WO2022014345A1 - 液晶配向剤、液晶配向膜及び液晶表示素子 - Google Patents

液晶配向剤、液晶配向膜及び液晶表示素子 Download PDF

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Publication number
WO2022014345A1
WO2022014345A1 PCT/JP2021/024966 JP2021024966W WO2022014345A1 WO 2022014345 A1 WO2022014345 A1 WO 2022014345A1 JP 2021024966 W JP2021024966 W JP 2021024966W WO 2022014345 A1 WO2022014345 A1 WO 2022014345A1
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group
liquid crystal
carbon atoms
crystal alignment
diamine
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PCT/JP2021/024966
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English (en)
French (fr)
Japanese (ja)
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美希 豊田
佳和 原田
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日産化学株式会社
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Priority to CN202180062698.8A priority Critical patent/CN116615689B/zh
Priority to JP2022536246A priority patent/JP7315106B2/ja
Priority to KR1020237003948A priority patent/KR20230038504A/ko
Publication of WO2022014345A1 publication Critical patent/WO2022014345A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
  • liquid crystal display element As a liquid crystal display element, various drive methods having different electrode structures and physical properties of liquid crystal molecules used have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical).
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • VA Very
  • Element Element
  • IPS In-Plane Switching
  • FFS Frringe Field Switching
  • the VA type liquid crystal display element has a wide viewing angle, a fast response speed, a large contrast, and can eliminate the need for rubbing processing in the production process. Widely used mainly for monitors.
  • a photopolymerizable compound is added to the liquid crystal composition in advance, and the liquid crystal cell is irradiated with ultraviolet rays while applying a voltage to increase the response speed of the liquid crystal.
  • Method see, for example, Patent Document 1 and Non-Patent Document 1 is the mainstream.
  • the liquid crystal display element generally has a liquid crystal alignment film for orienting liquid crystal molecules.
  • a material for the liquid crystal alignment film for example, polyamic acid, polyamic acid ester, polyimide, polyamide and the like are known.
  • the liquid crystal alignment film is required to have various properties in addition to the liquid crystal alignment. For example, in the PSA type liquid crystal display element, when static electricity is accumulated in the liquid crystal cell, or when electric charge is accumulated in the liquid crystal cell by applying a positive / negative asymmetric voltage generated by driving, these accumulated charges are accumulated.
  • Patent Document 2 proposes a polyimide-based liquid crystal alignment film having a pyrrole structure.
  • Patent Document 3 proposes a polyimide-based liquid crystal alignment film having a diphenylamine structure.
  • an object of the present invention is a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having a high voltage retention rate and a high light transmittance, quick relaxation of accumulated charges, and excellent afterimage characteristics.
  • the present invention is to provide the liquid crystal alignment film and a liquid crystal display element using the same.
  • the present invention is at least one selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine (1) represented by the following formula (1) and a polyimide which is an imidized product of the polyimide precursor. It is in a liquid crystal alignment agent characterized by containing a polymer (P), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
  • R represents a monovalent organic group
  • R 1 and R 2 represent a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 6 carbon atoms. A part of the hydrogen atom of the hydrocarbon group in R 1 and R 2 may be substituted.
  • the liquid crystal alignment agent of the present invention it is possible to obtain a liquid crystal alignment film having a high voltage retention and a high light transmittance, quick relaxation of accumulated charges, and excellent afterimage characteristics.
  • the mechanism by which the above effects of the present invention are obtained is not always clear, but it is considered that the following is one of the causes. That is, the diamine, which is the raw material of the polymer component used in the liquid crystal alignment agent of the present invention, is high because the presence of a substituent at the ortho position of the amino group causes steric hindrance and suppresses the formation of charge transfer.
  • a liquid crystal alignment film having a light transmittance can be obtained, and since the polymer obtained from the above diamine has a conjugated structure, the accumulated charge can be quickly relaxed and a liquid crystal alignment film having excellent afterimage characteristics can be obtained. it is conceivable that.
  • the liquid crystal alignment agent of the present invention is selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine (1) represented by the following formula (1) and a polyimide which is an imidized product of the polyimide precursor. It contains at least one polymer (P).
  • R, R 1 and R 2 are as defined above, respectively.
