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WO2019146319A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément à cristaux liquide ainsi que procédé de fabrication de celui-ci - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément à cristaux liquide ainsi que procédé de fabrication de celui-ci Download PDF

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Publication number
WO2019146319A1
WO2019146319A1 PCT/JP2018/046723 JP2018046723W WO2019146319A1 WO 2019146319 A1 WO2019146319 A1 WO 2019146319A1 JP 2018046723 W JP2018046723 W JP 2018046723W WO 2019146319 A1 WO2019146319 A1 WO 2019146319A1
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group
liquid crystal
formula
carbon atoms
compound
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English (en)
Japanese (ja)
Inventor
岡田　敬
嘉崇 村上
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JSR Corp
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JSR Corp
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Priority to KR1020207015907A priority Critical patent/KR102349617B1/ko
Priority to JP2019567917A priority patent/JP6962387B2/ja
Priority to CN201880078150.0A priority patent/CN111433665B/zh
Publication of WO2019146319A1 publication Critical patent/WO2019146319A1/fr
Anticipated expiration legal-status Critical
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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
    • C08G73/02—Polyamines
    • 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
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, and a method of manufacturing the liquid crystal element.
  • liquid crystal element As a liquid crystal element, a liquid crystal element of a horizontal alignment mode using a nematic liquid crystal having positive dielectric anisotropy represented by TN (Twisted Nematic) type, STN (Super Twisted Nematic) type or the like, or negative dielectric anisotropy
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • Various liquid crystal elements such as a VA (Vertical Alignment) liquid crystal element of a (homeotropic) alignment mode using a nematic liquid crystal having properties are known. These liquid crystal elements have a liquid crystal alignment film having a function of aligning liquid crystal molecules in a predetermined direction.
  • a liquid crystal aligning film is formed by apply
  • polymer components of liquid crystal aligning agents polyamic acids, soluble polyimides, polyamides, polyesters, polyorganosiloxanes and the like are known, and in particular polyamic acids and soluble polyimides have heat resistance, mechanical strength, and affinity with liquid crystal molecules. It has been used for a long time because it has excellent properties and the like (see Patent Documents 1 to 3).
  • Polyamic acids and soluble polyimides have relatively low solubility in organic solvents, and high boiling point solvents such as N-methyl-2-pyrrolidone (NMP), which is an aprotic polar solvent, are generally used as the solvent component of liquid crystal aligning agents. It is done.
  • NMP N-methyl-2-pyrrolidone
  • problems such as restriction of the material of the substrate occur, and for example, the application of a film substrate as a substrate of a liquid crystal element is limited.
  • dyes used as colorants for color filters are relatively weak to heat, and the use of dyes may be limited when heating at the time of film formation needs to be performed at high temperature .
  • the solubility of the liquid crystal aligning agent in the polymer component is sufficiently high, and the solvent having a sufficiently low boiling point is limited, and the selection range is narrow.
  • the polymer component is not uniformly dissolved in the solvent, coating unevenness (film thickness unevenness) or pinholes may occur in the liquid crystal alignment film formed on the substrate, or linearity can not be ensured at the end of the coating region.
  • the surface may not be flat. In this case, there is a concern that the product yield may decrease or the display performance such as the liquid crystal alignment and the electrical characteristics may be affected.
  • polyamic acid is better in solubility than polyimide, in order to cyclize polyamic acid to polyimide to ensure good electrical characteristics, heating during element production is relatively made. It needs to be done at high temperature.
  • the polymer component of the liquid crystal aligning agent exhibits high solubility even in a low boiling point solvent, so that when it is used as a liquid crystal aligning agent, it exhibits excellent coatability on the substrate, and the liquid crystal alignment and electricity New materials with excellent properties are required.
  • a liquid crystal television with a large screen and high definition is mainly used, and a small display terminal such as a smartphone and a tablet PC is in widespread use, and a demand for high quality liquid crystal panels is further increasing. Therefore, it is important to secure excellent display quality.
  • the present disclosure has been made in view of the above-described circumstances, and one object thereof is a liquid crystal aligning agent capable of obtaining a liquid crystal element having good coatability on a substrate and excellent liquid crystal alignment and voltage holding ratio. To provide.
  • a liquid crystal aligning agent containing a polyenamine [1] A liquid crystal alignment film formed using the liquid crystal alignment agent of the above-mentioned [1]. [3] A liquid crystal element comprising the liquid crystal alignment film of the above [2].
  • [4] A process of forming a coating on each of the conductive films of a pair of substrates having a conductive film using the liquid crystal aligning agent according to the above [1], a pair of substrates on which the coating is formed, liquid crystal Forming a liquid crystal cell by opposingly arranging the coated films facing each other through a layer, and irradiating the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates; And a method of manufacturing a liquid crystal element.
  • liquid crystal aligning agent containing polyenamine as a polymer component By using a liquid crystal aligning agent containing polyenamine as a polymer component, it is possible to obtain a liquid crystal element excellent in liquid crystal alignment and voltage holding ratio. Moreover, the said liquid crystal aligning agent is excellent in the coating property with respect to a board
  • hydrocarbon group is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • chain hydrocarbon group means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed only of a chain structure. However, it may be saturated or unsaturated.
  • alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure.
  • aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a ring structure.
  • aromatic hydrocarbon group it is not necessary to be composed of only an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure.
  • the liquid crystal aligning agent of this indication contains polyenamine as a polymer component.
  • Polyenamine is a polymer having a carbon-carbon double bond at the position adjacent to the amino group of polyamine, and includes polyenamino ketone, polyenamino ester, polyenamino nitrile and polyenamino sulfonyl.
  • the polyenamine to be used is ⁇ , ⁇ having one or more of one partial structure represented by the following formula (1) or formula (2) in one molecule, in terms of availability of monomers and ease of synthesis. It is preferably a reaction product of an unsaturated compound and a diamine compound.
  • X 1 is a carbonyl group or a sulfonyl group
  • L 1 is a leaving group which leaves by reaction with a diamine compound
  • L 2 is an oxygen atom
  • R 5 is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, and a plurality of X 1 , R 5 , L 1 and L 2 in one molecule are each independently as defined above “*” Indicates that it is a bond.
  • X 1 is preferably a carbonyl group in terms of a high degree of freedom of choice of monomers.
  • the L 1 in the above formula (1) is not particularly limited as long as it is a group capable of leaving by reaction with the amino group of the diamine compound, and examples thereof include an alkoxy group having 1 to 5 carbon atoms, a pyrrolidinyl group, a halogen atom, a hydroxyl group, Examples thereof include a substituted or unsubstituted phenoxy group, a heterocyclic group, and a monovalent group in which a hydroxyl group or a thiol group is introduced into the ring portion of the heterocyclic ring.
  • heterocyclic group means that n (n is an integer) hydrogen atoms are removed from the ring of a heterocyclic ring (eg, nitrogen-containing heterocyclic ring, oxygen atom heterocyclic ring, sulfur-containing heterocyclic ring, etc.) Means an n-valent group.
  • Preferred specific examples of the ⁇ , ⁇ -unsaturated compound include compounds having two or more of one of the partial structures represented by the following formulas (4-1) to (4-4) in one molecule, At least one selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6) (including tautomers).
  • the structure represented by each of following formula (4-1), formula (4-2), formula (4-4), formula (5) and formula (6) is represented by the said formula (1)
  • the structure corresponds to one having a partial structure
  • the structure represented by the following formula (4-3) corresponds to one having a partial structure represented by the above formula (2).
