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WO2017119461A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant Download PDF

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Publication number
WO2017119461A1
WO2017119461A1 PCT/JP2017/000178 JP2017000178W WO2017119461A1 WO 2017119461 A1 WO2017119461 A1 WO 2017119461A1 JP 2017000178 W JP2017000178 W JP 2017000178W WO 2017119461 A1 WO2017119461 A1 WO 2017119461A1
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Prior art keywords
group
liquid crystal
component
aligning agent
carbon atoms
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PCT/JP2017/000178
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English (en)
Japanese (ja)
Inventor
玲久 小西
大輝 山極
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to CN201780015102.2A priority Critical patent/CN109073935B/zh
Priority to JP2017560415A priority patent/JP6919574B2/ja
Priority to KR1020187022535A priority patent/KR102789943B1/ko
Publication of WO2017119461A1 publication Critical patent/WO2017119461A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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 invention relates to a liquid crystal alignment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.
  • Liquid crystal display elements used in liquid crystal televisions, navigators, smartphones, and the like are usually provided with a liquid crystal alignment film for controlling the alignment state of the liquid crystals.
  • the liquid crystal alignment film has a function of controlling the alignment of liquid crystal molecules in a certain direction in a liquid crystal display element or a retardation plate using a polymerizable liquid crystal.
  • a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on the surfaces of a pair of substrates. In this case, liquid crystal molecules are aligned in a certain direction with a pretilt angle by the liquid crystal alignment film, and respond by applying a voltage to an electrode provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the orientation change due to the response of the liquid crystal molecules.
  • liquid crystal alignment film a polyimide-based liquid crystal alignment film obtained by applying a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it is mainly used. It is used.
  • a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide
  • a high voltage holding ratio a small residual charge when a DC voltage is applied, and / or Alternatively, characteristics such as quick relaxation of accumulated residual charges due to DC voltage are required, but in recent years, a material having a high voltage holding ratio is particularly required for power saving of liquid crystal display elements.
  • liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels.
  • a backlight with a large calorific value may be used.
  • the liquid crystal alignment film is required to have high stability against light from the backlight.
  • a burn-in defect also called line burn-in
  • the liquid crystal alignment film in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time.
  • an alignment film having a high voltage holding capability is further required.
  • a liquid crystal aligning agent obtained by adding various crosslinking agents to polyamic acid is used, a liquid crystal display element having excellent voltage holding characteristics can be obtained, but the liquid crystal aligning property may be impaired.
  • the effect of the crosslinking agent may not be sufficiently exhibited depending on the combination with the polymer species contained in the liquid crystal aligning agent, and the voltage holding ratio may be insufficient.
  • the gist of the present invention is as follows.
  • a liquid crystal aligning agent comprising the following component (A), component (B), component (C) and an organic solvent.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group represented by the following formula (1), at least one of which is a protecting group that is replaced with a hydrogen atom by heat.
  • R 3 , R 4 , and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms that may have a substituent.
  • D is a thermally leaving group which is a protecting group that is replaced by a hydrogen atom by heat.
  • X 1 is a tetravalent organic group represented by the following formula (X-1)
  • Y 1 is a divalent organic group
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Each of A 1 and A 2 independently represents a hydrogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. Alkynyl group.
  • Component A compound containing two or more crosslinkable functional groups.
  • the liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film that maintains the voltage holding ratio even after being exposed to light irradiation, without impairing the liquid crystal aligning property over a long period of time.
  • the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can provide the outstanding display used for a liquid crystal television, a smart phone, a car navigation etc.
  • Component (A) contained in the liquid crystal aligning agent of the present invention includes a tetracarboxylic acid derivative component, a diamine compound having a structure of the following formula [A-1], a diamine having a structure of the following formula [A-2], A polyimide precursor obtained using a diamine component containing at least one diamine compound selected from diamine compounds having the structure of the following formula [A-3] and at least one polymer selected from polyimides (hereinafter referred to as specific (Also referred to as polymer (A)).
  • R 1 , R 2 and A are the same as defined above.
  • at least one or both of R 1 and R 2 is a thermally leaving group that is a protecting group that is replaced with a hydrogen atom by heat.
  • the thermal leaving group is preferably a protecting group that is not released at room temperature, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of storage stability of the liquid crystal aligning agent. is there.
  • thermally leaving group a group represented by the following formula (1) or a 9-fluorenylmethoxycarbonyl group is preferable.
  • A is a divalent group consisting of a single bond or a hydrocarbon group having 1 to 4 carbon atoms, preferably an alkylene group. From the viewpoint of elimination temperature, a tert-butoxycarbonyl group is preferred.
  • diamine having a structure represented by the above formula [A-1] in the molecule include diamines represented by the following formula [A-1-1].
  • R 1 and R 2 are the same as in the formula [A-1], including preferred examples thereof.
