 ') is an alkylene group having 1 to 20, for example, may be an alkyl group having the carbon number of 1 to 30 Each of the groups described is one in which one hydrogen atom is removed.

The compound represented by the above formula (I-1') is preferably a compound represented by the following formula (I-1'-1) to (I-1'-8).

C _u F _2u+1 -C _v H _2v -NH ₂ formula (I-1'-1)

C _w H _2w+1 -NH ₂ formula (I-1'-2)

In the above formula, 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, 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 from 0 to 2. However, s and t are not 0 at the same time.

The v of the above formula (I-1'-1) may preferably be an integer of from 1 to 18, more preferably an integer of from 1 to 12. The w of the above formula (I-1'-2) may preferably be an integer of from 5 to 20, more preferably from 10 to 18. The w of the above formula (I-1'-3) may preferably be an integer of from 1 to 17, more preferably an integer of from 3 to 12. The w of the above formula (I-1'-4) may preferably be an integer of from 1 to 15, more preferably an integer of from 1 to 8. The w of the above formula (I-1'-8) may preferably be an integer of from 1 to 15, more preferably an integer of from 1 to 8. The r of the above formula (I-1'-5) and the formula (I-1'-6) may preferably be an integer of 0 to 15, and more preferably an integer of 0 to 8. The q of the above formula (I-1'-6) may preferably be an integer of 1 to 12, more preferably an integer of 1 to 5. j of the above formula (I-1'-8) may preferably be an integer of 1 to 15, and more preferably an integer of 1 to 8.

Among the above compounds, the diamine compound (b2) is preferably the above formula (I-1'-2) to formula (I-1'-5), formula (I-1'-7) and formula (I-1). At least one of '-8'. Specifically, the following formula (I-1'-1') to formula (I-1'-8') are preferred.

C ₁₇ H ₃₅ -NH ₂ formula (I-1'-1')

The amine compound (b2) is used in an amount of from 0.05 moles to 0.30 moles, preferably from 0.10 moles to 0.30 moles, based on the third mixture being 1 mole, more preferably from 0.10 moles to 0.25 moles. .

If the photoreactive group-containing polyoxyalkylene (B) is not reacted with the amine compound (b2), the liquid crystal contact angle of the obtained liquid crystal alignment agent is too high.

In particular, the photoreactive group-containing polyoxyalkylene (B) of the present invention comprises a structure represented by the above formula (I-1), wherein the structure represented by the formula (I-1) and specific examples thereof may be Reference is made to the amine compound (b2) represented by the above formula (I-1'). The amine group of the amine compound (b2) can be bridged with the epoxy group of the epoxy group-containing polyoxyalkylene (b1).

Ethylene unsaturated compound (b3)

The ethylenically unsaturated compound (b3) of the present invention may comprise a structure of the following formula (I-2').

In the formula (I-2'), R ₁ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a phenyl group, a cyclohexylene group, and a hydrogen atom of one of the R ₁ functional groups is substituted or unsubstituted; R ₂ is an alkylene group, having a carbon number of 2 to 10 linear or branched alkylene group, part of hydrogen atoms of a functional group R ₂ is substituted or unsubstituted; R ₃ is a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, a hydrogen atom of one of the R ₃ functional groups being substituted or unsubstituted; R ₄ being a hydrogen atom or a 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 R ₂ and L may each be the same or different.

Specifically, examples of the compound of the above formula (I-2') may include acrylic acid, methacrylic acid, 2-propenyloxyethyl-2-hydroxyethylphthalic acid, 4-(2-methyl- Propylene oxime) benzoic acid, 2-propenyl oxiranyl ethyl hexyl hydrogen phthalate, 2-propenyl oxyethyl succinic acid, methacryloyloxyethyl succinic acid, 2-methyl propylene oxiranyl ethyl hexyl Hydrogen phthalic acid, monohydroxyethyl phthalate. More than one of the above examples can be selected for use. Commercial examples of the above-mentioned compounds may be 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 (manufactured by Toagosei Co., Ltd.).

Examples of the compound of the above formula (I-2') may also include a compound of the following formula (I-2'-1) to formula (I-2'-16).

In the formula (I-2'-10) to the formula (I-2'-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.

The ethylenically unsaturated compound (b3) is used in an amount of from 0.10 mol to 0.50 mol, preferably from 0.15 mol to 0.50 mol, based on the third mixture of 1 mol, and is from 0.15 mol to 0.45 m. Better.

If the photoreactive group-containing polyoxyalkylene (B) is not reacted with the ethylenically unsaturated compound (b3), the liquid crystal contact angle of the liquid crystal alignment agent is too high.