  • the monovalent organic group in R includes a monovalent organic group having an aromatic ring structure, a monovalent chain hydrocarbon group having 1 to 30 carbon atoms, or a monovalent alicyclic hydrocarbon having 3 to 30 carbon atoms. Hydrocarbon groups are preferred. A part of the hydrogen atom of the chain hydrocarbon group or the alicyclic hydrocarbon group may be substituted, and a part of the methylene group thereof is substituted with an oxygen atom, a carbonyl group or -COO-. May be.
  • Examples of the monovalent chain hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an alkynyl group having 2 to 30 carbon atoms.
  • R is a chain hydrocarbon group or an alicyclic hydrocarbon group
  • the substituent may be a halogen atom (fluorine atom, Chlorine atom, bromine atom, iodine atom), hydroxyl group, cyano group, alkyl group having 1 to 9 carbon atoms, alkoxy group having 1 to 9 carbon atoms, fluoroalkyl group having 1 to 9 carbon atoms and the like can be mentioned.
  • halogen atom fluorine atom, Chlorine atom, bromine atom, iodine atom
  • hydroxyl group cyano group
  • alkyl group having 1 to 9 carbon atoms alkoxy group having 1 to 9 carbon atoms
  • fluoroalkyl group having 1 to 9 carbon atoms and the like can be mentioned.
  • an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6
  • the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms may be composed of only an alicyclic structure, or may contain a chain structure as a part thereof.
  • Examples of the alicyclic structure include cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, and adamantane.
  • the monovalent organic group having the aromatic ring structure may be composed of only the aromatic ring structure, or may contain at least one of the chain structure and the alicyclic structure as a part thereof.
  • the aromatic ring structure may be a benzene ring, a condensed benzene ring such as a naphthalene ring or an anthracene ring, and a complex such as a thiophene ring, a pyrrole ring, a furan ring, a pyridine ring, a pyrimidine ring, and a triazine ring. It may be an aromatic ring.
  • the monovalent group having the aromatic ring structure may have only one aromatic ring structure or may have a plurality of aromatic ring structures.
  • the plurality of aromatic ring structures may be bonded by a single bond, and in this case, specific examples thereof include biphenyl and terphenyl.
  • a chain structure or an alicyclic structure may exist so as to connect a plurality of aromatic ring structures. At least one of these aromatic ring structures, chain structures and alicyclic structures may have a substituent.
  • the substituents include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a cyano group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and 1 to 9 carbon atoms. Fluoroalkyl groups and the like can be mentioned.
  • a preferred example of the monovalent organic group having the aromatic ring structure in R is a structure represented by the following formula (Ar).
  • Ra is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, cyano group, alkyl group having 1 to 9 carbon atoms, alkoxy group having 1 to 9 carbon atoms, or 1 to 9 carbon atoms.
  • the .m representing the fluoroalkyl group is an integer from 0 to 5, when m is 2 to 5, with.
  • * is the definition plurality of R a independently represents a bond.
  • Saturated or unsaturated monovalent hydrocarbon groups having 1 to 6 carbon atoms in R 1 and R 2 include alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, and 2 to 6 carbon atoms. Examples include an alkynyl group. Examples of the alicyclic hydrocarbon group having 3 to 6 carbon atoms in R 1 and R 2 include a cyclopentyl group and a cyclohexyl group. A part of the hydrogen atom of the hydrocarbon group in R 1 and R 2 may be substituted, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a hydroxyl group.
  • R, R 1 and R 2 are preferably alkyl groups having 1 to 5 carbon atoms independently of each other.
  • Specific examples of the alkyl groups having 1 to 5 carbon atoms in R, R 1 and R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert.
  • -Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group can be mentioned.
  • an alkyl group having 1 to 3 carbon atoms is preferable.
  • Preferred specific examples of the diamine (1) represented by the above formula (1) include the following formulas (d-1) to (d-4).
  • the polymer (P) contained in the liquid crystal aligning agent of the present invention is particularly applicable to the liquid crystal aligning agent for the liquid crystal display element of the TN method, STN method, VA method, PSA method, and SC-PVA mode.
  • a diamine component containing a diamine (s) having at least one structure selected from the group consisting of the following formulas (S1), (S2) and (S3) is used. It is preferable that the polymer is at least one selected from the group consisting of the polyimide precursor thus obtained and the polyimide which is an imidized product of the polyimide precursor.