  • the two n's are each independently an integer of 0 to 3, and are preferably 0 or 1 and more preferably 1 in view of availability of raw materials.
  • the amino group (—NH 2 ) in each benzene ring may be any of ortho, meta, or para with respect to the bonding position of the alkylene group. From the viewpoint of ease of polymerization and polymerization reactivity, the meta position or the para position is preferable, and the para position is more preferable.
  • Preferred examples of the diamine represented by the formula [A-1-1] include the following compounds.
  • R 3 and R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.
  • D is a thermally leaving group which is a protecting group that can be replaced by a hydrogen atom by heat, and includes the preferred embodiment and is as defined in the above formula [A-2].
  • a tert-butoxycarbonyl group is preferable.
  • a 1 and A 5 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms. From the viewpoint of reactivity with the functional group in the sealing agent, a single bond or a methylene group is preferable.
  • a 2 and A 4 are alkylene groups having 1 to 5 carbon atoms, preferably a methylene group or an ethylene group.
  • a 3 is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group. From the viewpoint of reactivity with the functional group in the sealant, a methylene group or an ethylene group is preferable.
  • B 1 and B 2 are each independently a single bond, —O—, —NH—, —NMe—, —C ( ⁇ O) —, —C ( ⁇ O) O—, —C ( ⁇ O) NH—, —C ( ⁇ O) NMe—, —OC ( ⁇ O) —, —NHC ( ⁇ O) —, or —N (Me) C ( ⁇ O) —.
  • D 1 is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. From the viewpoint of deprotection temperature, a tert-butoxycarbonyl group is preferred.
  • a is 0 or 1;
  • diamine represented by the formula (A-2-2) include the following formulas (2-1) to (2-21).
  • Me represents a methyl group
  • D 2 represents a tert-butoxycarbonyl group.
  • the formulas (2-1) to (2-4) are more preferable, and the formula (2-1) is particularly preferable.
  • the diamine having the structure represented by the above formula [A-3] those represented by the following formula [A-3-1] or the following formula [A-3-2] are particularly preferable.
  • the cases represented by the following formula [A-3-3] and the following formula [A-3-4] are particularly preferable because the liquid crystal alignment property of the obtained liquid crystal alignment film becomes high.
  • a 1 , A 5 , B 1 , and B 2 are the same as those described in Formula [A-2-1], including preferred examples. , A 1 , A 5 , B 1 and B 2 .
  • Each R 5 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. From the viewpoint of liquid crystal orientation, R 5 is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.
  • a 6 is a single bond or an alkylene group having 1 to 6 carbon atoms. From the viewpoint of liquid crystal alignment, a single bond, a methylene group, an ethylene group, or a propylene group is preferable, and a single bond or a methylene group is more preferable.
  • D 1 is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group, and a tert-butoxycarbonyl group is preferred from the viewpoint of deprotection temperature.
  • a is 0 or 1;
  • a 6 , R 5, and D 1 is, according to the preferred examples are also the formula [A-2-1], A 6 , R 5 , and it is the same definition as D 1.
  • Specific examples include the following formulas (3-1) to (3-5).
  • D 2 represents a tert-butoxycarbonyl group.
  • the formulas (3-1) to (3-4) are more preferable, and the formula (3-1) is particularly preferable.
  • diamine component used for the component (A) contained in the liquid crystal aligning agent of the present invention examples include diamines having a structure represented by the above formulas [A-1], [A-2] and [A-3]. Other diamines can be used together with at least one diamine selected.
  • Examples of other diamines include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4 ' -Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-d
  • diamine compounds used for the component (A) contained in the liquid crystal aligning agent of the present invention are the solubility of the component (A) in the solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal aligning property when used as a liquid crystal aligning film. Depending on the characteristics such as voltage holding ratio and accumulated charge, one or more kinds can be used.
  • the tetracarboxylic acid derivative component for producing the component (A) contained in the liquid crystal aligning agent of the present invention includes not only tetracarboxylic dianhydride but also tetracarboxylic acid and tetracarboxylic acid that are tetracarboxylic acid derivatives thereof.
  • Acid dihalides, tetracarboxylic acid dialkyl esters or tetracarboxylic acid dialkyl ester dihalides can also be used. Among them, it is preferable to use at least one selected from tetracarboxylic dianhydrides represented by the following formula [4] and tetracarboxylic dialkyl esters which are derivatives thereof.
  • the tetracarboxylic dianhydride represented by the following formula [4] and derivatives thereof are collectively referred to as a specific tetracarboxylic acid component.
  • Z represents at least one structure selected from the group consisting of the following formulas [4a] to [4q].
  • Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.
  • Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group.