In particular, the photoreactive group-containing polyoxyalkylene (B) of the present invention comprises a structure represented by the above formula (I-2), wherein the structure represented by the formula (I-2) and specific examples thereof may be Reference is made to the ethylenically unsaturated compound (b3) represented by the above formula (I-2'). The carboxyl group or the alcohol group of the ethylenically unsaturated compound (b3) can be bridged with the epoxy group of the epoxy group-containing polyoxyalkylene oxide (b1).

Other compounds (b4)

The second mixture of the present invention may further comprise another compound (b4) to react with the epoxy group-containing polyoxyalkylene (b1), the amine compound (b2) and the ethylenically unsaturated compound (b3) to form a Photoreactive group polyoxyalkylene (B).

The other compound (b4) of the present invention contains a structure represented by the formula (V): E ¹ -L ⁰ -L ¹ -Z Formula (V)

In the formula (V), E ¹ is an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms, Or a hydrocarbon group having a carbon number of 17 to 51 containing a steroid skeleton, and a part of the alkyl group and the alkoxy group of E ¹ is a hydrogen atom which is substituted or unsubstituted; L ⁰ is a single bond, * ¹ -O-, * ¹ -COO- or * ¹ -OCO-, wherein * ¹ represents a bond with E ¹ ; L ¹ is a single bond, an alkyl group having a carbon number of 1 to 20, a phenyl group, a phenyl group, a stretched ring a hexyl group, a dicyclohexylene group or a group represented by the following formula (I-1-1) or formula (I-1-2):

Wherein * ² represents a bond with Z; and when L ¹ is a single bond, L ⁰ is a single bond, and Z is a monovalent organic group which reacts with an epoxy group to form a bond group.

The linear or branched alkyl group having a carbon number of 1 to 30, as described in E ^{1 in} the above formula (V), may be, for example, a methyl group, an ethyl group, an n-propyl group or an isopropyl group. , n-butyl, t-butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropane Base, 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-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- Base, n-fluorenyl, n-undecyl, n-dodecyl, n-tridedecyl, n-tetradecyl, n-pentadecayl, n-hexadecanyl, n-heptadecanyl, n - 18 base, n-n 19 base, etc.

The cycloalkyl group having a carbon number of 3 to 10 as described in E ^{1 of} the above formula (V) may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclic fluorene group. Base. These cycloalkyl groups may be substituted with or without an alkoxy group having a carbon number of 1 to 20. Specific examples of the alkoxy group having 1 to 20 carbon atoms can be referred to the specific examples of the above description of the alkyl group having 1 to 30 carbon atoms. Specific examples of the alkoxy group having 1 to 20 carbon atoms may be referred to the alkyl group of the specific example described in the above description of the alkyl group having 1 to 30 carbon atoms, and a group bonded to an oxygen atom. E ¹ of the alkyl group and alkoxylated, may have at least a portion of the hydrogen atoms are substituted, the substituent group for a hydrogen atom, a nitrile group may be for example, a fluorine atom, trifluoromethyl and the like.

The hydrocarbon group having a carbon number of 17 to 51 in the steroid skeleton, as described in E ^{1 in} the above formula (V), may be, for example, a group represented by the following formula (S-1) to (S-3). Wherein * ⁵ represents the bond between the above group and L ⁰ of the formula (V).

Preferably, E ¹ may be selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a group of the above formula (S-1), and a group of the above formula (S-3). The group consists of one group. Z is preferably a carboxyl group. The alkylene group having a carbon number of 1 to 20 as described for L ^{1 in} the above formula (V), for example, may be one by one for each of the groups having the above-mentioned alkyl group having 1 to 30 carbon atoms. a group derived from a hydrogen atom.

The compound represented by the above formula (V) is preferably a compound represented by the following formulas (V-1) to (V-8).

C _u F _2u+1 -C _v H _2v -COOH formula (V-1)

C _w H _2w+1 -COOH formula (V-2)

In the above formula, 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, 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 from 0 to 2. However, s and t are not 0 at the same time.

Preferably, v of the above formula (V-1) is an integer of 1 to 18, and more preferably an integer of 1 to 12. The w of the above formula (V-2) may preferably be an integer of 5 to 20, more preferably 10 to 18. The w of the above formula (V-3) may preferably be an integer of from 1 to 17, more preferably an integer of from 3 to 12. w of the above formula (V-4) may preferably be an integer of 1 to 15, and more preferably an integer of 1 to 8. w of the above formula (V-8) is preferably an integer of from 1 to 15, more preferably an integer of from 1 to 8. The r of the above formula (V-5) and formula (V-6) is preferably an integer of from 0 to 15, and more preferably an integer of from 0 to 8. The q of the above formula (V-6) may preferably be an integer of 1 to 12, and more preferably an integer of 1 to 5. j of the above formula (V-8) may preferably be an integer of 1 to 15, and more preferably an integer of 1 to 8.