  • X 1 and X 2 are independently single-bonded,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON. (CH 3 )-, -N (CH 3 ) CO-, -NH-, -O-, -COO-, -OCO-, or-((CH 2 ) a1- A 1 ) m1- (a1 is 1-) It is an integer of 15, A 1 represents an oxygen atom or -COO-, m 1 is 1 to 2, and a plurality of a 1 and A 1 when m 1 is 2 may be the same or different. It may be.).
  • G 1 and G 2 each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms.
  • the arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. And may be substituted with at least one selected from the group consisting of fluorine atoms.
  • m and n are independently integers of 0 to 3, and the sum of m and n is 1 to 4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy alkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 1 is substituted with a fluorine atom. May be.
  • Examples of the divalent cyclic group in G 1 and G 2 include a cyclohexylene group and a phenylene group. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom.
  • m and n are independently integers of 0 to 3, and the total of m and n is 1 to 4. From the viewpoint of enhancing the liquid crystal orientation, the total of m and n is more preferably 2 to 4.
  • X 3 is a single bond, -CONH-, -NHCO-, -CON (CH 3 )-, -N (CH 3 ) CO-, -NH-, -O-, -CH 2 O. -, -COO- or -OCO-.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxy alkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 2 may be substituted with a fluorine atom. Further, R 2 is preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms from the viewpoint of enhancing the liquid crystal orientation.
  • X 4 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -OCH 2-, -COO- or -OCO-.
  • R 3 represents a structure having a steroid skeleton. Further, R 3 preferably has a structure containing a cholestanyl group, a cholesteryl group or a lanostannyl group.
  • Preferred specific examples of the formula (S1) include the following formulas (S1-x1) to (S1-x7).
  • R 1 is as defined above.
  • X p is-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-, -N (CH 3 ) CO-, -NH. -, -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
  • a 1 represents an oxygen atom or -COO- * (where a bond with an "*" binds to (CH 2 ) a2 ), and
  • a 2 is an oxygen atom or * -COO- (where *).
  • the bond with (CH 2 ) represents (CH 2) a2 ).
  • a 1 and a 3 are independently integers of 0 or 1
  • a 2 is an integer of 1 to 10
  • Cy represents a 1,4-cyclohexylene group or a 1,4-phenylene group. ..
  • X 3 is any of -O-, -CH 2 O-, -COO- or -OCO-, and R 2 is an alkyl group having 3 to 20 carbon atoms or an alkyl number of carbon atoms. preferably represents an alkoxyalkyl group of 2 to 20, more preferably when R 2 is an alkyl group having 3 to 20 carbon atoms, any hydrogen atoms that form the R 2 may be substituted by fluorine atoms ..
  • a preferable diamine (s) having a structure represented by any of the above formulas (S1) to (S3) a preferable diamine (s) having a structure represented by the above formulas (S1) to (S3) and at least one benzene.
  • a diamine having a ring is preferable.
  • Preferred examples of the diamine (s) include diamines represented by the following formula (d1) or formula (d2).
  • Y represents the side chain structure represented by the above formulas (S1) to (S3).
  • X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -COO-, -CONH-,-(CH 2 ) m- , -SO 2- , -O- (CH 2 ) m- O-, -OC (CH 3 ) 2- , -CO- (CH 2 ) m- , -CO- (CH 2 ) m , -CO- (CH 2 ) m -CO-, -NH- (CH) 2) m -, - NH- ( CH 2) m -NH -, - SO 2 - (CH 2) m -, - SO 2 - (CH 2) m -SO 2 -, - CONH- (CH 2) m -, -CONH- (CH 2 ) m -NHCO-, or -COO- (
  • Preferred specific examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-18). (N is an integer from 1 to 20.)
  • Preferred specific examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).
  • X p1 to X p8 are independently synonymous with X p in the above formulas (S1-x1) to (S1-x6), and are X s1.
  • ⁇ X s4 independently represent -O-, -CH 2 O-, -COO- or -OCO-.
  • X a to X f represent a single bond, -O-, -NH-, or -O- (CH 2 ) m- O- (m is an integer of 1 to 8), and R 1a to R 1h.