  • Z is, among others, from the viewpoint of ease of synthesis and ease of polymerization reactivity in producing a polymer, the formula [4a], the formula [4c] to the formula [4g], the formula [4k] to the formula [4m ] Or the formula [4p] is preferable. More preferable is the formula [4a], the formula [4e] to the formula [4g], the formula [4l], the formula [4m], or the formula [4p]. Particularly preferred is [4a], [4e], [4f], [4l], [4m] or [4p].
  • the specific tetracarboxylic acid component in component (A) is preferably from 50 to 100 mol%, particularly preferably from 70 to 100 mol%, particularly from 80 to 100 mol%, in 100 mol% of all tetracarboxylic acid derivative components. preferable.
  • the specific tetracarboxylic acid component depends on the properties such as the solubility of the specific polymer (A) in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal in the case of the liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. One type or two or more types can also be used.
  • tetracarboxylic acid components other than the specific tetracarboxylic acid component can also be used.
  • examples of other tetracarboxylic acid components include the following tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
  • tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenone Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1, 3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3 -Dicar
  • the other tetracarboxylic acid components have characteristics such as the solubility of the specific polymer (A) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal aligning property when the liquid crystal aligning film is used, the voltage holding ratio, and the accumulated charge. Depending on the situation, one kind or a mixture of two or more kinds may be used.
  • the component (B) contained in the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (2) and an imidized polymer of the polyimide precursor. (Hereinafter also referred to as the specific polymer (B)).
  • X 1 , Y 1, R 1, A 1 to A 2 are as defined above.
  • R 1 is preferably a hydrogen atom or a methyl group, a hydrogen atom is particularly preferred.
  • a 1 to A 2 are preferably a hydrogen atom or a methyl group.
  • R 1 Specific examples of the alkyl group for R 1 include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Etc. From the viewpoint of ease of imidization by heating, R 1 is preferably a hydrogen atom or a methyl group.
  • a preferable content ratio of the structural unit (2) is 5 to 90 mol%, more preferably 10 to 90 mol%, still more preferably 10 to 80 mol% in the same polymer.
  • the polymer of (B) component may have a structural unit of following formula (3) other than the structural unit represented by the said Formula (2).
  • the component (B) of the present invention may be a polymer having a structural unit represented by the formula (2) and a structural unit represented by the formula (3), and a polymer having a structural unit represented by the formula (2).
  • a mixture of the polymer and a polymer having the structural unit of the formula (3) may be used, but the former is preferable.
  • the content of the structural unit of the formula (3) contained in the polymer of the component (B) is 5 to 90 mol% in the polymer, preferably 10 to 90 mol%, preferably 20 to 90 mol%. More preferred.
  • X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. X 2 is two or more types may be mixed. Specific examples of X 2 include the following formulas (X-2) to (X-44).
  • R 8 to R 11 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group or a phenyl group. It is.
  • R 8 to R 11 have a bulky structure, the liquid crystal orientation may be lowered, so a hydrogen atom, a methyl group or an ethyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.
  • X 2 preferably contains a structure selected from (X-2) to (X-14) in view of availability of monomers.
  • X 2 preferably has a structure consisting only of an aliphatic group such as (X-2) to (X-7) and (X-10).
  • X-2) is more preferred.
  • X 2 is more preferably represented by the following formula (X2-1) or (X2-2) in order to exhibit good liquid crystal alignment.
  • a 1 and A 2 each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. Or an alkynyl group having 2 to 10 carbon atoms and an alkynyl group having 2 to 10 carbon atoms which may have a substituent.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.
  • alkenyl group examples include those obtained by replacing one or more CH—CH structures present in the above alkyl group with C ⁇ C structures, and more specifically, vinyl groups, allyl groups, 1-propenyl groups.
  • Alkynyl groups include those in which one or more CH 2 —CH 2 structures present in the alkyl group are replaced with C ⁇ C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
  • the above alkyl group, alkenyl group, and alkynyl group may have a substituent, and may further form a ring structure by the substituent.
  • forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
  • substituents are halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls.
  • halogen group examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a phenyl group is mentioned as an aryl group which is a substituent. This aryl group may be further substituted with the other substituent described above.
  • the organooxy group which is a substituent can have a structure represented by OR.
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • organooxy group examples include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
  • organothio group which is a substituent
  • R examples include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
  • the organosilyl group as a substituent can have a structure represented by —Si— (R) 3 .
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
  • the acyl group as a substituent can have a structure represented by —C (O) —R.
  • R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
  • Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
  • As the ester group which is a substituent a structure represented by —C (O) O—R or —OC (O) —R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • the thioester group which is a substituent can have a structure represented by —C (S) O—R or —OC (S) —R.
  • R examples include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • the phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) 2 .
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the substituent amide group include —C (O) NH 2 , —C (O) NHR, —NHC (O) R, —C (O) N (R) 2 , —NRC (O) R.
  • the structure represented by can be shown.
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
  • Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.