Among the above compounds, at least one of the above formula (V-2) to formula (V-5), formula (V-7) and formula (V-8) is preferred. Specifically, the following formula (V-1') to formula (V-8') are preferred.

C ₁₇ H ₃₅ -COOH formula (V-1')

The other compound (b4) is used in an amount of from 0 moles to 0.30 moles, preferably from 0 moles to 0.25 moles, more preferably from 0 moles to 0.20 moles, based on the third mixture being 1 mole.

The photoreactive group-containing polyoxyalkylene (B) is used in an amount of 3 parts by weight to 30 parts by weight, preferably 5 parts by weight to 30 parts by weight, based on 100 parts by weight of the polymer (A). It is more preferably from 25 parts by weight.

Method for preparing polyoxyalkylene (B) containing photoreactive group

The photoreactive group-containing polyoxyalkylene (B) used in the present invention can be obtained by using the above epoxy group-containing polyoxyalkylene oxide (b1), an amine compound (b2) and an ethylenically unsaturated compound (b3). The reaction is synthesized in the presence of a catalyst.

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

The above organic salt may, for example, be a primary organic amine or a secondary organic amine such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butyl A tertiary organic amine such as an amine, a pyridine, a 4-dimethylaminopyridine or a diazabicycloundecene, and a quaternary organic amine such as tetramethylammonium hydroxide. Among these organic amines, preferred are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide. Grade organic amine.

Specific examples of the above hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 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, 1-(2-cyanoethyl-2-n-undecyl imidazolium benzene 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'-positive Monoalkylimidazolium)ethyl-S-triazine, 2,4-diamino-6-[2'-B Methyl-4'-methylimidazolyl-(1')]ethyl-S-triazine, a trimeric isocyanate adduct of 2-methylimidazole, a trimeric isocyanate of 2-phenylimidazole An imidazole compound such as a trimeric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-S-triazine; diphenyl An organic phosphorus compound such as phosphine, triphenylphosphine or triphenylphosphite; benzyl triphenyl phosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, Ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium- Tetra-n-butyl phosphonium-O (O-diethyl phosphorodithionate), tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium benzotriazolate a quaternary phosphonium salt of n-butyl fluorene tetrafluoroborate, tetra-n-butyl phosphonium tetraphenyl borate, tetraphenylphosphonium tetraphenyl borate, etc.; 1,8-diazabicyclo[5.4.0] Diazabicycloalkenyl such as monoene-7 or its organic acid salt; zinc octoate, tin octoate, acetamidine An organometallic compound such as an aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, or the like a boron compound such as boron trifluoride or triphenyl borate; a metal halogen compound such as zinc chloride or tin tetrachloride; a dicyandiamide or an amine and an epoxy resin. a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as a product; a microcapsule coated with a polymer on the surface of a hardening accelerator such as the above-mentioned imidazole compound, organophosphorus compound or quaternary phosphonium salt Type of latent hardening accelerator; amine salt type latent hardening accelerator; latent hardening accelerator such as Lewis acid salt, Bronsted acid salt, etc. Wait.

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

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

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

The synthesis reaction of the photoreactive group-containing polyoxyalkylene (B) can be carried out in the presence of an organic solvent as needed. 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 group-containing polysiloxane (b1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. the same. Specific examples of the above organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

Solvent (C)

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a polymer (A), a photoreactive group-containing polyoxyalkylene (B) and other optional components and does not react therewith. Preferably, it is preferably a solvent used in the synthesis of the polyamic acid, and a poor solvent used in the synthesis of the polyamic acid may be used in combination.

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 ethoxy propionate, 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-dimethylacetamide or the like. The solvent (C) may be used singly or in combination of two or more.

The solvent (C) is used in an amount of from 800 to 3000 parts by weight, preferably from 1,000 to 3,000 parts by weight, and more preferably from 1,000 to 2,500 parts by weight, based on 100 parts by weight of the polymer (A).

Additive (D)

The liquid crystal aligning agent may also optionally add the additive (D), wherein the additive (D) includes a compound having at least two epoxy groups, a decane compound having a functional group, within a range not affecting the efficacy of the present invention, Or a combination thereof.

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

The compound having at least two epoxy groups may be used singly or in combination of two or more.

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

Specific examples of the decane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Dimethoxydecane, 3-ureidopropyltrimethoxy silane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Baseline, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltriazine Triamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecyl- 3,6-dimercaptoacetate, 9-triethoxydecyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-double ( Ethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxysilane Silane, or combinations of the above compounds.

The decane compound having a functional group may be used singly or in combination of two or more.

The decane compound having a functional group may be used in an amount of from 0 to 10 parts by weight, and preferably from 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the polymer (A).