  • X 1 represents a carbonyl group or a sulfonyl group
  • R 1 to R 5 and R 7 to R 10 represent
  • R 6 independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms
  • R 6 represents an alkanediyl group having 2 to 5 carbon atoms or —O— or — between carbon-carbon bonds of the alkanediyl group.
  • L 1 is a leaving group which is eliminated by reaction with a diamine compound
  • L 2 is an oxygen atom or a sulfur atom
  • a plurality of X 1 and R 1 in one molecule To R 10 , L 1 and L 2 each independently have the above-mentioned definition, “*” represents a bond.
  • the formula (4-1), (4-2), specific examples of L 1 in the formula (4-4) and the formula (5), the description of L 1 in the formula (1) is applied Ru.
  • the monovalent organic group of R 1 to R 5 and R 7 to R 10 is preferably a monovalent alkyl group having 1 to 20 carbon atoms, an alkoxy group or a cycloalkyl group.
  • the ⁇ , ⁇ -unsaturated compound has two or more of one of the partial structures represented by the above formulas (4-1) to (4-4) in one molecule, the moiety in one molecule
  • the number of structures is preferably two to four, more preferably two.
  • compounds represented by each of the following formulas (M-1) to (M-4) can be preferably used.
  • B 1 to B 4 are a single bond or a divalent organic group.
  • X 1 , R 1 to R 6 , L 1 and L 2 are It is synonymous with the said Formula (4-1)-Formula (4-4).
  • examples of the divalent organic group of B 1 to B 4 include a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon of the hydrocarbon group. And-a divalent group having -O-, -S-, -NH- and the like between-carbon bonds, and the like.
  • B 1 to B 4 may be groups which are bonded to the above-mentioned formulas (4-1) to (4-4) by an aromatic ring group.
  • the aromatic ring group is preferably a phenylene group or a naphthalene group, and particularly preferably a phenylene group.
  • the aromatic ring group may have a methyl group, an ethyl group, an alkoxy group or the like as a substituent in the ring portion.
  • ⁇ , ⁇ -unsaturated compound examples include compounds represented by the following formulas (A-1) to (A-14), and the like.
  • one kind of ⁇ , ⁇ -unsaturated compound may be used alone, or two or more kinds may be used in combination.
  • the “ ⁇ , ⁇ -unsaturated compound” is meant to include tautomers of compounds exhibiting tautomerism.
  • the partial structure in which L 1 in the above formula (4-1) is a hydroxyl group mutually converts with the partial structure represented by the following formula (4-1A), but in the synthesis of polyenamine, the following formula It is allowed that a compound having two or more partial structures represented by (4-1A) in one molecule is present.
  • L 1 in the above formula (4-2) is a hydroxyl group and a compound represented by the above formula (6), and a partial structure represented by the following formula (4-2A)
  • the compounds are mutually converted to each other.
  • the tautomers of the compounds represented by the above formulas (A-5), (A-9) and (A-10) are shown below.
  • each of the above formulas (A-8), (A-9), (A-11), (A-12) and (A-14) corresponds to a compound having two or more partial structures represented by the above formula (4-1) in one molecule
  • the compound represented by the above formula (A-10) is a compound represented by the above formula (A) It corresponds to a compound having two or more partial structures represented by 4-2) in one molecule.
  • the compound represented by the above formula (A-13) corresponds to a compound having two or more partial structures represented by the above formula (4-3) in one molecule
  • the above formula (A-6) The compound represented by each of (A-7) and (A-7) corresponds to a compound having two or more partial structures represented by the above formula (4-4) in one molecule.
  • the compounds represented by the above formulas (A-1) to (A-3) correspond to the compounds represented by the above formula (5)
  • the compound represented by each of 5) corresponds to the compound represented by the said Formula (6).
  • the diamine compound used for the synthesis of polyenamine is not particularly limited, and known diamine compounds can be used. Among these, since polyenamine can make the liquid crystal alignment property of the obtained liquid crystal element excellent, a group consisting of compounds represented by the following formulas (d-1) to (d-4) It is preferable to have a partial structure derived from at least one diamine compound selected from the following (hereinafter, also referred to as "specific diamine").
  • X 11 and X 12 each independently represent a single bond, —O—, —S—, —OCO— or —COO—, and Y 11 is an oxygen atom or a sulfur atom
  • X 14 and X 15 are each independently represent a single bond, -O -, - COO- or a -OCO-, R 17 is an alkanediyl group having 1 to 3 carbon atoms There, A 11 is a single bond or an alkanediyl group having a carbon number of 1 ⁇ 3 .
  • a is 0 or 1
  • b is an integer of 0 ⁇ 2
  • c is an integer of 1 ⁇ 20
  • a and b are not simultaneously 0.
  • a 12 is a single bond, an alkanediyl group having 1 to 12 carbon atoms, or 1 to 6 carbon atoms
  • a 13 represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and
  • a 14 represents a monovalent organic compound having a steroid skeleton. Group
  • examples of the alkanediyl group having 1 to 3 carbon atoms of R 11 and R 12 include, for example, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group And propane-2,3-diyl group. Among these, preferred is a methylene group, an ethylene group or a propane-1,3-diyl group.
  • X 11 and X 12 are preferably a single bond, -O- or -S-.
  • Y 11 is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • the bonding position of the primary amino group on the benzene ring is not particularly limited. For example, when there is one primary amino group on the benzene ring, the bonding position may be any of 2-position, 3-position and 4-position with respect to other groups, in 3-position or 4-position. It is preferably present, and more preferred is 4-position. In addition, in the case where there are two primary amino groups on the benzene ring, the bonding position may be, for example, the 2,4-position or the 2,5-position relative to other groups, and in particular, the 2,4-position Is preferred.
  • the hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent atom in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom It may be substituted by a group or a fluorine atom.
  • examples of the monovalent hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 5 to 10 carbon atoms Examples thereof include phenyl group and tolyl group), aralkyl group having 5 to 10 carbon atoms (such as benzyl group) and the like.
  • the compound include 1,3-bis (4-aminobenzyl) urea, 1,3-bis (4-aminophenethyl) urea, 1,3-bis (3-aminobenzyl) urea, 1- (4-aminobenzyl) ) -3- (4-aminophenethyl) urea, 1,3-bis (2- (4-aminophenoxy) ethyl) urea, 1,3-bis (3- (4-aminophenoxy) propyl) urea, 1, 3-Bis (4-aminobenzyl) thiourea, 1,3-bis (2-aminobenzyl) urea, 1,3-bis (2-aminophenethyl) urea,
  • X 13 is a single bond, -O- or -S-, preferably a single bond or -O-.
  • m 2 is preferably 1 to 10, more preferably 1 to 8.
  • each primary amino group on the benzene ring is not particularly limited, it is preferable that each primary amino group be in the 3- or 4-position relative to the other group, and more preferably in the 4-position.
  • the hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom. It may be substituted by a valent group or a fluorine atom.
  • Preferred specific examples of the compound represented by the above formula (d-2) include, for example, bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, bis (4-aminophenoxy) propane, bis (4) -Aminophenoxy) butane, bis (4-aminophenoxy) pentane, bis (4-aminophenoxy) hexane, bis (4-aminophenoxy) heptane, bis (4-aminophenoxy) octane, bis (4-aminophenoxy) nonane
  • the group “—C c H 2c + 1 ” is preferably linear, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Groups, n-octadecyl group, n-nonadecyl group and the like.