  • alkenyl group as a substituent examples include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
  • alkynyl group that is a substituent examples include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
  • the reactivity of the amino group and the liquid crystal orientation may be lowered.
  • a 1 and A 2 a hydrogen atom or a carbon atom that may have a substituent is 1
  • An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.
  • Y 1 is a divalent organic group derived from diamine, and examples thereof include the following Y-1 to Y-118.
  • Y 1 is more preferably at least one selected from structures represented by the following formulas (5) and (6) from the viewpoint of the liquid crystal alignment property and the pretilt angle of the obtained liquid crystal alignment film.
  • R 12 is a single bond or a divalent organic group having 1 to 30 carbon atoms
  • R 13 is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms
  • a is R is an integer of 1 to 4, and when a is 2 or more, R 12 and R 13 may be the same or different
  • R 14 in formula (6) is a single bond, —O—, —S—. , —NR 15 —, an amide bond, an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms
  • R 15 is a hydrogen atom or a methyl group.
  • Formula (5) and Formula (6) include the following structures.
  • High structural linearity since it is possible to enhance the orientation of the liquid crystal when the liquid crystal alignment film, as Y 1 is, Y-7, Y-21 , Y-22, Y-23, Y-25, Y-43, Y-44, Y-45, Y-46, Y-48, Y-63, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, Y- 99, Y-100 and Y-118 are more preferable.
  • the proportion of the above structure that can enhance the liquid crystal orientation is preferably 20 mol% or more of Y 1 as a whole, more preferably 60 mol% or more, and further preferably 80 mol% or more.
  • the side chain has a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of these in Y 1. .
  • Y 1 examples include Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y- 86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, Y-97 are preferred.
  • the proportion of the above structure for increasing the pretilt angle is preferably 1 to 30 mol%, more preferably 1 to 20 mol% of the entire Y 1 .
  • the polyimide precursor used in the present invention is obtained from a reaction between a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamic acid and polyamic acid ester.
  • the component (C) contained in the liquid crystal aligning agent of the present invention is a compound containing two or more crosslinkable functional groups.
  • the crosslinkable functional group include, but are not limited to, a hydroxyl group, a hydroxyalkylamide group, a (meth) acrylate group, a blocked isocyanate group, an oxetane group, and an epoxy group.
  • a hydroxyl group, a blocked isocyanate group, or an epoxy group is preferable, and a hydroxyl group or an epoxy group is more preferable.
  • (C) component may have 2 or more of the same crosslinkable functional groups in the structure, and may have 2 or more of 2 or more types of different crosslinkable functional groups.
  • Examples of the compound containing two or more hydroxyl groups include compounds represented by the following formula (7).
  • X 3 is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, n is an integer of 2 to 6, and R 6 and R 7 are respectively Independently a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and R 6 and R 7 At least one of them is represented by the following formula (6).
  • R 8 to R 11 each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.
  • X 3 is preferably an aliphatic hydrocarbon group from the viewpoint of liquid crystal alignment and solubility, and more preferably has 1 to 10 carbon atoms, as described above.
  • n represents an integer of 2 to 6, and n is preferably 2 to 4 from the viewpoint of solubility.
  • Examples of the compound containing two or more blocked isocyanate groups include compounds represented by the following formula (9).
  • Z's are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or an organic group represented by the following formula (10), and at least one of Z is represented by the following formula (10). It is an organic group.
  • Examples of the compound containing two or more blocked isocyanate groups other than the above formula (11) include the following compounds.
  • Specific examples of the compound containing two or more epoxy groups include the following compounds.
  • Specific examples of the compound containing two or more (meth) acrylate groups include the following compounds.
  • the content ratio of the component (A) is preferably 20 to 80% by mass during the liquid crystal alignment. 20 to 60% by mass is more preferable, and 30 to 50% by mass is particularly preferable.
  • the content of the component (B) is preferably 20 to 80% by mass, more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass with respect to the component (A).
  • the content of the component (C) is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, particularly 3 to 15% by weight, based on the total of the components (A) and (B). preferable.
  • the polyamic acid which is a polyimide precursor used for the component (A) and the component (B) is produced by the following method. Specifically, a tetracarboxylic acid component such as tetracarboxylic dianhydride and a diamine component are -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of an organic solvent, for 30 minutes to 24 hours. Preferably, it can be produced by reacting for 1 to 12 hours.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent.
  • the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved.
  • Specific examples of the organic solvent used in the reaction include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide. Or 1,3-dimethyl-imidazolidinone.
  • the solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3].
  • An organic solvent can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • An alkyl group is shown.
  • These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
  • the concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass because polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the obtained polyamic acid can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid ester which is a polyimide precursor can be manufactured by the manufacturing method of (1), (2) or (3) shown below.
  • (1) When manufacturing from polyamic acid A polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be manufactured.