The additive (D) is preferably used in an amount of from 0.5 part by weight to 50 parts by weight, based on the total amount of the polymer (A) used, and more preferably from 1 part by weight to 45 parts by weight.

Method for producing liquid crystal alignment agent

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and it can be produced by a general mixing method. For example, the polymer (A) prepared in the above manner and the polyoxyalkylene (B) containing a photoreactive group are first uniformly mixed to form a mixture. Next, the solvent (C) is added under the conditions of a temperature of 0 ° C to 200 ° C, and the additive (D) is selectively added, and finally, stirring is continued until dissolved by a stirring device. Further, it is preferred to add the solvent (C) at a temperature of from 20 ° C to 60 ° C.

The liquid crystal alignment agent of the present invention has a viscosity of usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps at 25 °C.

Liquid crystal alignment film and method of manufacturing liquid crystal display element

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

The liquid crystal alignment film and the method for producing a liquid crystal display device of the present invention may include applying the liquid crystal alignment agent of the present invention to the conductive film of a pair of substrates having a conductive film, and then heating the substrate to form a coating film. a first step of arranging the pair of substrates on which the coating film is formed to form a liquid crystal cell; and, in the case of applying a voltage, irradiating the liquid crystal cell with the voltage of the pair of substrates having the conductive film 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 applied to the surface of the substrate on which the transparent conductive film is formed, preferably a lithographic plate can be used. The coating of the liquid crystal alignment agent is carried out by a printing method, a spin coating printing method, a roll coating method, or an inkjet method. The substrate referred to herein may be, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) ) Plastic transparent substrate. The transparent conductive film provided on the surface of the substrate may be formed of a NESA film (registered trademark of PPG Corporation, USA) formed of tin oxide (SnO ₂ ), and formed of indium oxide and tin oxide (In ₂ O ₃ -SnO ₂ ). ITO film. The patterned transparent conductive film may be formed by, for example, forming an unpatterned transparent conductive film, a photo-etching pattern forming method, and using a mask having a predetermined pattern when the transparent conductive film is formed. Achieved. When the liquid crystal alignment agent is applied, in order to provide good adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound or a functional titanium compound may be applied to the surface of the substrate on which the coating film is formed. Wait until it is processed.

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 prebaking temperature may be from 30 ° C to 200 ° C, preferably from 40 ° C to 150 ° C, more preferably from 40 ° C to 100 ° C. The pre-bake time may be from 0.25 minutes to 10 minutes, preferably from 0.5 minutes to 5 minutes. Thereafter, the solvent is completely removed, and a step of sintering (post-baking) is performed on the substrate in order to form a polymer which is necessary and a structure in which the structure of the proline is thermally imidized. The post-baking temperature may be from 80 ° C to 300 ° C, preferably from 120 ° C to 250 ° C. The post-baking time may be from 5 minutes to 200 minutes, preferably from 10 minutes to 100 minutes. Therefore, the film formed may have a thickness of from 0.001 μm to 1 μm, preferably from 0.005 μm to 0.5 μm.

The heating step after the application of the liquid crystal alignment agent removes 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 polylysine or a quinone imine polymer having a quinone imine structure and a proline structure. Thereafter, the formed coating film is further heated, and the polymer is subjected to a dehydration ring-closure reaction to form a ruthenium-imided 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.

[Second Step: Construction of Liquid Crystal Cell]

In this step, two substrates on which the liquid crystal alignment film is formed are provided, and liquid crystal is provided between the two substrates disposed opposite each other to form a liquid crystal cell. Here, in the case where the coating film is subjected to the rubbing treatment, the two substrates are arranged to face each other in accordance with the direction of the rubbing treatment, and are formed at a predetermined angle to each other, for example, vertically intersecting or anti-parallel.

The method of producing a liquid crystal cell can be exemplified by the following two methods.

The first method is a conventional method (vacuum injection method). First, two substrates are disposed opposite each other to form a gap (cell gap; Cell Gap) between the liquid crystal alignment films disposed opposite each other. The periphery of the two substrates is adhered by an adhesive, and the liquid crystal cells are filled by filling the liquid crystal into the cell gap which is separated by the surface of the substrate and the adhesive, and then sealing the injection holes to obtain liquid crystal cells.