  • the two primary amino groups in the diaminophenyl group are preferably in the 2,4- or 3,5-position relative to the group "X 4 ", and more preferably in the 2,4-position.
  • the hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent atom in which at least one hydrogen atom on the hydrocarbon group is substituted by a fluorine atom. Or a fluorine atom.
  • Preferred specific examples of the compound represented by the above formula (d-3) include, for example, compounds represented by each of the following formulas (d-3-1) to (d-3-12) it can.
  • fluoroalkanediyl group having 1 to 6 carbon atoms a perfluoroalkanediyl group having 1 to 4 carbon atoms is preferable, and -CF 2- , perfluoroethylene group, 1,3-perfluoropropanediyl group, 1,4 Perfluorobutanediyl is more preferred.
  • a 13 is preferably -O-.
  • the steroid skeleton in the A 14, Shikuropentano - perhydro phenanthridine consisting Ren core structure or a carbon - one or more than one carbon bond refers to a structure in which a double bond.
  • the monovalent organic group having such a steroid skeleton is preferably one having 17 to 40 carbon atoms.
  • Preferred specific examples of the compound represented by the above formula (d-4) include 1-cholesteryloxymethyl-2,4-diaminobenzene, from the viewpoint of giving a high pretilt angle to a coating film in the use of a liquid crystal alignment film.
  • the use ratio of the specific diamine can be arbitrarily set according to the diamine compound to be used.
  • the amount thereof used is preferably 1 mol% or more, and more preferably 3 mol% or more, based on all diamines.
  • the amount used is 10 mol% or more with respect to all the diamines. It is preferable to set it as 30 mol% or more, and more preferable to set it as 50 mol% or more.
  • the use thereof from the viewpoint of imparting good orientation When using at least one selected from the group consisting of a compound represented by the above formula (d-3) and a compound represented by the above formula (d-4), the use thereof from the viewpoint of imparting good orientation.
  • the proportion (the total amount of two or more compounds used) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all diamines.
  • 1 type of the compounds illustrated above can be used individually or in combination of 2 or more types.
  • diamine compounds other than the above specific diamines (hereinafter, also referred to as "other diamines”) can be used.
  • specific examples of the other diamine include the compounds shown below.
  • polyenamine having a structural unit derived from the diamine compound can be obtained by using each diamine compound shown below.
  • the diamine compound having a carboxyl group (hereinafter, also referred to as “carboxyl group-containing diamine”) can be used for the purpose of improving the electrical characteristics (in particular, the relaxation effect of accumulated charge) of the liquid crystal element obtained.
  • the carboxyl group-containing diamine is preferably used in combination with a diamine compound having a nitrogen-containing aromatic heterocycle, which will be described later, in that the effect of improving the electrical characteristics of the liquid crystal device to be obtained is further enhanced.
  • the carboxyl group-containing diamine used is preferably an aromatic diamine, and specific examples thereof include compounds represented by the following formulas (d-5-1) and (d-5-2), respectively.
  • R 20 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
  • Z 1 represents , A single bond, an oxygen atom, or an alkanediyl group having 1 to 3 carbon atoms
  • r 2, r 5 and r 6 each independently represents an integer of 1 or 2
  • r 1, r 3 and r 4 each independently represent 0 to 2
  • examples of the alkyl group having 1 to 10 carbon atoms for R 20 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Groups, heptyl groups, octyl groups, nonyl groups, decyl groups and the like, and these may be linear or branched.
  • Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a hexyloxy group.
  • Examples of the C 1-3 alkanediyl group as Z 1 include a methylene group, an ethylene group and a trimethylene group. r1, r3 and r4 are preferably 0 or 1, more preferably 0.
  • examples of the compound represented by the above formula (d-5-1) include 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid and 2,5-diaminobenzoic acid And the like; as a compound represented by the above formula (d-5-2), for example, 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid, 4,4′-diaminobiphenyl-2,2′-dicarboxylic acid Acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-Diaminobiphenyl-3-carbox
  • a carboxyl group-containing diamine When a carboxyl group-containing diamine is used, its use ratio is preferably 2 mol% or more, more preferably 3 to 90 mol%, and still more preferably 5 to 70 mol% with respect to the total diamine.
  • the diamine compound having a nitrogen-containing aromatic heterocyclic ring can be used for the purpose of improving the electrical characteristics (in particular, the effect of reducing burn-in due to a direct current voltage) of the liquid crystal element to be obtained.
  • the nitrogen-containing aromatic heterocycle possessed by the diamine compound include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, benzimidazole, purine, quinoline, naphthyridine, carbazole, acridine and the like.
  • diamine compound having a nitrogen-containing aromatic heterocycle examples include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3. , 6-diaminocarbazole, N-ethyl-3, 6-diaminocarbazole, N-phenyl-3, 6-diaminocarbazole, 3, 6-diaminoacridine, the following formula (d-6-1) to formula (d-6) And the compounds represented by each of -8) and the like.
  • these 1 type can be used individually or in combination of 2 or more types.
  • the proportion of the diamine compound having a nitrogen-containing aromatic heterocyclic ring is preferably 2 mol% or more, more preferably 3 to 50 mol%, and still more preferably 5 to 40 mol%, based on all diamines. Is more preferred.
  • a diamine compound having a protective group improves the solubility of polyenamine in a solvent, and when polyenamine is used in combination with another polymer, with other polymers. Can be used to improve the affinity of
  • the protecting group-containing diamine preferably has a partial structure in which a protecting group is bonded to a nitrogen atom, and specifically, a diamine having a group represented by the following formula (7-1) or formula (7-2) Compounds are mentioned.
  • a 21 is a single bond or a divalent organic group having 1 or more carbon atoms
  • Y 1 is a protecting group
  • R 21 to R 23 are And each independently represents a hydrogen atom or a monovalent organic group having a carbon number of 1 or more
  • m is an integer of 0 to 6.
  • "*" represents a bond.
  • the protective group of Y 1 is preferably a group which is released by heat, and for example, a carbamate type protective group, an amide type protective group, an imide type protective group And sulfonamide protecting groups.
  • a carbamate protective group is particularly preferable.
  • tert-butoxycarbonyl group examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group and a 1,1-dimethyl- Examples thereof include 2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like.
  • tert-butoxycarbonyl group is particularly preferable in that it is highly removable by heat and the amount of remaining of the deprotected portion in the membrane can be further reduced.
  • the monovalent organic group of R 21 and R 22 is preferably a monovalent hydrocarbon group of 1 to 10 carbon atoms, and more preferably an alkyl group or cycloalkyl group of 1 to 10 carbon atoms.
  • the monovalent organic group of R 23 is preferably a monovalent alkyl group of 1 to 10 carbon atoms or a protecting group.
  • Examples of the divalent organic group of A 21 include a divalent hydrocarbon group, and a group having —O—, —CO—, —COO—, —NH— or the like between carbon-carbon bonds of the hydrocarbon group. It can be mentioned.
  • a 21 is preferably bonded to an aromatic ring, and particularly preferably to a benzene ring.
  • Examples of the protective group-containing diamine include compounds represented by the following formulas (d-7-1) to (d-7-12), and the like.
  • the protective group-containing diamines may be used alone or in combination of two or more. (Wherein, TMS represents a trimethylsilyl group)
  • a protective group-containing diamine When a protective group-containing diamine is used, its use ratio is preferably 2 mol% or more, more preferably 3 to 80 mol%, and preferably 5 to 70 mol%, based on all diamines. Is more preferred.