  • the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 mol with respect to 1 mol of the polyamic acid repeating unit.
  • organic solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl- Examples include imidazolidinone.
  • solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the above formulas [D-1] to [D-3]
  • the indicated solvents can be used. These solvents may be used alone or in combination.
  • the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of polymer solubility. These may be used alone or in combination of two or more. Good.
  • the concentration at the time of production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the polyamic acid ester can be manufactured from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be produced by reacting.
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the polymer concentration at the time of production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine. Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can be produced by reacting for a period of time.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base added is preferably 2 to 4 moles relative to the diamine component because it can be easily removed and a high molecular weight product can be easily obtained.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
  • the production method (1) or (2) is particularly preferable.
  • the polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyimide used in the present invention can be produced by imidizing the aforementioned polyamic acid ester or polyamic acid.
  • chemical imidization in which a basic catalyst is added to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
  • Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
  • the solvent used at the time of the polymerization reaction mentioned above can be used.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like.
  • triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
  • the temperature for carrying out the imidization reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below and redissolved in an organic solvent to obtain a liquid crystal aligning agent. It is preferable.
  • Chemical imidation can be performed by stirring the polyamic acid to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the temperature for carrying out the imidization reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
  • the liquid crystal aligning agent of the present invention is preferable.
  • the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the liquid crystal aligning agent of this invention has the form of the solution in which the above-mentioned specific polymer (A), specific polymer (B), and (C) component were melt
  • the molecular weight of the specific polymer (A) and the specific polymer (B) is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, still more preferably 10, 000 to 100,000.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the content (concentration) of the polymer containing the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed. However, it is preferably 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by weight or less from the viewpoint of storage stability of the solution. Among these, 2 to 7% by mass is preferable, and 3 to 6% by mass is particularly preferable.
  • the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the specific structure polymer is uniformly dissolved.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or ⁇ -butyrolactone is preferable.
  • the solubility of the polymer in the solvent is high, it is preferable to use the solvents represented by the formulas [D-1] to [D-3].
  • the good solvent in the liquid crystal aligning agent is preferably 20% by mass to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.
  • the liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied.
  • a solvent also referred to as a poor solvent
  • it can be used.
  • a poor solvent is given to the following, it is not limited to these examples.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or dipropylene glycol dimethyl ether are preferable.
  • These poor solvents are preferably 1 to 80% by mass of the whole solvent contained in the liquid crystal aligning agent. Of these, 10 to 80% by mass is preferable. More preferred is 20 to 70% by mass.
  • liquid crystal aligning agent of the present invention in addition to the above, as long as the effects of the present invention are not impaired, a polymer other than the polymer described in the present invention, the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, etc.
  • Dielectric or conductive material for changing characteristics, silane coupling agent for improving adhesion between liquid crystal alignment film and substrate, crosslinkability for increasing hardness and density of liquid crystal alignment film When firing the compound, and further, the coating film, an imidization accelerator for the purpose of efficiently proceeding imidization by heating of the polyimide precursor may be added.
  • the liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking.
  • the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, an acrylic substrate, a polycarbonate substrate such as a polycarbonate substrate, or the like can be used.
  • Use of a substrate on which an ITO electrode or the like is formed is preferable from the viewpoint of simplification of the process.
  • an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light, such as aluminum, can also be used.
  • Examples of the method for applying the liquid crystal aligning agent include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent. Usually, in order to sufficiently remove the organic solvent contained, drying is performed at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baking is performed at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes.
  • the thickness of the coating film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is 5 to 300 nm, preferably 10 to 200 nm.
  • Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and a photo-alignment processing method.
  • the rubbing process can be performed using an existing rubbing apparatus.
  • Examples of the material of the rubbing cloth at this time include cotton, nylon, and rayon.
  • As the conditions for rubbing treatment generally, conditions of a rotational speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm / s, and an indentation amount of 0.1 to 1.0 mm are used. Thereafter, the residue generated by rubbing is removed by ultrasonic cleaning using pure water or alcohol.
  • the photo-alignment treatment method there is a method of imparting liquid crystal alignment ability by irradiating the coating film surface with radiation deflected in a certain direction, and further subjecting to a temperature of 150 to 250 ° C. in some cases.
  • the radiation ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable.
  • radiation may be irradiated while heating the coated substrate at 50 to 250 ° C.
  • Dose of the radiation is preferably 1 ⁇ 10,000mJ / cm 2, particularly preferably 100 ⁇ 5,000mJ / cm 2.
  • the liquid crystal alignment film can stably align liquid crystal molecules in a certain direction.
  • a higher extinction ratio of polarized ultraviolet rays is preferable because higher anisotropy can be imparted.
  • the extinction ratio of linearly polarized ultraviolet light is preferably 10: 1 or more, and more preferably 20: 1 or more.