The second method is called One Drop Filling (ODF). For example, an ultraviolet curable adhesive is applied to a predetermined portion of the substrate on one of the two substrates on which the liquid crystal alignment film is formed. Next, after a plurality of liquid crystals are dropped on a predetermined portion of the liquid crystal alignment film, the liquid crystal alignment film is placed opposite to the liquid crystal alignment film of the other substrate to bond the two substrates. The liquid crystal is spread over the entire surface of the substrate, and then the entire substrate is irradiated with ultraviolet light to harden the adhesive to manufacture a liquid crystal cell. Regardless of which of the above methods is employed, after the liquid crystal cell is formed, the substrate is heated to a temperature at which the liquid crystal used is converted to an isotropic property, and then 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 separator containing alumina balls can be used. The liquid crystal may be, for example, a nematic liquid crystal or a smectic liquid crystal, and a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring may be used. An alkane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in these liquid crystals, for example, cholesteric liquid crystals such as chlorinated cholesterol, cholesterol phthalate, and cholesterol carbonate may be added; and the products sold under the trade names "C-15" and "CB-15" (made by Merck) are sold. A strong dielectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate. The thickness of the liquid crystal molecule layer may be from 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 simultaneously irradiated with light. The voltage applied here may be, for example, a direct current or an alternating current of 5V to 50V. Further, the irradiated light may be, for example, ultraviolet light and visible light containing light having a wavelength of 150 nm to 800 nm, and ultraviolet light containing light having a wavelength of 300 nm to 400 nm is preferable. The light source for illuminating light may be, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like. In addition, the light source can be used in combination with a filter, a diffraction grating, etc. to obtain ultraviolet light of the above preferred wavelength range.

The irradiation amount of light may be from 1000 J/m ² or more to less than 100,000 J/m ² , preferably from 1000 J/m ² to 50,000 J/m ² . For example, it is known that when manufacturing a liquid crystal display element of a PSA mode, a light irradiation amount of 100,000 J/m ² is required, but the liquid crystal display element of the present invention can utilize an irradiation light amount of less than 100,000 J/m ² or even less than 50,000 J/m ² . A liquid crystal display element having a predetermined pretilt angle characteristic is produced, and the manufacturing cost of the liquid crystal display element is lowered. Further, deterioration of electrical properties due to strong light irradiation and deterioration of reactivity of liquid crystal molecules can be suppressed.

Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. The polarizing plate can be exemplified by a polarizing film called "H film" which is extended by polyvinyl alcohol and which absorbs iodine liquid, and a polarizing film which is sandwiched between the polarizing film and a protective film of cellulose acetate interposed therebetween. board.

The liquid crystal display element of the invention can be applied to various devices, such as a watch, a portable game machine, a word processor, a notebook computer, a navigation system, a camera, a PDA, a digital camera, a mobile phone, a smart phone, various screens. Various display devices such as LCD TVs and electronic billboards.

Hereinafter, a liquid crystal alignment agent, a liquid crystal alignment film, and a method for producing a liquid crystal display element of the present invention and their effects will be specifically described using a plurality of synthesis examples and examples.

Preparation of polymer (A) Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced. Then, in a four-necked flask, 4.86 g (0.045 mol) of p-diamine benzene (abbreviated as a2-1) and 2.6 g (0.005 mol) were added as shown in formula (IV-1-2). The compound (abbreviated as a2-4) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were stirred at room temperature until dissolved. Next, 11.2 g (0.05 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (abbreviated as a1-1) and 20 g of NMP were added, and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-1-1).

Synthesis Example A-1-2 to Synthesis Example A-1-3

Synthesis Example A-1-2 to Synthesis Example A-1-3 The polymer (A-1-2) to the polymer (A-1-3) were separately prepared in the same manner as in Synthesis Example A-1-1. And the difference is: change the type of monomer and its use (as shown in Table 1).

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced. Then, in a four-necked flask, 5.41 g (0.05 mol) of p-diaminobenzene (abbreviated as a2-1) and 80 g of N-methyl-2-pyrrolidone (N-methyl-2-) were added. Pyrrolidone, abbreviated as NMP), and stirred until dissolved at room temperature. Next, 11.2 g (0.05 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (abbreviated as a1-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride and 19.75 g of pyridine were added, the temperature was raised to 60 ° C, and stirring was continued for 2 hours to carry out the oxime imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-2-1).

Synthesis Example A-2-2 to Synthesis Example A-2-10

Synthesis Example A-2-2 to Synthesis Example A-2-10 The same procedure as in Synthesis Example A-2-1 was carried out to prepare a polymer (A-2-2) to a polymer (A-2-10), respectively. And the difference is: change the type of monomer and its use (as shown in Table 1).

Preparation of photocatalytic group-containing polyoxyalkylene (B) Synthesis Example B-1

A stirrer, a condenser, and a thermometer were placed on a three-necked flask having a volume of 500 ml. Then, in a three-necked flask, 0.60 mol of 2-glycidylethyltrimethoxydecane (hereinafter referred to as GETMS), 0.4 mol of methyltrimethoxydecane (hereinafter referred to as MTMS), and 600 g were added. Propylene glycol monomethyl ether (hereinafter abbreviated as PGME), and an aqueous solution of triethylamine (hereinafter abbreviated as TEA) (20 g of TEA/200 g of H ₂ O) was added thereto over 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 in 30 minutes. When the internal temperature of the solution reached 75 ° C, heating and stirring were continued for polycondensation for 6 hours. . After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate to obtain a solution of the epoxy group-containing polyoxymethane compound.

