CN114466882A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polymer, and diamine - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polymer, and diamine Download PDFInfo
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- CN114466882A CN114466882A CN202080066918.XA CN202080066918A CN114466882A CN 114466882 A CN114466882 A CN 114466882A CN 202080066918 A CN202080066918 A CN 202080066918A CN 114466882 A CN114466882 A CN 114466882A
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- liquid crystal
- carbon atoms
- diamine
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 72
- 150000004985 diamines Chemical class 0.000 title claims description 82
- 229920000642 polymer Polymers 0.000 title claims description 70
- 229920001721 polyimide Polymers 0.000 claims abstract description 57
- 239000004642 Polyimide Substances 0.000 claims abstract description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
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- 125000004428 fluoroalkoxy group Chemical group 0.000 claims abstract description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
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- 239000000758 substrate Substances 0.000 claims description 31
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- 125000001033 ether group Chemical group 0.000 claims description 2
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- 238000003786 synthesis reaction Methods 0.000 description 12
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- 125000003118 aryl group Chemical group 0.000 description 6
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- 238000005481 NMR spectroscopy Methods 0.000 description 4
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- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 3
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- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- HBJPJUGOYJOSLR-UHFFFAOYSA-N naphthalene-2,7-diamine Chemical compound C1=CC(N)=CC2=CC(N)=CC=C21 HBJPJUGOYJOSLR-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 1
- TXQWFIVRZNOPCK-UHFFFAOYSA-N pyridin-4-ylmethanamine Chemical compound NCC1=CC=NC=C1 TXQWFIVRZNOPCK-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G73/1075—Partially aromatic polyimides
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/34—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups and esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
-
- 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Liquid Crystal (AREA)
Abstract
The invention provides a liquid crystal aligning agent which can obtain a liquid crystal aligning film with high liquid crystal aligning capability even under the condition of being exposed to overheating. A liquid crystal aligning agent containing at least one type of poly selected from the group consisting of polyimide precursors having a group represented by the following formula (1) and polyimidesCompound (P). (in the formula, X1Represents an alkylene group having 1 to 14 carbon atoms, wherein one or two non-adjacent methylene groups in the alkylene group are optionally substituted by-O-or-COO-. X2Represents a single bond, -OCO-, -COO-, or CONR2‑(R2Represents a hydrogen atom or a methyl group). Q represents a naphthylene group and Y represents a group containing at least one cyclohexylene group. The arbitrary hydrogen atom of the naphthylene or cyclohexylene is optionally substituted by at least one selected from the group consisting of alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, fluorine-containing alkyl with 1-3 carbon atoms, fluorine-containing alkoxy with 1-3 carbon atoms and fluorine atom. R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoroalkoxy group having 1 to 12 carbon atoms, -CN, -F, -OH, -CO2H，‑OCOR3or-CO2R3，R3Represents a methyl group or an ethyl group. Denotes a bond. ) X is1‑Q‑X2‑Y‑R(1)。
Description
Technical Field
The present invention relates to a liquid crystal aligning agent; a liquid crystal alignment film obtained from the liquid crystal aligning agent; and a liquid crystal display element having the liquid crystal alignment film; and novel diamines and polymers suitable for these liquid crystal aligning agents, liquid crystal alignment films, and liquid crystal display elements.
Background
Conventionally, various driving methods have been developed for liquid crystal display elements, such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS (In-Plane Switching) type, and FFS (fringe field Switching) type, In which the electrode structure and the properties of the liquid crystal molecules used are different. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, for example, polyamic acid ester, polyimide, polyamide, and the like are known.
In the VA-type liquid crystal display device, the manufacturing process includes a step of irradiating ultraviolet rays while applying a voltage to liquid crystal molecules. In such a VA-type liquid crystal display device, the following techniques are known: a photopolymerizable compound is added to a liquid crystal composition in advance, and ultraviolet rays are irradiated using a liquid crystal Alignment film such as a polyimide film while applying a voltage to a liquid crystal cell, thereby increasing the response speed of the liquid crystal (PSA (Polymer stabilized Alignment) type element, for example, see patent document 1 and non-patent document 1). As a liquid crystal aligning agent used for the PSA type element, a liquid crystal aligning agent having a specific ring structure in a side chain has been proposed (see patent document 2). The specific ring structure has high ability to vertically align liquid crystal, and a VA-type liquid crystal display element using the liquid crystal aligning agent has good display characteristics.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-307720
Patent document 2: WO 2006/070819A
Non-patent document
Non-patent document 1: hanaoka, SID 04DIGEST, P.1200-1202
Disclosure of Invention
Problems to be solved by the invention
However, in recent liquid crystal display elements, due to the effect of thinning and increasing the size of substrates used, a temperature difference occurs between different portions in the same substrate during firing, and the liquid crystal alignment film in an excessively heated portion deteriorates the ability to align liquid crystals, and as a result, the resulting liquid crystal display element has a problem of partial display failure.