  • the polymer (P) contained in the liquid crystal alignment agent of the present invention may be composed of one component or two or more components of a polyimide precursor and / or a polyimide which is an imidized product of the polyimide precursor.
  • the polyimide precursor is a polymer from which polyimide can be obtained by imidization of a polyamic acid, a polyamic acid ester, or the like.
  • Preferred specific embodiments of the polymer (P) include, but are not limited to, the following two types.
  • polymer which is an imidized product of the polyimide precursor
  • the above-mentioned copolymer or polymer blend may be used alone or in combination of both.
  • the polyamic acid (P), which is a polyimide precursor of the polymer (P), is a diamine component containing the diamine (1), preferably a diamine component containing a diamine (s) in addition to the diamine (1). It can be obtained by a polymerization reaction with a tetracarboxylic acid component.
  • the amount of the diamine (1) used is preferably 1 to 100 mol%, more preferably 1 to 99 mol%, still more preferably 5 to 95 mol% with respect to the diamine component to be reacted with the tetracarboxylic acid component. ..
  • the amount of diamine (s) used is preferably 1 to 99 mol% with respect to the diamine component to be reacted with the tetracarboxylic acid component, and 1 to 95. More preferably mol%.
  • the diamine component used in the production of the polyamic acid (P) may contain a diamine other than the diamine (1) and the diamine (s) (hereinafter, also referred to as other diamines). Examples of other diamines are given below, but the present invention is not limited thereto.
  • a 1 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO-, -OCO-, -CON ( CH 3 )-or -N (CH 3 ) CO- is indicated, m1 and m2 independently indicate an integer of 0 to 4, and m1 + m2 indicates an integer of 1 to 4. Equation (3b-2).
  • a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • m5 represents 1 to 5 in the formula (3b-3).
  • a 3 and a 4 are each independently a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2- , -C (CF 3 ) 2- , -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO -, - OCO -, - CON (CH 3) - or -N (CH 3) CO- indicates, m6 is an integer of 1 to 4).
  • n is an integer of 1 to 6.
  • diamines p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, among others, from the viewpoint of preferably obtaining the effects of the present invention.
  • the amount of the other diamines used is preferably 1 to 99 mol%, more preferably 5 to 95, based on the total diamine components used. It is mol%.
  • the amount of the diamines (s) used is preferably 98 mol% or less with respect to the diamine component to be reacted with the tetracarboxylic acid component. More preferably, it is 94 mol% or less.
  • the amount of the diamine represented by the above formulas (5-1) to (5-10) is preferably 5 to 40 mol% with respect to the total diamine component used in the production of the polyamic acid (P). , More preferably 10-40 mol%.
  • a diamine having a photopolymerizable group at the end 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, a diamine having a photopolymerizable group at the end, and the above formula
  • the diamine represented by any of R1) to (R5) and the diamine represented by the above formulas (z-1) to (z-18) are used at least one in the case of producing the polyamic acid (P).
  • the amount used can be preferably 1 to 40 mol%, more preferably 5 to 40 mol%, based on the total diamine component used in the production of the polyamic acid (P).
  • the tetracarboxylic acid component to be reacted with the diamine component is not only tetracarboxylic acid dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid.
  • tetracarboxylic acid dianhydride such as acid dialkyl ester dihalide can also be used.
  • the tetracarboxylic dianhydride or a derivative thereof examples include aromatic, aliphatic or alicyclic tetracarboxylic dianhydride, or derivatives thereof.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the aromatic ring.
  • Aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure as a part thereof.
  • the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it does not have to be composed only of an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure as a part thereof.
  • the tetracarboxylic dianhydride or a derivative thereof is preferably represented by the following formula (T) or a derivative thereof.
  • X represents a structure selected from the group consisting of the following formulas (x-1) to (x-13).
  • R 1 to R 4 are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms, respectively.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
  • j and k are integers of 0 or 1
  • a 1 and A 2 are independent, single bond, ether (-O-), carbonyl (-CO-), ester (-COO-), and phenylene, respectively.
  • * 1 is a bond that binds to one acid anhydride group
  • * 2 is a bond that binds to the other acid anhydride group.
  • 2 pieces of A 2 may being the same or different.
  • X is the above formulas (x-1) to (x-7) and (x-11) to (x).
  • the one selected from -13) can be mentioned.