Next, 0.05 mol of the amine compound (b2-1) and 0.5 mol of the ethylenically unsaturated compound (b3-1) were added to a solution of the epoxy group-containing polyoxosiloxane 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 in 30 minutes, and when the internal temperature of the solution reached 100 ° C, heating and stirring were continued for 24 hours. After completion of the reaction, the organic layer was taken out and washed with water, and dried with magnesium sulfate to remove the solvent, whereby a polyoxyalkylene (B-1) containing a photoreactive group was obtained.

Synthesis Example B-2 to Synthesis Example B-8

The photoreactive group-containing polyoxyalkylene (B-2) of Synthesis Example B-2 to Synthesis Example B-8 to the photoreactive group-containing polyoxyalkylene (B-8) was synthesized in the same manner as in Synthesis Example B- 1 is prepared in the same manner, and is different in that the kind of the reactant of the polyoxyalkylene (B) containing the photoreactive group and the amount thereof, the kind of the catalyst and the solvent, the amount thereof, and the reaction temperature are changed. And polycondensation time (as shown in Table 2).

Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-4

The polysiloxane (B'-1) to polyoxyalkylene (B'-1) of Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-1 was prepared in the same manner as in Synthesis Example B-1. And the difference is that the type of the reactant of the polyoxyalkylene (B) and the amount thereof, the kind of the catalyst and the solvent, the amount thereof, the reaction temperature, and the polycondensation time (as shown in Table 2) are changed.

Preparation of liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Example 1

a. Liquid crystal alignment agent

100 parts by weight of the polymer (A-1-1), 3 parts by weight of the photoreactive group-containing polyoxyalkylene (B-1), and 1200 parts by weight of N-methyl-2-pyrrolidone (abbreviation) It is C-1) and 300 parts by weight of ethylene glycol n-butyl ether (abbreviated as C-2), and the liquid crystal alignment agent of Example 1 is formed by continuously stirring to dissolve at room temperature with a stirring device.

b. Liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent was applied by spin coating to a glass substrate having a conductive film made of ITO, and then pre-baked on a hot plate at a temperature of 70 ° C for 3 minutes, and in a circulating oven at a temperature. After baking at 220 ° C for 20 minutes, a coating film can be obtained.

Using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet rays containing a bright line of 313 nm for 50 seconds from a direction inclined by 40° from the normal line of the substrate, thereby imparting liquid crystal. The alignment energy can be used to form a liquid crystal alignment film. At this time, the illuminance of the illuminated surface at a wavelength of 313 nm was 2 mW/cm ² . The same operation was repeated to produce two (one pair) substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm is applied to the outer periphery of the surface on which the liquid crystal alignment film is formed on the pair of substrates by screen printing, and the liquid crystals of the respective substrates are provided. The alignment film surface was opposed to each other, and the substrate was bonded to the substrate in such a manner that the irradiation direction of the polarized ultraviolet light was reversed, and the pressure was applied to the substrate at a pressure of 10 kg by a hot press.

Thereafter, the liquid crystal is injected from the liquid crystal injection port, and the liquid crystal injection port is sealed with an epoxy resin-based adhesive. In order to eliminate the flow alignment during liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Finally, the polarizing plate was bonded to the outer surfaces of the substrate so that the polarizing directions thereof were perpendicular to each other and the polarization direction of the ultraviolet rays of the liquid crystal alignment film was 45°, whereby the liquid crystal display element of Example 1 was obtained. The liquid crystal display elements of Example 1 were evaluated for each evaluation method described later, and the results are shown in Table 3.

Embodiment 2 to Embodiment 15

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Example 2 to Example 15 were separately prepared in the same manner as in Example 1, and the difference was that the kind of the component and the amount thereof were changed, as shown in Table 3. Show. The evaluation methods of the liquid crystal display elements obtained in Examples 2 to 15 described later were evaluated, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 5

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Comparative Example 1 to Comparative Example 5 were separately prepared in the same manner as in Example 1, except that the type of the component and the amount thereof were changed, as shown in Table 4. . The evaluation methods described later in the liquid crystal display elements obtained in Comparative Examples 1 to 5 were evaluated, and the results are shown in Table 4.

Evaluation method 1. Amidization rate

The ruthenium amination rate means the ratio of the number of ruthenium rings calculated as a percentage based on the total number of guanamine functional groups and the number of quinone rings in the polymer, expressed as a percentage.