The present invention has been made in view of the above problems, and provides a liquid crystal aligning agent capable of providing a liquid crystal alignment film having a high liquid crystal aligning capability even when exposed to excessive heating; and a liquid crystal display element which is less likely to cause display failure.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above properties can be obtained by incorporating a polymer having a specific structure into a liquid crystal aligning agent, thereby completing the present invention.
The present invention is based on this finding, and the gist thereof is as follows.
A liquid crystal aligning agent contains at least one polymer (P) selected from the group consisting of a polyimide precursor having a group represented by the following formula (1) and a polyimide.
*-X1-Q-X2-Y-R (1)
(in the formula, X1Represents an alkylene group having 1 to 14 carbon atoms, wherein one or two non-adjacent methylene groups in the alkylene group are optionally substituted by-O-or-COO-. X2Represents a single bond, -OCO-, -COO-, or CONR2－(R2Represents a hydrogen atom or a methyl group). Q represents a naphthylene group, and Y represents a group containing at least one cyclohexylene group. The naphthalene or cyclohexylene arbitrary hydrogen atoms are optionally selected from the carbon number of 1 ~ 3 alkyl, carbon number of 1 ~ 3 alkoxy, carbon number of 1 ~ 3 fluorine containing alkyl, carbon number of 1 ~ 3 fluorine containing alkoxy, or fluorine atom consisting of at least one of the group. R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoroalkoxy group having 1 to 12 carbon atoms, -CN, -F, -OH, -CO2H、－OCOR3or-CO2R3，R3Represents a methyl group or an ethyl group. Denotes a bond. )
Effects of the invention
According to the present invention, there is provided a liquid crystal aligning agent capable of providing a liquid crystal alignment film having a high capability of aligning liquid crystal even when exposed to excessive heating; and a liquid crystal display element which is less likely to cause display failure and has a high display quality grade.
The mechanism of obtaining the liquid crystal aligning agent and the liquid crystal display device having the excellent characteristics according to the present invention is not necessarily clear, but is estimated as follows.
As a factor of the decrease in the homeotropic alignment ability in the case of exposure to high temperature, thermal decomposition of the side chain having the homeotropic alignment ability, embedding in the film due to thermal movement of the side chain, and the like are considered. On the other hand, in the studies of the present inventors, it is found that in the case of a polymer containing a rigid structure, the glass transition temperature of the polymer is increased and the thermal stability is improved. The polymer having a specific structure of the present invention has a rigid structure such as naphthalene group, and is expected to provide a liquid crystal alignment film having high liquid crystal alignment ability because of improved thermal stability.
Detailed Description
< Polymer (P) >
The liquid crystal aligning agent of the present invention contains at least one polymer (P) selected from the group consisting of a polyimide precursor having a group represented by the above formula (1) and a polyimide.
In the above formula (1), X1Preferably represents-O-, -COO-, - (CH)2)c- (c is an integer of 1 to 10), -CH2O－、－CO－O－、－(CH2)c-CO-O- (c is an integer of 1 to 10), - (CH)2)c-O-CO- (c is an integer of 1 to 10), -CH2O－(CH2)c- (c is an integer of 1 to 10), -CH2O－(CH2)c－(O)d- (c is an integer of 1 to 10, d is an integer of 0 or 1), -CO-O- (CH)2)c－(O)d- (c is an integer of 1 to 10, d is an integer of 0 or 1), -O- (CH)2)c－(O)d- (c is an integer of 1 to 10, d is an integer of 0 or 1), -CO-O- (CH)2)c-O-CO- (c is an integer of 1 to 10), -CO-O- (CH)2)c-CO-O- (c is an integer of 1 to 10).
X2Preferably represents a single bond.
Y preferably represents a group represented by the following formula (Z).
(in the formula, X3Represents a single bond, - (CH)2)a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH)3) -, -NH-, -O-, -COO-, -OCO-or- ((CH)2)a1－A1)m1-. Wherein a1 each independently represents an integer of 1 to 15, and A1Each independently represents an oxygen atom or-COO-, m1Represents an integer of 1 to 2. Y is1Represents a cyclohexylidene group, any hydrogen atom of the cyclohexylidene group being optionally substitutedAt least one substituent selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, and a fluorine atom. n represents an integer of 1 to 10. )
In the above formula (Z), X is preferably3Represents a single bond, and n represents an integer of 1 to 4, preferably 2 to 4.