  • a diamine compound having at least one selected from the group consisting of a secondary or tertiary amine structure represented by the following formula (9) and a nitrogen-containing heterocyclic structure (hereinafter referred to as “secondary or tertiary Amine structure / nitrogen-containing heterocyclic structure-containing diamine) may also be used.
  • Use of a secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine is preferable in that the improvement effect of the reduction in sticking due to a DC voltage can be enhanced.
  • R 51 and R 52 each independently represent a divalent aromatic ring group, and R 53 represents a hydrogen atom or a monovalent organic group having one or more carbon atoms. Indicates that it is a bond.
  • the divalent aromatic ring group R 51 and R 52 an aromatic hydrocarbon group, a nitrogen-containing aromatic heterocyclic group and the like.
  • Preferred is an aromatic hydrocarbon group, and examples thereof include a phenylene group and a naphthylene group.
  • R 51 and R 52 are particularly preferably phenylene groups.
  • Examples of the monovalent organic group represented by R 53 include alkyl groups such as methyl, ethyl and propyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl, tert-butoxycarbonyl and the like And the like.
  • R 53 is preferably a hydrogen atom or a methyl group.
  • nitrogen-containing heterocycle examples include nitrogen-containing heteroalicyclic structures such as piperidine, piperazine, pyrrolidine and hexamethyleneimine, and the nitrogen-containing aromatic heterocycles exemplified above.
  • secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine include, for example, bis (4-aminophenyl) amine, 2,4-diaminopyrimidine, 1,4-bis- (4-aminophenyl) -Piperazine, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, a diamine compound having a nitrogen-containing aromatic heterocyclic ring Examples thereof include compounds exemplified in the description, compounds represented by the following formulas (d-9-1) to (d-9-8), and the like.
  • secondary or tertiary amine structure / nitrogen-containing heterocyclic structure containing diamine may be used individually by 1 type, and may be used combining 2 or more types.
  • a secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine When a secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine is used, its use ratio is preferably 2 mol% or more, preferably 3 to 60 mol%, based on all diamines. More preferably, 5 to 50 mol% is more preferable.
  • a diamine compound represented by the following formula (8) (hereinafter, also referred to as “secondary amino group-containing diamine compound”) may be used as another diamine.
  • a secondary amino group-containing diamine compound when using polyenamine and another polymer as a polymer component of a liquid crystal aligning agent in combination, it is possible to control phase separation with other polymers. preferable.
  • a 31 represents a divalent aromatic ring group
  • R 31 represents an alkanediyl group having 1 to 5 carbon atoms
  • R 32 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms is there.
  • examples of the divalent aromatic ring group of A 31 include groups in which two hydrogen atoms have been removed from the ring portion of an aromatic ring such as a benzene ring, a naphthalene ring or an anthracene ring.
  • a 31 is preferably a phenylene group.
  • the alkanediyl group of R 31 may be linear or branched, and examples thereof include a methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group.
  • the monovalent hydrocarbon group represented by R 32 includes alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and alkylene groups such as vinyl and propenyl , Etc.
  • R 32 is preferably a methyl group or an ethyl group.
  • secondary amino group-containing diamine compound examples include, for example, compounds represented by the following formulas (d-8-1) to (d-8-4).
  • a secondary amino group containing diamine compound may be used individually by 1 type, and may be used combining 2 or more types.
  • the use ratio thereof is preferably 2 mol% or more, more preferably 3 to 90 mol%, and more preferably 5 to 70 mol% with respect to all diamines. It is further preferable to
  • aliphatic diamines such as 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), the following formula (d-11-1) to the formula (d-11-6)
  • a cycloaliphatic diamine such as a compound represented by each of p-phenylenediamine, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene
  • tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and ethylenediaminetetraacetic acid dianhydride; 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride, 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentylacetic acid dianhydride , 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5- Dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione,
  • the tetracarboxylic acid diester can be obtained by ring-opening the above-mentioned tetracarboxylic acid dianhydride using an alcohol such as methanol, ethanol or propanol.
  • the tetracarboxylic acid diester dihalide can be obtained, for example, by reacting the tetracarboxylic acid diester obtained above with a suitable chlorinating agent such as thionyl chloride.
  • bislactone compounds examples include endocyclic enol esters, exocyclic enol esters, endocyclic acyl imide esters, exocyclic acyl imide esters, oxime esters and the like.
  • Specific examples of the bislactone compound used for the synthesis include, for example, compounds represented by the following formulas (b-1) to (b-11).
  • a reaction product of an ⁇ , ⁇ -unsaturated compound and a diamine compound means an ⁇ , ⁇ -unsaturated compound and a diamine as monomers used for synthesis, as long as the effects of the present disclosure are not impaired. It is acceptable to use together with the compound other monomers other than the ⁇ , ⁇ -unsaturated compound and the diamine compound.
  • the proportion of the other monomer (preferably tetracarboxylic acid dianhydride) to be used is preferably 40 mol% or less, preferably 30 mol% or less, based on the total amount of monomers used in the synthesis of polyenamine. More preferable.
  • the synthesis method of polyenamine is not particularly limited, it can be synthesized, for example, by vinyl nucleophilic substitution polymerization.
  • the synthesis reaction is preferably carried out in an organic solvent.
  • the organic solvent used for the reaction include aprotic polar solvents (N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc.), phenolic solvents (phenol, cresol etc.), Alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like can be mentioned.
  • the proportion of the organic solvent used is preferably such that the total amount of the ⁇ , ⁇ -unsaturated compound and the diamine compound is 0.1 to 50% by mass with respect to the total amount of the reaction solution.
  • the reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours.
  • the above reaction may be carried out in the presence of a catalyst such as trifluoroacetic acid, if necessary.
  • the reaction solution obtained by dissolving polyenamine When the reaction solution obtained by dissolving polyenamine is obtained by the above reaction, the reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or a precipitate obtained by pouring the reaction solution into a large amount of poor solvent Even if the polyenamine contained in the reaction solution is isolated using a known isolation method such as a method of drying under reduced pressure, a method of evaporating the reaction solution under reduced pressure using an evaporator, etc. Good.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the obtained polyenamine is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. .
  • 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 5 or less, more preferably 3 or less.
  • the polyenamine used for preparation of a liquid crystal aligning agent may be only 1 type, and may combine 2 or more types.
  • the content of polyenamine in the liquid crystal aligning agent is the total amount of polymer components contained in the liquid crystal aligning agent from the viewpoint of sufficiently enhancing the coatability to the substrate and improving the liquid crystal alignment and voltage holding ratio of the liquid crystal element.
  • the amount is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more.
  • the content of polyenamine is preferably 90% by mass or less, more preferably 80% by mass or less, and preferably 70% by mass or less based on all polymers contained in the liquid crystal aligning agent. More preferable.
  • the liquid crystal aligning agent of this indication may contain other components other than polyenamine as needed.
  • Other components are not particularly limited as long as the effects of the present disclosure are not impaired.
  • Specific examples of the other components include a polymer different from polyenamine (hereinafter, also referred to as “other polymer”), a compound having a crosslinkable group (hereinafter, also referred to as “crosslinkable group-containing compound”), Functional silane compounds, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, solvents and the like can be mentioned.
  • the blend ratio of the other components can be appropriately selected according to each compound, as long as the effects of the present disclosure are not impaired.
  • polymers can be used for the purpose of improving the solubility in solvents and electrical properties.