The detection method is that the polymer of the synthesis example is dried under reduced pressure, and then dissolved in a suitable deuteration solvent, for example, deuterated dimethyl hydrazine, using tetramethyl decane as a reference material, The result of 1H-Nuclear magnetic resonance (1H-NMR) was measured at room temperature (for example, 25 ° C), and the yield (%) of ruthenium was obtained by the formula (1).

△1: the peak area of the chemical shift of the NH matrix near 10 ppm; Δ2: the peak area of other protons; α: the NH of the precursor of the polymer (polyproline) The ratio of the number of protons of a radical to the number of other protons.

2. Liquid crystal contact angle

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

○: 13°>liquid crystal contact angle ≧15°

×: The liquid crystal contact angle was >15°.

According to Table 3, the photoreactive group-containing polyoxyalkylene (B) in the liquid crystal alignment agent is composed of an epoxy group-containing polyoxyalkylene (b1), an amine compound (b2), and ethylenic unsaturation. The compound (b3) is obtained by reacting, and the obtained liquid crystal display element can have a low liquid crystal contact angle. Further, when the imidization ratio of the polymer (A) in the liquid crystal alignment agent is from 30% to 80%, the liquid crystal contact angle of the obtained liquid crystal display element can be further lowered.

On the other hand, according to Table 4, if the reaction of the polyoxyalkylene (B) in the liquid crystal alignment agent is not carried out, the epoxy group-containing polyoxyalkylene (b1), the amine compound (b2) or the ethyl group is not used. In the unsaturated compound (b3), the contact angle of the obtained liquid crystal display element is too high.

Therefore, by applying the liquid crystal alignment agent of the present invention, the method for producing the same, the liquid crystal alignment film, and the liquid crystal display element, a low liquid crystal contact angle can be achieved, and the liquid crystal can be uniformly covered on the liquid crystal alignment film.

While the invention has been described above in terms of several embodiments, it is not intended to limit the scope of the invention, and the invention may be practiced in various embodiments without departing from the spirit and scope of the invention. The scope of protection of the present invention is defined by the scope of the appended claims.

Claims (15)