  • the ratio of the tetracarboxylic dianhydride or its derivative represented by the above formula (T) is preferably 1 mol% or more, more preferably 5 mol% or more, based on 1 mol of the total tetracarboxylic acid component used. It is preferable, 10 mol% or more is more preferable.
  • the tetracarboxylic dianhydride and its derivative used for producing the polyamic acid (P) may contain a tetracarboxylic dianhydride other than the above formula (T) or a derivative thereof.
  • the polyamic acid (P) is produced by reacting the diamine component and the tetracarboxylic acid component in a solvent (condensation polypolymerization).
  • the solvent is not particularly limited as long as it dissolves the produced polymer.
  • Specific examples of the above solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl.
  • -2-Imidazolidinone can be mentioned.
  • the polymer When the polymer has high solvent solubility, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3].
  • a solvent can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • the reaction can be carried out at any concentration, but the concentration of the diamine component and the tetracarboxylic acid component with respect to the above solvent is preferably 1 to 50 mass by mass. %, More preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration and then the solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component shall be 0.8 to 1.2. Is preferable. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polymer.
  • the polyamic acid ester which is a polyimide precursor is, for example, [I] a method of reacting a polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [II]. III] It can be obtained by a known method such as a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
  • the polyimide contained in the liquid crystal alignment agent of the present invention is a polyimide obtained by ring-closing the above-mentioned polyimide precursor.
  • the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing the polyimide precursor to obtain polyimide include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
  • the temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the system.
  • the catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. It is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, and tributylamine trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride and pyromellitic anhydride, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution may be added to a solvent for precipitation.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
  • the polymer put into a solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
  • impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones and hydrocarbons. It is preferable to use three or more kinds of solvents selected from these because the efficiency of purification is further improved.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimide is preferably 5,000 to 1,000,000, more preferably 10,000 to 150. It is 000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good orientation of the liquid crystal display element can be ensured.
  • the polymer (P) in the present invention may be a terminal-sealed polymer by using an appropriate terminal-sealing agent together with the above-mentioned tetracarboxylic acid component and diamine component in the production thereof.
  • the end-sealed polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.
  • Examples of the terminal of the polymer (P) in the present invention include an amino group, a carboxy group, an acid anhydride group or a derivative thereof.
  • An amino group, a carboxy group, an acid anhydride group, or a derivative thereof can be obtained by a usual condensation reaction or the following terminal encapsulant, and the derivative can be obtained, for example, by using the following terminal encapsulant. Obtainable.
  • terminal encapsulant examples include acetic anhydride, maleic anhydride, nagic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, and the following formulas.
  • Dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, Monoamine compounds such as n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenylisocyanate and naphthylisocyanate can be mentioned.
  • chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chlor
  • the ratio of the terminal encapsulant to be used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, based on 100 mol parts of the total diamine component used.
  • the liquid crystal alignment agent of the present invention is a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in a suitable solvent.
  • the liquid crystal alignment agent of the present invention in addition to the polymer (P), other weights are used for the purpose of improving, for example, electrical characteristics (eg, high voltage retention characteristics), vertical orientation, and solution characteristics.
  • a coalescence hereinafter, also referred to as another polymer
  • the content ratio of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polymers contained in the liquid crystal alignment agent. preferable.
  • the other polymer is not particularly limited, and is, for example, a group consisting of a polyimide precursor obtained by using the diamine component not containing the diamine (1) and the tetracarboxylic acid component, and a polyimide which is an imidized product of the polyimide precursor.
  • the main skeleton is mentioned.
  • At least one selected from the group consisting of the polymer (B), polyamide, polyurea, polyorganosiloxane, poly (meth) acrylate and polyester is preferable.
  • other polymers may be used in combination of 2 or more types.
  • Polymer (B) As the polymer (B), at least one selected from the group consisting of a polyimide precursor obtained by using the diamine component containing the diamine (s) and an imidized product of the polyimide precursor from the viewpoint of enhancing electrical characteristics.
  • the polymer of is more preferable.
  • the preferred embodiment of the diamine (s) used to obtain the polymer (B) is the same as the diamine (s) exemplified in the polymer (P). Further, as the diamine component used to obtain the polymer (B), in addition to the above diamine (s), other diamines exemplified by the above polymer (P) can also be used.