  • Other polymers include, for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polystyrene derivative, (styrene-maleimide) type
  • the polymer which has a polymer, a poly (meth) acrylate, etc. as a main frame is mentioned.
  • (meth) acrylate is meant to include acrylate and methacrylate.
  • another polymer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid crystal aligning agent of the present disclosure includes polyamic acid, polyamic acid ester and polyimide as other polymers.
  • the liquid crystal alignment agent of the present disclosure includes polyorganosiloxane and (styrene-maleimide) based on other polymers. It is more preferable to contain at least one selected from the group consisting of polymers.
  • the (styrene-maleimide) polymer is preferably a (styrene-phenylmaleimide) polymer.
  • the blending ratio of the other polymers should be 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of polyenamine contained in the liquid crystal aligning agent. Is preferable, and 30 to 500 parts by mass is more preferable.
  • the polymer component of the liquid crystal aligning agent As preferred embodiments of the polymer component of the liquid crystal aligning agent, the following (I) to (IV) can be mentioned.
  • the polymer component comprises polyenamine and a (styrene-phenylmaleimide) polymer.
  • the aspect which a polymer component consists of polyenamine is particularly preferable in that a liquid crystal element excellent in coating properties, liquid crystal alignment property and electrical property can be obtained.
  • the liquid crystal aligning agent of the present disclosure includes at least one crosslinkable group selected from the group consisting of a cyclocarbonate group, an epoxy group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated bond group. You may contain the compound which it has (Hereafter, it is also mentioned a "crosslinkable group containing compound.”). The inclusion of the crosslinkable group-containing compound is preferable in that the adhesion of the liquid crystal alignment film to the substrate and the electrical characteristics and reliability of the liquid crystal element can be improved.
  • the crosslinkable group-containing compound has a polymerizable unsaturated bond group
  • examples of the polymerizable unsaturated bond group include a (meth) acryloyl group, an ethylenic carbon-carbon double bond, a vinylphenyl group and a vinyloxy group (CH 2 CHCH-O-), a vinylidene group, a maleimide group and the like are mentioned, and a cyclocarbonate group, an epoxy group or a (meth) acryloyl group is preferable in that it is highly reactive with light or heat.
  • the molecular weight of the crosslinkable group-containing compound is preferably 3,000 or less, more preferably 2,000 or less in terms of storage stability.
  • crosslinkable group-containing compound examples include, as a cyclocarbonate group-containing compound, for example, a compound represented by the following formula (11-1), a compound represented by the following formula (11-2), etc.
  • the compound having an epoxy group examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, 1,6-hexanediol diglycidyl ether, glycerin di Glycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N -Diglycidylaminomethyl) cyclohexane
  • Examples of the compound having a blocked isocyanate group include a compound represented by the following formula (11-5), a compound represented by the following formula (11-6), etc.
  • Examples of the compound having a (meth) acryloyl group include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the following formula (11-7)
  • Examples of the compound having an oxetanyl group include a compound represented by the following formula (11-9), a compound represented by the following formula (11-10), and the like.
  • an epoxy-group containing compound the epoxy-group-containing polyorganosiloxane of WO2009 / 096598 can be used.
  • the blending ratio is preferably 40 parts by mass or less with respect to a total of 100 parts by mass of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it to 30 parts by mass.
  • a crosslinkable group containing compound can be used individually by 1 type or in combination of 2 or more types.
  • the liquid crystal aligning agent of the present disclosure is prepared as a composition in the form of a solution in which the polymer component, and the component that is optionally blended, is preferably dissolved in an organic solvent.
  • organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like.
  • the solvent component may be one of these or a mixed solvent of two or more.
  • the solvent component of the liquid crystal aligning agent of the present disclosure is at least one member selected from the group consisting of compounds represented by the following formulas (E-1) to (E-5), and at 1 atm.
  • a solvent having a boiling point of 180 ° C. or less (hereinafter, also referred to as “specific solvent”) may be used.
  • a specific solvent as at least a part of the solvent component, it is possible to obtain a liquid crystal element excellent in liquid crystal alignment and electrical characteristics even when heating at the time of film formation is performed at a low temperature (for example, 200 ° C. or less). Preferred.
  • polyenamine is excellent in solubility in solvents, and therefore, even when a low boiling point solvent such as a specific solvent is used as a solvent component, coating properties on a substrate (suppression of film thickness unevenness and pinholes, coating area It is preferable in that the liquid crystal element can be obtained which is excellent in the linearity and flatness of the end portions and in which both of the liquid crystal alignment property and the electrical property are excellent.
  • R 41 is an alkyl group having 1 to 4 carbon atoms or R 40 -CO- (wherein R 40 is an alkyl group having 1 to 3 carbon atoms), and R 42 is a carbon atom
  • R 44 is an alkanediyl group having 1 to 4 carbon atoms.
  • R 45 and R 46 are each independently an alkyl group having 1 to 8 carbon atoms.
  • R 49 is a hydrogen atom or a hydroxyl group
  • R 50 is a divalent hydrocarbon group having 1 to 9 carbon atoms, or R 3 if the R 49 is a hydrogen atom;
  • R 49 is a hydroxyl group, it is a divalent hydrocarbon group having 1 to 9 carbon atoms, or a carbon number of 2 carbon atoms when R 49 is a hydroxyl group.
  • R 51 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent group having a hydrogen atom of the hydrocarbon group having 1 to 6 carbon atoms substituted with a hydroxyl group, Or a monovalent group having —CO— between carbon-carbon bonds of a hydrocarbon group having 2 to 6 carbon atoms
  • R 52 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • the specific solvent examples include propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether as a compound represented by the above formula (E-1) Partial ethers of polyhydric alcohols such as ethylene glycol monopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether: ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene Glycol monomethyl ether acetate, propylene glycol Polyhydric partial ester of an alcohol, such as glycol monomethyl ether acetate and the like; As a compound represented by the said Formula (E-2), cyclobutanone, cyclopentanone, cyclohex
  • the solvent component of the liquid crystal alignment agent may be composed only of the specific solvent, but may be a mixed solvent of another solvent other than the specific solvent and the specific solvent.
  • Other solvents include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, ⁇ -butyrolactone, ⁇ -butyrolactam, N, N-dimethylformamide, Besides highly polar solvents such as N, N-dimethylacetamide; 4-hydroxy-4-methyl-2-pentanone, butyl lactate, methyl methoxypropionate, ethyl ethoxy propionate, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isoamyl isobutyrate, diisopentyl Ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol,
  • a highly polar solvent can be used for the purpose of further improving the solubility and the leveling property.
  • hydrocarbon solvents that do not contain an amide structure can be used for the purpose of enabling application to plastic substrates and low temperature firing.
  • the content ratio of the specific solvent is preferably 20% by mass or more and 40% by mass or more based on the total amount of the solvent contained in the liquid crystal aligning agent. Is more preferable, 50 mass% or more is further preferable, and 80 mass% or more is particularly preferable.
  • the liquid crystal aligning agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment property and electrical property can be obtained even when the solvent component in the liquid crystal aligning agent is only a specific solvent.
  • the liquid crystal aligning agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment properties and electrical properties can be obtained even when it does not substantially contain N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • substantially free of NMP means that the content of NMP is preferably 5% by mass or less, more preferably 3% or less, based on the total amount of the solvent contained in the liquid crystal aligning agent. The content is at most mass%, more preferably at most 0.5 mass%.
  • the solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by mass.