A liquid crystal alignment agent comprising: a polymer (A) selected from the group consisting of a polyamic acid polymer, a polyamidene polymer, a polyamidene block copolymer, or any combination of the above; The photoreactive group polyoxyalkylene (B) comprises a structure as shown in the formula (I-1): In the formula (I-1), the E ¹ is an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an alkoxy group or an unsubstituted carbon number of 3 to 10. a cycloalkyl group or a hydrocarbon group having a carbon number of 17 to 51 containing a steroid skeleton, wherein the alkyl group of the E ¹ and at least a part of hydrogen atoms of the alkoxy group are substituted or unsubstituted; the L ⁰ is a single bond, * ¹ -O-, * ¹ -COO- or * ¹ -OCO-, wherein * ¹ represents a bond to the E ¹ ; the L ¹ is a single bond, an alkyl group having a carbon number of 1 to 20, a phenyl group, a biphenyl group, a cyclohexylene group, a dicyclohexylene group or a group represented by the following formula (I-1-1) or formula (I-1-2): Wherein * ² represents a bond of the group represented by the formula (I-1-1) or the formula (I-1-2) with the nitrogen atom of the formula (I-1); when the L ¹ is In the case of a single bond, the L ⁰ is a single bond, and the * ³ represents a bond; and the solvent (C). The liquid crystal alignment agent according to claim 1, wherein the photoreactive group-containing polyoxyalkylene (B) comprises a structure represented by the formula (I-2): In the formula (I-2), the R ₁ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a phenyl group, a cyclohexylene group, and a part of hydrogen of the R ₁ functional group. The atom is substituted or unsubstituted; the R ₂ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, and a part of the hydrogen atom of the R ₂ functional group is substituted or unsubstituted; ₃ is a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, and a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; the R ₄ is a hydrogen atom or a methyl group. The L is -OCO-, -O- or -S-; the a is an integer from 0 to 10; the b is an integer from 0 to 1; when the b is 0, the a is not 0; the R ₂ And the L may each be the same or different; and, the * ⁴ represents a bond.  The liquid crystal alignment agent according to the above aspect of the invention, wherein the polymer (A) has a ruthenium azide ratio of 30% to 80%.    A liquid crystal alignment film formed by using a liquid crystal alignment agent as described in claims 1 to 3.    A liquid crystal display element comprising the liquid crystal alignment film according to item 4 of the patent application.   A method for producing a liquid crystal alignment agent which comprises mixing a polymer (A) comprising a first mixture reaction comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2) The polymer (A) is selected from the group consisting of a poly-proline polymer, a polyimine polymer, a polyamidene block copolymer or a combination of the above; a photoreactive group-containing a polyoxyalkylene (B) obtained by reacting a second mixture, wherein the second mixture comprises an epoxy group-containing polyoxyalkylene (b1) and an amine compound (b2), and the amine compound ( B2) comprises a structure of the formula (I-1'): E ¹ -L ⁰ -L ¹ -NH ₂ Formula (I-1') In the formula (I-1'), the E ¹ is a carbon number of 1 An alkyl group of 30, a cycloalkyl group having 3 to 10 carbon atoms substituted or unsubstituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or a carbon number of 17 to 51 containing a steroid skeleton a hydrocarbon group, the alkyl group of the E ¹ and a part of the hydrogen atom of the alkoxy group being substituted or unsubstituted; the L ⁰ being a single bond, * ¹ -O-, * ¹ -COO- or * ¹ -OCO- wherein the * ^represents the bond at E ^1; which L ¹ is a single bond, an alkylene group having a carbon number of 1 to 20, extending Group, biphenyl stretch, cyclohexylene, cyclohexylene or two of the formula (I-1-1) or formula (I-1-2) shown in the group: Wherein * ² represents a bond of the group represented by the formula (I-1-1) or the formula (I-1-2) to a nitrogen atom; and when the L ¹ is a single bond, the L ⁰ is Single bond; and solvent (C). The method for producing a liquid crystal alignment agent according to the sixth aspect of the invention, wherein the second mixture further comprises an ethylenically unsaturated compound (b3), and the ethylenically unsaturated compound (b3) comprises the formula (I-2) ') structure: In the formula (I-2'), the R ₁ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a phenyl group, a cyclohexylene group, and a part of the R ₁ functional group. a hydrogen atom is substituted or unsubstituted; the R ₂ is a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, and a part of the hydrogen atom of the R ₁ functional group is substituted or unsubstituted; R ₃ is a single bond, a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, and a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; the R ₄ is a hydrogen atom or a L is -OCO-, -O- or -S-; the a is an integer from 0 to 10; the b is an integer from 0 to 1; when the b is 0, the a is not 0; the R ₂ And the L may be the same or different. The method for producing a liquid crystal alignment agent according to the above-mentioned item 6, wherein the epoxy group-containing polyoxyalkylene (b1) comprises a group represented by the formula (II-1). At least one of the group represented by II-2) and the group represented by the formula (II-3): In the formula (II-1), the B represents an oxygen atom or a single bond; the c represents an integer of 1 to 3; and, d represents an integer of 0 to 6, wherein when d represents 0, the B is single bond; In the formula (II-2), the e represents an integer of 0 to 6; In the formula (II-3), the D represents an alkylene group having a carbon number of 2 to 6; and the E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The method for producing a liquid crystal alignment agent according to the sixth or seventh aspect of the invention, wherein the epoxy group-containing polyoxane (b1) comprises hydrolyzing and partially condensing a third mixture. a copolymer obtained, the third mixture comprising a decane monomer (b1-1) as shown in formula (II-4): Si(R _a ) _w (OR _b ) _4-w (II-4) In the formula (II-4), R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group having an epoxy group or An alkoxy group containing an epoxy group, and at least one such R _a is an alkyl group having an epoxy group or an alkoxy group having an epoxy group; when the R _a is a plural number, each of the R _{a is the} same or different; _b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; when the R _b is a plural number, each of the R _{b is the} same or different; Represents an integer from 1 to 3.  The method for producing a liquid crystal alignment agent according to claim 9, wherein the total amount of the monomers in the third mixture is 1 mol, and the amount of the decane monomer (b1-1) is 0.6 mol. Ears to 1 mole.    The method for producing a liquid crystal alignment agent according to claim 9, wherein the total amount of the monomers in the third mixture is 1 mol, and the amine compound (b2) is used in an amount of 0.05 mol. 0.30 mol; the ethylenically unsaturated compound (b3) is used in an amount of from 0.10 mol to 0.50 mol.    The method for producing a liquid crystal alignment agent according to the above-mentioned item 6, wherein the use of the photoreactive group-containing polyoxane (B) is based on 100 parts by weight of the polymer (A). The amount is from 3 parts by weight to 30 parts by weight, and the solvent (C) is used in an amount of from 800 parts by weight to 3,000 parts by weight.    The method for producing a liquid crystal alignment agent according to the above aspect, wherein the polymer (A) has a ruthenium iodide ratio of 30% to 80%.    A liquid crystal alignment film comprising a liquid crystal alignment agent formed by a liquid crystal alignment agent, wherein the liquid crystal alignment agent is formed by the method for producing a liquid crystal alignment agent according to any one of claims 6 to 13.    A liquid crystal display element comprising the liquid crystal alignment film of claim 14.