R preferably represents an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms.
The group represented by the formula (1) preferably represents groups represented by the following formulae (1-1) to (1-12).
(c is an integer of 1 to 10. d is an integer of 0 or 1. m is an integer of 1 to 2. n is an integer of 1 to 12.)
< specific diamine >
The polymer (P) is, for example, a polymer obtained from a diamine component containing a diamine having a group represented by the above formula (1) (hereinafter referred to as "specific diamine").
The specific diamine is preferably at least one diamine selected from the group consisting of diamines represented by the following formulae (2-1) and (2-2).
(in the formula, X11、X21a、X21bWith X of the above formula (1)1Synonymy, Q1、Q2a、Q2bSynonymous with Q of the above formula (1), X12、X22a、X22bWith X of the above formula (1)2Synonymy, Y1、Y2a、Y2bSynonymous with Y in the above formula (1), R1、R2a、R2bThe same meaning as R in the above formula (1). L represents a single bond, -O-, -C (CH)3)2-, -NR- (R represents a hydrogen atom or a methyl group), -CO-, -NHCO-, -COO-, - (CH)2)m－、－SO2－、－O－(CH2)m－O－、－O－C(CH3)2－、－CO－(CH2)m－、－NH－(CH2)m－、－SO2－(CH2)m－、－CONH－(CH2)m－、－CONH－(CH2)m－NHCO－、－COO－(CH2)m-OCO-. m represents an integer of 1 to 8. )
Specific examples of the specific diamine include at least one diamine selected from the group consisting of: in the formula (2-1), the group "-X11－Q1－X12－Y1－R1"a diamine which represents a group represented by the above formulae (1-1) to (1-12); and in formula (2-2), the group "-X21－Q2a－X22a－Y2a－R2a"and group" -X22－Q2b－X22b－Y2b－R2b"represents a diamine of the groups represented by the above formulas (1-1) to (1-12), respectively. Specific examples of the more preferable diamine include at least one diamine selected from the following diamines: in the formula (2-1), the group "-X11－Q1－X12－Y1－R1"represents a group represented by the above formulas (1-1) to (1-12) and two amino groups with respect to the group" -X11－Q1－X12－Y1－R1"diamines bonded in ortho-and para-positions. Particularly, at least one diamine selected from the group consisting of diamines represented by the following formulae (d-1) to (d-12) is preferable.
(m represents 2. n represents 3, 5 or 7. c represents 1 to 6. d represents 0 or 1.)
< other diamines >
As the diamine component used for producing the polymer (P), any diamine other than the specific diamine may be used. Examples of other diamines are: diamines having a carboxyl group such as p-phenylenediamine, m-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3, 5-diaminobenzoic acid, 4 ' -diaminodiphenylmethane, 3, 3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 3, 3 ' -diaminodiphenyl ether, 4 ' -diaminobenzophenone, 3, 3 ' -diaminobenzophenone, 1, 2-bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 2-bis (4-aminophenoxy) ethane, 1, 2-bis (4-amino-2-methylphenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, p-phenylenediamine, m-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3, 5-diaminobenzoic acid, etc., 1, 4 ' -bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 3-bis (4-phenyl) propane, 3-bis (4-aminophenoxy) ethane, 3-bis (4-aminophenoxy) propane, 3-benzene, 3-bis (4-benzene, 1, 2, 1, 2, or a mixture of a compound and a mixture of a mixture, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 4- (2- (4-aminophenoxy) ethoxy) -3-fluoroaniline, bis (2- (4-aminophenoxy) ethyl) ether, 4-amino-4 '- (2- (4-aminophenoxy) ethoxy) biphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2' -bis [ 4- (4-aminophenoxy) phenyl ] propane, 2 '-bis [ 4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2' -bis (4-aminophenyl) propane, A diamine having a urea bond such as 1, 3-bis (4-aminophenylethyl) urea, a diamine represented by the following formulae (a-1) to (a-6), preferably a diamine having a photopolymerizable group at the terminal such as 2- (2, 4-diaminophenoxy) ethyl methacrylate or 2, 4-diamino-N, N-diallylaniline, a diamine having a radical-initiating function such as the following formulae (R1) to (R5), a diamine having a heterocyclic ring such as the following formulae (z-1) to (z-18), a diamine having a diphenylamine skeleton such as the following formulae (Dp-1) to (Dp-3), a diamine having a group "— (D)" such as the following formulae (5-1) to (5-11) (D represents a group which is eliminated by heating, a protective group substituted with a hydrogen atom, preferably a t-butoxycarbonyl group), a diamine having an oxazoline structure such as the following formulae (Ox-1) to (Ox-2), a diamine having a structure exhibiting vertical alignment of a liquid crystal in a side chain such as the following formulae (V2-1) to (V2-13), an organosiloxane-containing diamine such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and the like.