  • the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film.
  • the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. There is a tendency.
  • the liquid crystal aligning film of this indication is formed of the liquid crystal aligning agent prepared as mentioned above.
  • the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above.
  • the operation mode of the liquid crystal in the liquid crystal element is not particularly limited.
  • TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type, FFS (Fringe) It can be applied to various modes such as Field Switching type, OCB (Optically Compensated Bend) type, and PSA type (Polymer Sustained Alignment).
  • the liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. Step 1 differs in the substrate used according to the desired operation mode. Steps 2 and 3 are common to each operation mode.
  • a liquid crystal aligning agent is coated on a substrate, and preferably a coated surface is formed to form a coating film on the substrate.
  • the substrate for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used.
  • a transparent conductive film provided on one surface of the substrate a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 -SnO 2 ), etc.
  • a TN type, STN type or VA type liquid crystal element two substrates provided with a patterned transparent conductive film are used.
  • a substrate provided with electrodes patterned in a comb shape and an opposite substrate provided with no electrodes are used.
  • the application of the liquid crystal alignment agent to the substrate is carried out preferably by offset printing, flexo printing, spin coating, roll coater method or ink jet printing on the electrode formation surface.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent.
  • the prebake temperature is preferably 30 to 200 ° C.
  • the prebake time is preferably 0.25 to 10 minutes.
  • a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure in the polymer component.
  • the baking temperature (post-baking temperature) at this time is preferably 80 to 250 ° C., more preferably 80 to 200 ° C.
  • the post bake time is preferably 5 to 200 minutes.
  • polyenamine has good solubility in a specific solvent, and is excellent in liquid crystal alignment and electrical properties even when the post-baking temperature is, for example, 200 ° C. or less, preferably 180 ° C. or less, more preferably 160 ° C. or less.
  • a liquid crystal element can be obtained.
  • the film thickness of the film thus formed is preferably 0.001 to 1 ⁇ m.
  • ⁇ Step 2 Alignment treatment>
  • a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is carried out.
  • the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.
  • the orientation treatment the coating formed on the substrate is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon or cotton, or the coating formed on the substrate is irradiated with light.
  • a photoalignment treatment or the like which imparts a liquid crystal alignment ability to the coating film.
  • the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but in order to further enhance the liquid crystal alignment ability
  • the film may be subjected to orientation treatment.
  • a liquid crystal alignment film suitable for a vertical alignment type liquid crystal element can also be suitably used for a PSA type liquid crystal element.
  • the light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film after the pre-baking step but before the post-baking step, a pre-baking step and a post-baking step At least one of them can be performed by a method of irradiating the coating film while heating the coating film, or the like.
  • the radiation to be applied to the coating film it is possible to use, for example, ultraviolet light and visible light including light of a wavelength of 150 to 800 nm. Preferably, it is ultraviolet light containing light of a wavelength of 200 to 400 nm. If 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 these may be performed in combination.
  • the irradiation direction in the case of non-polarized radiation is oblique.
  • a low pressure mercury lamp for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be mentioned.
  • the radiation dose is preferably 400 to 50,000 J / m 2 , more preferably 1,000 to 20,000 J / m 2 .
  • an organic solvent eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate etc.
  • Step 3 Construction of Liquid Crystal Cell> Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell.
  • a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell.
  • two substrates are disposed opposite to each other with a gap so that the liquid crystal alignment film faces each other, and peripheral portions of the two substrates are bonded using a sealing agent.
  • a liquid crystal is injected and filled in a cell gap surrounded by a sealing agent to seal the injection hole, a method by an ODF method, and the like.
  • the sealing agent for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.
  • liquid crystals examples include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
  • 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.
  • a liquid crystal cell is constructed in the same manner as described above except that a photopolymerizable compound is injected or dropped together with the liquid crystal. After that, light is irradiated to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.
  • the voltage applied here may be, for example, 5 to 50 V direct current or alternating current.
  • the light to be irradiated for example, ultraviolet light and visible light containing light of a wavelength of 150 to 800 nm can be used, but ultraviolet light containing light of a wavelength of 300 to 400 nm is preferable.
  • a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example.
  • the light irradiation amount is preferably 1,000 to 200,000 J / m 2 , and more preferably 1,000 to 100,000 J / m 2 .
  • a polarizing plate is attached to the outer surface of the liquid crystal cell to form a liquid crystal element.
  • the polarizing plate include a polarizing plate in which a polarizing film called “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate consisting of the H film itself.
  • the substrate In the manufacturing process of the liquid crystal element, the substrate may be left as it is (drawn) after forming the liquid crystal alignment film on the substrate due to mechanical trouble or tact adjustment. At that time, moisture in the air may be adsorbed or absorbed by the liquid crystal alignment film, and the electric characteristics of the constructed liquid crystal element may be deteriorated, which may cause display unevenness and the like.
  • the liquid crystal alignment film obtained by using the above-mentioned liquid crystal alignment agent is a liquid crystal having good electric characteristics (a good resistance to placing) even when the substrate is left with the liquid crystal alignment film formed. It is excellent in the point which can obtain an element.
  • the liquid crystal element of the present disclosure can be effectively applied to various applications.
  • the present invention can be applied to various display devices such as liquid crystal televisions and information displays, light control films, retardation films and the like.
  • the liquid crystal device of the present disclosure is also suitably used for a liquid crystal device using a dye as a colorant for the color filter layer.
  • a dye a known dye that can be used for a liquid crystal element can be used.
  • the contents of this indication are not limited to the following examples.
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods. ⁇ Weight average molecular weight, number average molecular weight and molecular weight distribution> Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. Moreover, the molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.
  • GPC column Tosoh Corp.
  • TSKgel GRC XLII Mobile phase: lithium bromide and phosphoric acid containing N, N-dimethylformamide solution column temperature: 40 ° C. Flow rate: 1.0 mL / min Pressure: 68 kgf / cm 2
  • Synthesis Examples 2-14 to 2-19 The same operation as in Synthesis Example 2-1 is carried out except that the type and amount of monomers to be used are changed as shown in Table 1 below, to obtain polyamic acids (polymers (C-1) to (C-6), respectively. ) Was obtained.
  • Synthesis Example 3-2 By performing the same operation as in Synthesis Example 3-1 except that the side chain carboxylic acid (ca-2) shown below is used instead of the side chain carboxylic acid (ca-1) in Synthesis Example 3-1 An NMP solution containing the polymer (C-8) was obtained.
  • Synthesis Example 3-3 By performing the same operation as in Synthesis Example 3-1 except that the side chain carboxylic acid (ca-3) shown below is used instead of the side chain carboxylic acid (ca-1) in Synthesis Example 3-1 An NMP solution containing the polymer (C-9) was obtained.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC was 30,000, and the molecular weight distribution Mw / Mn was 2.
  • Example 1 Preparation of Liquid Crystal Alignment Agent (AL-1)
  • the solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent (AL-1).
  • the liquid crystal aligning agent (AL-1) prepared above is coated on a glass substrate using a spinner, and a hot plate at 80 ° C. The film was prebaked for 1 minute, and then the inside of the chamber was heated (post-baked) in a 230 ° C. oven purged with nitrogen for 30 minutes to form a coating having an average film thickness of 0.1 ⁇ m. This coated film was observed with a microscope with a magnification of 100 times and 10 times to examine the presence of film thickness unevenness and pinholes.