  • the film irradiated with the polarized radiation may be contact-treated with a solvent containing at least one selected from water and an organic solvent.
  • the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves a decomposition product generated by light irradiation.
  • Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Examples include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Two or more of these solvents may be used in combination.
  • At least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable.
  • Water, 2-propanol, and a mixed solvent of water and 2-propanol are particularly preferable.
  • the contact treatment between the film irradiated with polarized radiation and the solution containing the organic solvent is preferably performed by a treatment such that the film and the liquid are sufficiently in contact with each other, such as an immersion treatment or a spraying treatment.
  • a method of immersing the film in a solution containing an organic solvent preferably 10 seconds to 1 hour, more preferably 1 to 30 minutes is preferable.
  • the contact treatment may be performed at normal temperature or preferably at 10 to 80 ° C., more preferably 20 to 50 ° C.
  • a means for enhancing contact such as ultrasonic waves can be applied as necessary.
  • rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, or drying, or both May be done.
  • the film subjected to the contact treatment with the solvent may be heated at 150 ° C. or higher for the purpose of drying the solvent and reorienting the molecular chains in the film.
  • the heating temperature is preferably 150 to 300 ° C. A higher temperature promotes reorientation of molecular chains. However, if the temperature is too high, molecular chains may be decomposed. Therefore, the heating temperature is more preferably 180 to 250 ° C., and particularly preferably 200 to 230 ° C. If the heating time is too short, the effect of reorientation of the molecular chain may not be obtained, and if it is too long, the molecular chain may be decomposed, and is preferably 10 seconds to 30 minutes. More preferred is ⁇ 10 minutes.
  • the liquid crystal display element of this invention comprises the liquid crystal aligning film obtained by the manufacturing method of the said liquid crystal aligning film.
  • the liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film from a liquid crystal aligning agent by the method for producing a liquid crystal alignment film, then preparing a liquid crystal cell by a known method, and using it as a liquid crystal display element. is there.
  • a liquid crystal cell manufacturing method a liquid crystal display element having a passive matrix structure will be described. Note that an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
  • TFT Thin Film Transistor
  • a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
  • These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a film made of SiO 2 —TiO 2 formed by a sol-gel method.
  • the liquid crystal alignment film of the present invention is formed on each substrate.
  • the other substrate is superposed on one substrate so that the alignment film surfaces face each other, and the periphery is bonded with a sealant.
  • a spacer is usually mixed in the sealing material.
  • spacers for controlling the substrate gap are also sprayed on the in-plane portion where no sealing material is provided. A part of the sealing material is provided with an opening that can be filled with liquid crystal from the outside.
  • a liquid crystal material is injected into a space surrounded by two substrates and the sealing material through an opening provided in the sealing material. Thereafter, the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer.
  • the sealing agent for example, a resin that is cured by ultraviolet irradiation or heating having a reactive group such as an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, an allyl group, or an acetyl group is used.
  • a cured resin system having reactive groups of both an epoxy group and a (meth) acryloyl group.
  • An inorganic filler may be added to the sealant for the purpose of improving adhesiveness and moisture resistance.
  • the inorganic filler that can be used is not particularly limited. Specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, Calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc.
  • Two or more of the above inorganic fillers may be mixed and used.
  • NMP N-methyl-2-pyrrolidone
  • PB propylene glycol monobutyl ether
  • IPA isopropanol
  • DA-1 1,2-bis (4-aminophenoxy) ethane
  • DA-2 see formula (DA-2) below
  • DA-3 1,2-bis (4-aminophenoxy) methane
  • DA-4 p-phenylenediamine
  • DA-5 1,2-bis (4-aminophenoxy) propane
  • DA-6 see formula (DA-6) below
  • DA-7 4,4′diaminodiphenylamine
  • DA-8 See the following formula (DA-8), DA-9: 4,4′diaminodiphenylmethane
  • DAH-1 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • DAH-2 see formula (DAH-2) below
  • DAH-3 see formula (DAH-3) below
  • DAH-4 cyclobutanetetra Carboxylic dianhydride
  • DAH-5 pyromellitic dianhydride 1,3DM-CBDE-Cl: dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate
  • AD-1 to 3 Crosslinkable additive
  • AD-4 Imidization accelerator
  • the molecular weight of the polyimide was measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as polyethylene glycol and polyethylene oxide equivalent values.
  • GPC device manufactured by Shodex (GPC-101), Column: manufactured by Shodex (series of KD803 and KD805), column temperature: 50 ° C.
  • a polyimide resin powder (SPI-1) was obtained by taking 32.70 g of the obtained polyimide resin powder in a 200 ml sample tube containing a stir bar, adding 239.8 g of NMP, and stirring and dissolving at 70 ° C. for 20 hours.