  • a diamine having the radical initiation function a diamine having a photosensitizing function showing a sensitizing effect by light irradiation, and a diamine having the group "-N (D)-" are preferably used.
  • One or more diamines (s) used for producing the polymer (B) can be used when producing the polymer (B), and the amount used thereof is used for producing the polymer (B). It is preferably 5 to 90 mol%, more preferably 10 to 90 mol%, based on the total diamine component to be obtained.
  • Examples of the tetracarboxylic acid component used for producing the polymer (B) include compounds exemplified as the tetracarboxylic acid component used for producing the polyamic acid (P). Of these, the tetracarboxylic dianhydride represented by the above formula (T) or a derivative thereof is preferable.
  • One or more of the one represented by the above formula (T) or a derivative thereof used for producing the polymer (B) can be used in the case of producing the polymer (B), and the amount used thereof is determined. It is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total tetracarboxylic acid component used in the production of the polymer (B).
  • the liquid crystal alignment agent of the present invention may contain other components other than the above, if necessary.
  • Such components include, for example, a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group, and a polymerizable unsaturated group.
  • crosslinkable compound examples include compounds represented by any of the following formulas (CL-1) to (CL-11).
  • Examples of the compound for adjusting the dielectric constant and the electric resistance of the liquid crystal alignment film include monoamines having a nitrogen-containing aromatic heterocycle such as 3-picorylamine.
  • a monoamine having a nitrogen-containing aromatic heterocycle is used, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. It is 20 parts by mass.
  • Preferred specific examples of the functional silane compound are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltriethoxysilane.
  • the organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfonate, and ⁇ -butyrolactone.
  • ⁇ -Valerolactone 1,3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropaneamide, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) ) -2-Pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively "good solvent”) Also known as).
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the organic solvent contained in the liquid crystal alignment agent is a mixture in which a solvent (also referred to as a poor solvent) for improving the coatability when applying the liquid crystal alignment agent and the surface smoothness of the coating film is used in combination with the above solvent.
  • a solvent also referred to as a poor solvent
  • the use of solvent is preferred. Specific examples of the poor solvent used in combination are described below, but the present invention is not limited thereto.
  • diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
  • ethylene glycol dimethyl ether ethylene glycol diethyl ether
  • ethylene glycol dibutyl ether 1,2-butoxyetan
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether.
  • diisobutylcarbinol diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene.
  • Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, and the like.
  • Preferred combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-.
  • Examples thereof include diisobutylketone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone and diisobutylketone, N-ethyl-2-pyrrolidone and N, N-dimethyllactamide and diisobutylketone.
  • the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is 1 to 10% by mass.
  • a particularly preferable solid content concentration depends on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. In the case of the printing method, it is particularly preferable that the solid content concentration is 3 to 9% by mass and the solution viscosity is 12 to 50 mPa ⁇ s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to 1 to 5% by mass and thereby the solution viscosity to 3 to 15 mPa ⁇ s.
  • the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
  • the liquid crystal alignment film of the present invention can be used for a horizontally oriented type or a vertically oriented type liquid crystal alignment film, and is particularly suitable for a vertically oriented type liquid crystal display element such as a VA method or a PSA mode described later.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film.
  • the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (3) or steps (1) to (4).
  • Step (1) Step of applying the liquid crystal alignment agent on the substrate
  • the liquid crystal alignment agent of the present invention can be applied to one surface of a substrate provided with a patterned transparent conductive film, for example, by a roll coater method, a spin coating method, or a printing method.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
  • an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
  • Step (2) Step of firing the coating film After the liquid crystal alignment agent is applied, preheating is preferably performed first for the purpose of preventing the applied alignment agent from dripping.
  • the prebake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C.
  • the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Further, it is preferable that a heating (post-baking) step is carried out.
  • the post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
  • the post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
  • the film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.
  • the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
  • the alignment ability-imparting treatment includes a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and photoalignment in which polarized or unpolarized radiation is applied to the coating film. Processing etc. can be mentioned.
  • the radiation to irradiate the coating film for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used.
  • the radiation when the radiation is polarized, it may be linearly polarized or partially polarized.
  • the irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination thereof.
  • the direction of irradiation is diagonal.