  • the evaluation is “good (A)” when neither film thickness unevenness nor pinhole is observed even when observed with a 100 ⁇ microscope, and at least one of film thickness unevenness and pinholes with a 100 ⁇ microscope Although observed, when both the film thickness unevenness and the pinhole were not observed with the 10 ⁇ microscope, “OK (B)”, and at least one of the film thickness unevenness and the pinhole was clearly observed with the 10 ⁇ microscope. When it observed, it was set as "defect (C).” In this example, neither the film thickness unevenness nor the pinhole was observed even with a 100 ⁇ microscope, and the coatability was evaluated as “good (A)”.
  • the coatability on the edge portion was evaluated.
  • the liquid crystal aligning agent (AL-1) prepared above was applied on a transparent electrode-coated glass substrate made of an ITO film using a printing machine for applying a liquid crystal alignment film, and dried as described above. .
  • Observing the shape and flatness of the edge portion “Good (A)” when the linearity is high and a flat surface, “Good (B)” when the linearity is high but there are irregularities, and there are irregularities, And when there was liquid return from the edge (the linearity is low), it was regarded as “defect (C)". As a result, in this example, it was judged as "good (A)".
  • the evaluation is “good (A)” when the measured values at four points are within ⁇ 25 ⁇ with respect to the average film thickness ⁇ and a uniform film thickness is obtained, ⁇ 25 ⁇ with respect to the average film thickness ⁇ If all the measured values at four points were within the range of ⁇ 50 ⁇ with respect to the average film thickness ⁇ although there were measured values outside the range of “good (B)”, with respect to the average film thickness ⁇ When there was a measured value out of the range of ⁇ 50 ⁇ and the variation of the measured value was large, it was regarded as “defect (C)”. As a result, in this Example, it was evaluation of "good (A)."
  • the liquid crystal aligning agent (AL-1) prepared above was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 ⁇ m.
  • the coating film was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth.
  • ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film.
  • a pair (two sheets) of substrates having a liquid crystal alignment film was formed.
  • An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 ⁇ m is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured.
  • liquid crystal injection port After filling a nematic liquid crystal (manufactured by Merck, MLC-6221) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and both sides of the substrate are polarized.
  • a horizontal alignment type liquid crystal display element was manufactured by bonding the plates together.
  • VHR voltage holding ratio
  • a liquid crystal display element (referred to as "element A”) was produced by the same method as in "3. Production of rubbing horizontal type liquid crystal display element” described above.
  • the liquid crystal display element (“element” is referred to as “element” in the same manner as the “3. manufacture of a rubbing horizontal type liquid crystal display element” above) without exposing another pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured. Subsequently, the pretilt angles of the two liquid crystal display elements are determined according to the method described in Non-patent document (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19. p2013 (1980)), He-Ne.
  • ⁇ (( ⁇ 1 ⁇ 2) / ⁇ 1) ⁇ 100 (2)
  • ⁇ 1 is the pretilt angle of the element B
  • ⁇ 2 is the pretilt angle of the element A.
  • Examples 5 to 7 and 14 to 20 and Comparative Example 1 Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing a rubbing horizontal type liquid crystal display element similarly to Example 1 and performing various evaluations The The results are shown in Table 3 below. In Table 3 below, the observation results of film thickness unevenness and pinholes are shown in the column of "coating properties", the observation results of edge portions are shown in the column of "edge shape", and evaluation results based on film thickness variations are shown. It is shown in the column of "film thickness uniformity”. In Examples 6 and 7, a crosslinking agent was blended together with the polymer component. In Table 2, "-" means that the polymer in the corresponding column was not used.
  • Example 2 ⁇ Manufacture and evaluation of optical FFS liquid crystal display device>
  • Example 2 Preparation of Liquid Crystal Alignment Agent (AL-2) The same solvent composition as in Example 1 except that the polymer to be used was changed to 100 parts by mass of the polymer (P-2) and 50 parts by mass of the polymer (C-9) And liquid crystal aligning agent (AL-2) was prepared by solid content concentration.
  • A-2 Liquid Crystal Alignment Agent
  • the coating property was evaluated in the same manner as in Example 1 except that (AL-2) was used instead of (AL-1) as the liquid crystal aligning agent.
  • the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.
  • the coating film surface is irradiated with ultraviolet light of 1,000 J / m 2 including a linearly polarized light emission line of 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform photoalignment treatment, and liquid crystal alignment on the substrate A film was formed.
  • a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 ⁇ m, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed.
  • the substrates were superposed and pressure-bonded so that the projection directions of the polarization axes on the substrate surface at this time were antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour.
  • nematic liquid crystal manufactured by Merck, MLC-7028
  • a liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell.
  • the polarizing plates are attached to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and at an angle of 90 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface.
  • the liquid crystal display element was manufactured by this.
  • one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above-mentioned "3.
  • Production of optical FFS liquid crystal display element A liquid crystal display device (referred to as “device A”) was manufactured by the method of In addition, the liquid crystal display element (the “element” is selected by the same method as the above “3. manufacture of the optical FFS liquid crystal display element” without exposing the other pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".
  • Comparative Example 2 Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain a liquid crystal aligning agent (BL-2). Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using a liquid crystal aligning agent (BL-2), it manufactures an optical FFS type liquid crystal display element similarly to Example 2, and variously I made an evaluation. The results are shown in Table 3 below.
  • Example 3 ⁇ Manufacture and evaluation of VA type liquid crystal display device> [Example 3] 1. Preparation of Liquid Crystal Alignment Agent (AL-3) The same solvent composition as in Example 1 except that the polymer used was changed to 100 parts by mass of polymer (P-3) and 300 parts by mass of polymer (C-6). And liquid crystal aligning agent (AL-3) was prepared by solid content concentration. 2. Evaluation of Coating Properties Coating properties were evaluated in the same manner as in Example 1 except that (AL-3) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.
  • VA-Type Liquid Crystal Display Device The liquid crystal aligning agent (AL-3) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and the hot plate is used at 80 ° C. Pre-baking was performed for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 ⁇ m. By repeating this operation, a pair of substrates (two sheets) having a liquid crystal alignment film was formed.
  • An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 ⁇ m is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured. Next, after filling a negative type liquid crystal (MLC-6608, manufactured by Merck Ltd.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and both sides of the substrate are sealed.
  • MLC-6608 negative type liquid crystal
  • one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above-mentioned “3.
  • a liquid crystal display element (referred to as "element A”) was manufactured by a method.
  • a liquid crystal display element (“element B”) is formed by the same method as “3.
  • production of a VA type liquid crystal display element” without exposing the other pair of substrates (two sheets) to the NMP atmosphere. ”) was manufactured.
  • evaluation of the pull-through resistance was performed in the same manner as in Example 1 above.
  • the withdrawal resistance was an evaluation of "A”.
  • Example 4 and Comparative Example 3 Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing a VA type liquid crystal display element similarly to Example 3 and performing various evaluations . The results are shown in Table 3 below.
  • Example 9 ⁇ Manufacture and evaluation of PSA type liquid crystal display device> [Example 9] 1. Preparation of Liquid Crystal Alignment Agent (AL-9) Same solvent composition as Example 1 except that the polymer used was changed to 200 parts by mass of Polymer (P-6) and 50 parts by mass of Polymer (C-7) A liquid crystal aligning agent (AL-9) was prepared at a solid content concentration. 2. Evaluation of Coating Property The coating property was evaluated in the same manner as in Example 1 except that (AL-9) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.