  • Example 1 In a 50 mL Erlenmeyer flask containing a stirrer, 2.929 g of the polyimide solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 3 were taken. 2.83g of NMP, 3.45g of GBL and 3.60g of PB were added, 0.495g of 10% NMP solution of AD-1 and 0.139g of AD-4 were added and stirred overnight with a magnetic stirrer to align the liquid crystal Agent (AL-1) was obtained.
  • SPI-1 polyimide solution obtained in Synthesis Example 2
  • Example 2 In a 50 mL Erlenmeyer flask containing a stirrer, 2.929 g of the polyimide solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 3 were taken. 3.32 g of NMP, 3.45 g of GBL and 3.60 g of PB were added, 0.0297 g of AD-2 and 0.139 g of AD-4 were added, and the mixture was stirred overnight with a magnetic stirrer (AL-2 )
  • Example 3 In a 50 mL Erlenmeyer flask containing a stirrer, 2.929 g of the polyimide solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 3 were taken. 3.32 g of NMP, 3.45 g of GBL and 3.60 g of PB were added, 0.0297 g of AD-3 and 0.139 g of AD-4 were added, and the mixture was stirred overnight with a magnetic stirrer (AL-3 )
  • Example 4 In a 50 mL Erlenmeyer flask containing a stir bar, 3.249 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 6 were taken. . 5.40 g of NMP and 5.40 g of BCS were added, 0.45 g of 10% NMP solution of AD-1 was added and stirred overnight with a magnetic stirrer to obtain a liquid crystal aligning agent (AL-4).
  • PAA-4 polyamic acid solution obtained in Synthesis Example 5
  • Example 5 In a 50 mL Erlenmeyer flask containing a stir bar, 3.249 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 6 were taken. . 5.85 g of NMP and 5.40 g of BCS were added, 0.027 g of AD-2 was added, and the mixture was stirred overnight with a magnetic stirrer to obtain a liquid crystal aligning agent (AL-5).
  • PAA-4 polyamic acid solution obtained in Synthesis Example 5
  • PAA-5 polyamic acid solution obtained in Synthesis Example 6
  • Example 6 In a 50 mL Erlenmeyer flask containing a stir bar, 3.249 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 6 were taken. . 5.85 g of NMP and 5.40 g of BCS were added, 0.045 g of AD-3 was added and stirred overnight with a magnetic stirrer to obtain a liquid crystal aligning agent (AL-6).
  • PAA-4 polyamic acid solution obtained in Synthesis Example 5
  • Example 7 In a 50 mL Erlenmeyer flask containing a stir bar, 3.30 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 8 and 3.96 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 9 were placed. It was. Add 1.54g of NMP, 5.12g of GBL and 3.60g of BCS, then add 0.495g of 10% NMP solution of AD-1 and stir overnight with a magnetic stirrer to obtain a liquid crystal aligning agent (AL-7). It was.
  • Example 8 In a 50 mL Erlenmeyer flask containing a stirring bar, 1.87 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 11 and 4.80 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 9 were taken. . 5.58 g of NMP and 5.40 g of BCS were added, and 0.45 g of 10% NMP solution of AD-1 was further added and stirred overnight with a magnetic stirrer to obtain a liquid crystal aligning agent (AL-8).
  • PAA-9 polyamic acid solution obtained in Synthesis Example 11
  • This cell was heat-treated at 120 ° C. for 30 minutes to complete a liquid crystal cell.
  • a voltage of 1V was applied for 60 ⁇ s at a temperature of 60 ° C., and the voltage after 500 ms was measured to determine how much the voltage was maintained. Obtained as retention.
  • Example 10 and 11 Comparative Examples 9 and 10
  • a liquid crystal cell was prepared and evaluated in the same manner as in Example 9 except that the liquid crystal aligning agent shown in Table 1 was used instead of the liquid crystal aligning agent AL-1.
  • Table 1 shows the results of initial orientation and voltage holding ratio of each liquid crystal cell.
  • Example 12 The liquid crystal aligning agent (AL-4) obtained in Example 4 was filtered through a filter having a pore size of 1.0 ⁇ m, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 2 minutes. It was. Thereafter, the film was baked for 30 minutes in a hot air circulating oven at a temperature of 230 ° C. to obtain an imidized film having a thickness of 100 nm. The fired film was irradiated with UV light of 254 nm through a polarizing plate at 150 mJ / cm 2 . Thereafter, baking was further performed in a hot air circulation oven at 230 ° C. for 30 minutes.
  • a substrate with a liquid crystal alignment film was obtained.
  • two substrates with the above-mentioned liquid crystal alignment film were prepared, and a 6 ⁇ m spacer was dispersed on the one liquid crystal alignment film.
  • a sealant was printed from above, and another substrate was bonded so that the liquid crystal alignment film faces and the photo-alignment direction were parallel, and then the sealant was cured to produce an empty cell.