  • a liquid crystal layer (3-1) In the case of a VA type liquid crystal display element
  • Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and between the two substrates arranged opposite to each other. Place the liquid crystal display in.
  • the first method is a conventionally known method. First, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded together using a sealing agent, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealing agent to contact the film surface, and then the injection holes are formed. Seal.
  • the second method is a method called the ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. Then, the other substrate is bonded so that the liquid crystal alignment film faces each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. Regardless of which method is used, it is desirable to remove the flow orientation during liquid crystal filling by further heating the liquid crystal composition used to a temperature at which an isotropic phase is obtained and then slowly cooling the liquid crystal composition to room temperature.
  • the liquid crystal alignment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates.
  • a liquid crystal display element PSA type liquid crystal display element
  • the liquid crystal alignment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through a step of arranging a liquid crystal alignment film containing the liquid crystal alignment film and applying a voltage between the electrodes.
  • a method of manufacturing a liquid crystal display element may be adopted in the same manner as in (3-1) above and then through a step of irradiating ultraviolet rays described later. .. According to this method, a liquid crystal display element having an excellent response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display element.
  • the compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group and a methacrylate group represented by the above formulas (M-1) to (M-7).
  • the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the polymerizable group may be contained in the polymer used for the liquid crystal aligning agent, and as such a polymer, for example, a diamine component containing a diamine having the photopolymerizable group at the end is used in the reaction. Examples thereof include the obtained polymer.
  • Step (4) Step of irradiating ultraviolet rays
  • the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (3-2) or (3-3).
  • the voltage applied here can be, for example, a direct current or an alternating current of 5 to 50 V.
  • the light to be irradiated for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
  • the light source of the irradiation light for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excima laser and the like can be used.
  • the irradiation amount of light is preferably 1,000 to 200,000 J / m 2 , and more preferably 1,000 to 100,000 J / m 2 .
  • a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
  • a polarizing plate attached to the outer surface of the liquid crystal cell a polarizing plate called an "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between a cellulose acetate protective film or the H film itself.
  • a polarizing plate made of the above can be mentioned.
  • NMP N-methyl-2-pyrrolidone
  • BCS butyl cellosolve
  • THF tetrahydrofuran
  • DMF N, N-dimethylformamide
  • DMAc N, N-dimethylacetamide
  • Measuring device GPC (LC-20 series) manufactured by Shimadzu Corporation, column temperature: 50 ° C., eluent: N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr ⁇ H2O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L), flow velocity: 1.0 mL / min, standard sample for preparing calibration lines: TSK standard polyethylene oxide manufactured by Toso Co., Ltd. (Molecular weight of about 900,000, 150,000, 100,000, 30,000) and Polyethylene glycol manufactured by Polymer Laboratory (molecular weight of about 12,000, 4,000, 1,000).
  • FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
  • the (chemical) imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and is derived from the peak integrated value of this proton and the NH group of the amic acid that appears in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using the integrated proton peak value.
  • x is the integrated proton peak value derived from the NH group of the amic acid
  • y is the integrated peak value of the reference proton
  • ⁇ is the integrated value of the amic acid in the case of polyamic acid (imidization rate is 0%).
  • Imidization rate (%) (1- ⁇ ⁇ x / y) ⁇ 100
  • Example 1 The liquid crystal alignment agent (A-1) was prepared by adding NMP (6.0 g) and BCS (8.0 g) to the polyamic acid solution (1) (6.0 g) obtained in Synthesis Example 1 and stirring at room temperature for 2 hours.
  • NMP (6.0 g) and BCS (8.0 g) were added to the polyamic acid solution (1) (1.8 g) obtained in Synthesis Example 1 and the polyamic acid solution (4) (4.2 g) obtained in Synthesis Example 4. ) was added and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (A-2).
  • the liquid crystal alignment agents (A-1), (A-2), (B-1) to (B-4) obtained above are uniform solutions with no abnormalities such as turbidity or precipitation. It was confirmed that. Using the obtained liquid crystal alignment agent, the transmittance, the voltage retention rate, the residual DC voltage, and the afterimage characteristics were evaluated.