  • liquid crystal compound represented by the following formula (L1-1) was represented by 5% by mass with respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Ltd.), and by the following formula (L2-1)
  • the liquid crystal composition LC1 was obtained by adding 0.3 mass% of the photopolymerizable compounds and mixing them.
  • a liquid crystal alignment film printing machine (Nippon Photography printing) on each electrode surface of two glass substrates each having a conductive film consisting of an ITO electrode, the liquid crystal alignment agent (AL-9) prepared above (Presto) for 2 minutes on a hot plate at 80 ° C. to remove the solvent, and then for 10 minutes on a hot plate at 230 ° C. (post bake).
  • a coating having a thickness of 0.06 ⁇ m was formed.
  • the coated films were subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair (two sheets) of substrates having a liquid crystal alignment film.
  • the pattern of the used electrode is the same pattern as the electrode pattern in the PSA mode.
  • an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 ⁇ m is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces one another. It was pressure-bonded together and the adhesive was cured.
  • the liquid crystal composition LC1 prepared above was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell.
  • an AC 10V frequency 60Hz was applied between the conductive film of the liquid crystal cell, in a state where the liquid crystal is driven, using an ultraviolet irradiation apparatus using a metal halide lamp as a light source, the irradiation amount of 100,000J / m 2 It irradiated ultraviolet rays at.
  • this irradiation amount is the value measured using the actinometer measured by wavelength 365 nm reference
  • polarizing plates are attached to both outer sides of the substrate so that the polarization directions thereof are orthogonal to each other and at an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface.
  • a liquid crystal display device was manufactured.
  • one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, the same as the above-mentioned "4.
  • Production of PSA type liquid crystal display element" A liquid crystal display element (referred to as "element A”) was manufactured by a method. Further, a liquid crystal display element (“element B”) is prepared by the same method as the “4. PSA type liquid crystal display element” described above without exposing another pair of substrates (two sheets) to the NMP atmosphere. ”) was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".
  • Examples 10 and 11 and Comparative Example 5 Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Further, using the obtained liquid crystal aligning agent, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1, and in the same manner as in Example 9, a PSA type liquid crystal display element is produced. Various evaluations were performed in the same manner. The evaluation results are shown in Table 3 below. In Examples 10 and 11, a crosslinking agent was blended with the polymer component.
  • Example 8 ⁇ Manufacture and evaluation of vertical light type liquid crystal display element> [Example 8] 1. Preparation of Liquid Crystal Alignment Agent (AL-8) The same solvent composition as in Example 1 except that the polymer used was changed to 200 parts by mass of polymer (P-7) and 50 parts by mass of polymer (C-8) And liquid crystal aligning agent (AL-8) was prepared at solid content concentration. 2. Evaluation of Coatability The coatability was evaluated in the same manner as in Example 1 except that (AL-8) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.
  • liquid crystal aligning agent (AL-8) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 ⁇ m.
  • this coated film surface is irradiated with polarized ultraviolet light of 1,000 J / m 2 containing an emission line of 313 nm from a direction inclined 40 ° from the substrate normal to obtain liquid crystal alignment ability. Granted. The same operation was repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.
  • An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 ⁇ m is applied by screen printing to the outer periphery of the surface having a liquid crystal alignment film of one of the above substrates, and then the liquid crystal alignment film surfaces of a pair of substrates are made to face each other.
  • the polarizing plates are bonded to both outer surfaces of the substrate so that the polarization directions are orthogonal to each other and at an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface.
  • the liquid crystal display element was manufactured by this.
  • one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above "3.
  • a liquid crystal display device (referred to as “device A”) was manufactured by the method of
  • the liquid crystal display element (the “element” is formed by the same method as the “3. manufacture of the vertical light type liquid crystal display element” described above without exposing another pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".
  • Examples 12, 13 and Comparative Examples 4, 6 Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing an optical perpendicular type liquid crystal display element similarly to Example 8 and performing various evaluations The The results are shown in Table 3 below. In Examples 12 and 13, a crosslinking agent was blended together with the polymer component.
  • Example 21 to 23 a liquid crystal aligning agent (BL-) was prepared in the same manner as in Examples 21 to 23 except that 300 parts by mass of polymer (C-5) was used instead of 200 parts by mass of polymer (P-6). 7) to (BL-9) were prepared respectively (see Table 4 below). Moreover, while evaluating the coating property of a liquid crystal aligning agent like Example 1 except the point which changed the liquid crystal aligning agent to be used, and the point which changed post-baking temperature from 230 degreeC to 200 degreeC, Example 9 In the same manner as in the above, a PSA type liquid crystal display device was manufactured and various evaluations were performed. The results are shown in Table 5 below. In Table 5, insufficient solubility of the polymer in the solvent was observed, and the items which could not be evaluated by this were indicated as “ ⁇ ” (the same applies to Comparative Examples 10 and 11).
  • a liquid crystal aligning agent (BL-10) was prepared in the same manner as in Example 24 except that the polymer composition was changed as shown in Table 4 below. Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light VA type liquid crystal display device was manufactured and evaluated in the same manner as in 8. The results are shown in Table 5 below.
  • Example 11 A liquid crystal aligning agent (BL-11) was prepared in the same manner as in Example 25 except that the polymer composition in Example 25 was changed as shown in Table 4 below. Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light FFS-type liquid crystal display device was manufactured in the same manner as 2 and various evaluations were performed. The results are shown in Table 5 below.
  • the numerical value of the solvent composition represents the mass ratio (mass%) to the total amount of the solvent used for preparation of the liquid crystal aligning agent.
  • the abbreviation of the solvent has the following meaning.
  • CHN cyclohexanone DIBK: diisobutyl ketone
  • BC butyl cellosolve
  • PGME propylene glycol monomethyl ether
  • PGMEA propylene glycol monomethyl ether acetate
  • EDM diethylene glycol methyl ethyl ether
  • the dye can be suitably used even when a color filter layer of a liquid crystal element is formed using a dye having poor heat resistance as a colorant.
  • the evaluation of the edge shape is “ B "and was inferior to the example.
  • the evaluation of film thickness uniformity was also "B”.
  • the evaluation of the voltage holding ratio was “C”, and in Comparative Example 4, it was “B”.
  • the solubility was insufficient with respect to the solvent composition not containing the amide polar solvent (NMP), and a good result was not obtained (comparative examples 7 to 11). . From these results, it was found that the liquid crystal aligning agent containing polyenamine is excellent in coating property, liquid crystal alignment property and voltage holding ratio. In addition, the liquid crystal aligning agent containing polyenamine was also excellent in retention resistance.

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Abstract

Selon l'invention, une polyénamine est incorporée en tant que composant polymère à un agent d'alignement de cristaux liquides. Selon un mode de réalisation de l'invention, la polyénamine consiste en un produit de réaction d'un composé α，β－insaturé possédant à l'intérieur de chaque molécule une sorte de sous-structure représentée par la formule (1) ou la formule (2), et d'un composé diamine. Dans les formules (1) et (2), Ｘ１ représente un groupe carbonyle ou un groupe sulfonyl, Ｌ１ représente un groupe partant qui part sous l'effet d'une réaction avec le composé diamine, Ｌ２ représente un atome d'oxygène ou un atome de soufre, et Ｒ５ représente un atome d'hydrogène ou un groupe organique monovalent d'au moins un atome de carbone.
PCT/JP2018/046723 2018-01-25 2018-12-19 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément à cristaux liquide ainsi que procédé de fabrication de celui-ci Ceased WO2019146319A1 (fr)

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