  • Liquid crystal ML-7026-100 manufactured by Merck Japan Co., Ltd.
  • Example 13 and 14 Comparative Examples 11 and 12
  • a liquid crystal cell was prepared and evaluated in the same procedure as in Example 9 except that the liquid crystal aligning agent shown in Table 1 was used instead of the liquid crystal aligning agent AL-4.
  • Table 1 shows the results of initial orientation and voltage holding ratio of each liquid crystal cell.
  • Example 16 The liquid crystal aligning agent (AL-8) obtained in Example 8 was filtered through a filter having a pore size of 1.0 ⁇ m, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 2 minutes. It was. Thereafter, the film was baked for 20 minutes in a hot air circulating oven at a temperature of 230 ° C. to obtain an imidized film having a thickness of 110 nm. The fired film was subjected to orientation treatment by rubbing. Thereafter, it was washed with running water for 1 minute and dried at 80 ° C. for 10 minutes. Thereby, a substrate with a liquid crystal alignment film was obtained.
  • This cell was heat-treated at 120 ° C. for 30 minutes to complete a liquid crystal cell.
  • a voltage of 1V is applied at 20 ° C. for 60 ⁇ s, the voltage after 500 ms is measured, and the voltage holding ratio is defined as the voltage holding ratio. Asked.
  • component 1 is a polymer component containing a thermal leaving group.
  • a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used as a wide range display such as a liquid crystal television, a smartphone, and a car navigation.
  • a liquid crystal television a liquid crystal television
  • a smartphone a smartphone
  • a car navigation a wide range display
  • the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2016-001659 filed on Jan. 7, 2016 are incorporated herein as the disclosure of the specification of the present invention. Is.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui permet d'obtenir un film d'alignement de cristaux liquides qui maintient un rapport de conservation de tension adéquat même après avoir été exposé à un rayonnement lumineux, sans subir de détérioration dans les propriétés d'alignement de cristaux liquides. Un agent d'alignement de cristaux liquides est caractérisé en ce qu'il contient le composé (A), le composé (B) et le composé (C) décrits ci-dessous et un solvant organique. Composé (A) : au moins un polymère choisi parmi des polyimides et des précurseurs de polyimide, qui sont obtenus à l'aide d'un composé dérivé d'acide tétracarboxylique et d'un composé de diamine qui contient au moins un composé de diamine choisi parmi des composés de diamine ayant une structure de formule (A-1), des composés de diamine ayant une structure de formule (A-2) et des composés de diamine ayant une structure de formule (A-3) ; Composé (B) : au moins un polymère choisi parmi le groupe comprenant des précurseurs de polyimide ayant une unité structurale représentée par la formule (2) et des polymères imidisés des précurseurs de polyimide ; Composé (C) : un composé ayant deux groupes fonctionnels réticulables ou plus (dans les formules, les symboles sont tels que définis dans la description.)
PCT/JP2017/000178 2016-01-07 2017-01-05 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant Ceased WO2017119461A1 (fr)

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JP2019101196A (ja) * 2017-11-30 2019-06-24 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
JP2019101195A (ja) * 2017-11-30 2019-06-24 日産化学株式会社 液晶配向膜の製造方法、液晶配向膜、及び液晶表示素子
CN111602088A (zh) * 2018-01-19 2020-08-28 日产化学株式会社 液晶取向剂、液晶取向膜及使用其的液晶表示元件
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US11667844B2 (en) 2018-11-20 2023-06-06 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
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KR20220056789A (ko) * 2020-10-28 2022-05-06 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자 및 그의 제조 방법
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JP2019101196A (ja) * 2017-11-30 2019-06-24 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
JP2019101195A (ja) * 2017-11-30 2019-06-24 日産化学株式会社 液晶配向膜の製造方法、液晶配向膜、及び液晶表示素子
CN111602088A (zh) * 2018-01-19 2020-08-28 日产化学株式会社 液晶取向剂、液晶取向膜及使用其的液晶表示元件
CN111801401A (zh) * 2018-11-20 2020-10-20 株式会社Lg化学 液晶取向组合物、使用其制备液晶取向膜的方法及使用其的液晶取向膜、液晶显示器
US11667844B2 (en) 2018-11-20 2023-06-06 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
CN111801401B (zh) * 2018-11-20 2023-06-30 株式会社Lg化学 液晶取向组合物、使用其制备液晶取向膜的方法及使用其的液晶取向膜、液晶显示器
KR102880471B1 (ko) * 2018-12-27 2025-11-03 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 액정 표시 소자 및 신규 모노머
JP2022071804A (ja) * 2020-10-28 2022-05-16 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
JP7517208B2 (ja) 2020-10-28 2024-07-17 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
WO2023068085A1 (fr) * 2021-10-18 2023-04-27 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé

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