  • the liquid crystal alignment agents (A-1), (A-2), (B-1) to (B-4) obtained above are spin-coated on a quartz substrate and dried on a hot plate at 70 ° C. for 90 seconds. I let you. Then, it was fired in an IR oven at 230 ° C. for 20 minutes to form a coating film having a film thickness of 100 nm, and a substrate with a liquid crystal alignment film was obtained. This substrate with a liquid crystal alignment film was placed inside, and another quartz substrate was used to sandwich a contact liquid (manufactured by Shimadzu Device Manufacturing Co., Ltd.) for the purpose of preventing light interference.
  • a contact liquid manufactured by Shimadzu Device Manufacturing Co., Ltd.
  • UV-3600 manufactured by Shimadzu Corporation
  • the temperature was 25 ° C. and the scan wavelength was 380 to 800 nm.
  • a reference liquid was used in which a contact liquid was sandwiched between two uncoated quartz substrates. The evaluation is based on the transmittance of the wavelength of 590 nm, and the values are shown in Table 3 below.
  • liquid crystal alignment agent (A-1), (A-2), (B-1) to (B-4) obtained above, a liquid crystal cell was produced by the procedure as shown below.
  • the liquid crystal alignment agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 70 ° C. for 90 seconds, and then baked in an IR oven at 230 ° C. for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. ..
  • thermosetting sealant (XN-1500T manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.) was printed on the periphery.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and the cells were bonded to the previous substrate, and then the sealant was cured to prepare an empty cell.
  • a liquid crystal MLC-3023 (manufactured by Merck Group) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell.
  • UV was irradiated from the outside of the liquid crystal cell through a cut filter having a wavelength of 325 nm or less at 10 J / cm 2.
  • the illuminance of UV was measured using UV-MO3A manufactured by ORC.
  • UV UV lamp: FLR40SUV32 /
  • UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied.
  • A-1) was irradiated for 30 minutes.
  • the voltage retention rate was measured using a liquid crystal cell for evaluating the voltage retention rate after UV irradiation. A voltage of 1 V was applied for 60 ⁇ sec in a hot air circulation oven at 60 ° C., and then the voltage after 16.67 msec was measured, and how much the voltage could be maintained was calculated as the voltage retention rate. VHR-1 manufactured by Toyo Corporation was used for measuring the voltage holding ratio. The values are shown in Table 3 below. The higher the value, the better.
  • the liquid crystal alignment agent has an ITO electrode substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which an ITO electrode pattern having a pixel size of 200 ⁇ m ⁇ 600 ⁇ m and a line / space of 3 ⁇ m is formed, and a height of 3.
  • a sealant (XN-1500T manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.) was placed around the ITO electrode substrate on which an ITO electrode pattern having an ITO electrode pattern having a line / space of 3 ⁇ m coated with a liquid crystal alignment film was formed, leaving a liquid crystal injection port. ) was printed.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and the cells were bonded to the previous substrate, and then the sealant was cured to prepare an empty cell.
  • a liquid crystal MLC-3023 manufactured by Merck Group
  • UV was irradiated from the outside of the liquid crystal cell through a cut filter of 325 nm or less at 10 J / cm 2.
  • the illuminance of UV was measured using UV-MO3A manufactured by ORC.
  • UV UV lamp: FLR40SUV32 /
  • UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied.
  • A-1) was irradiated for 30 minutes.
  • the liquid crystal alignment film obtained by using the liquid crystal alignment agent (A-1) of Example 1 corresponds to the liquid crystal alignment agents (B-1) and (B-2) of Comparative Examples 1 and 2.
  • High transmittance was obtained as compared with the liquid crystal alignment film obtained by using.
  • the liquid crystal alignment film obtained by using the liquid crystal alignment agent (A-2) of Example 2 can be obtained by using the corresponding liquid crystal alignment agents (B-3) and (B-4) of Comparative Examples 3 and 4. Higher transmittance was obtained as compared with the liquid crystal alignment film.
  • the difference of 0.5% in the transmittance is a remarkable difference in the art.
  • liquid crystal alignment agent obtained in the examples when used, a liquid crystal alignment film having a high voltage retention rate can be obtained even in the voltage retention evaluation. Further, it can be seen that a liquid crystal alignment film showing good characteristics can be obtained in the evaluation of the residual DC voltage and the evaluation of the afterimage characteristics.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcoder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television, and the like. It can be widely applied to information displays and the like, especially to ultra-high-definition liquid crystal displays such as 4K and 8K.

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