(d1 represents an integer of 2 to 10.)
(n represents an integer of 2 to 10.)
(Boc represents a tert-butoxycarbonyl group.)
(wherein, in the formula, Xv1～Xv4、Xp1～Xp8Each independently represents- (CH)2)a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH)3)－、－NH－、－O－、－CH2O－、－CH2-OCO-, -COO-, or-OCO-, Xv5represents-O-, -CH2O－、－CH2-OCO-, -COO-, or-OCO-, XV6～XV7、Xs1～Xs4Each independently represents-O-, -COO-or-OCO-. Xa～XfRepresents a single bond, -O-, -NH-, -O- (CH)2)m－O－、－C(CH3)2－、－CO－、－COO－、－CONH－、－(CH2)m－、－SO2－、－O－C(CH3)2－、－CO－(CH2)m－、－NH－(CH2)m－、－NH－(CH2)m－NH－、－SO2－(CH2)m－、－SO2－(CH2)m－SO2－、－CONH－(CH2)m－、－CONH－(CH2)m-NHCO-, or-COO- (CH)2)m－OCO－，Rv1～Rv4、R1a～R1hEach independently represents-CnH2n+1(n is an integer of 1 to 20), -O-CnH2n+1(n is an integer of 2 to 20). m represents an integer of 1 to 8. )
Further, other diamines include: aliphatic diamines such as m-xylylenediamine, alicyclic diamines such as 4, 4-methylenebis (cyclohexylamine), and diamines described in International publication No. 2016/125870.
In view of improving the response speed of the liquid crystal display element obtained in the step (1-3B) or (1-3C) described later, one or more of the above-mentioned 4, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, diamine having a photopolymerizable group at the terminal, diamines represented by the above-mentioned formulae (R1) to (R5), and diamines represented by the above-mentioned formulae (z-1) to (z-18) may be used in the production of the polymer (P). The content of the diamine is preferably 5 to 70 mol% based on the whole diamine component, and from the viewpoint of improving the voltage holding ratio of the liquid crystal alignment film obtained, the content is more preferably 5 to 60 mol%, and particularly preferably 5 to 50 mol%.
One or two or more of the other diamines may be used.
< tetracarboxylic acid component >
The tetracarboxylic acid component is a component containing at least one selected from the group consisting of tetracarboxylic acids and tetracarboxylic acid derivatives. Examples of tetracarboxylic acid derivatives include: tetracarboxylic acid dihalides, tetracarboxylic acid dianhydrides, tetracarboxylic acid diester dichlorides, tetracarboxylic acid diesters, and the like.
The polyimide precursor as the polymer (P) can be obtained, for example, by polymerizing a diamine component containing a diamine having a group represented by the above formula (1) with a tetracarboxylic acid component.
Examples of the tetracarboxylic acid component used for producing the polymer (P) include: aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or derivatives thereof. Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. The aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, the structure does not need to be composed of only a chain hydrocarbon structure, and a part of the structure may have an alicyclic structure or an aromatic ring structure. The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Wherein none of the four carboxyl groups is bonded to an aromatic ring. Further, the alicyclic structure need not be solely composed, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure. The tetracarboxylic acid component preferably contains a tetracarboxylic dianhydride represented by the following formula (3).
(X represents a structure selected from any of the following (X-1) to (X-13))
(in the formula, R1～R4Represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and may be the same or different. R5And R6Represents a hydrogen atom or a methyl group, and may be the same or different. j and k independently represent 0 or 1, A1And A2Each independently represents a single bond, an ether group, a carbonyl group, an ester group, a phenylene group, a sulfonyl group, or an amide group. [ 1] represents a bond to one acid anhydride group, and [ 2] represents a bond to the other acid anhydride group. )
Preferable specific examples of the above (x-12) and (x-13) include the following formulas (x-14) to (x-29). Denotes a bond.
As a preferred example of the tetracarboxylic dianhydride represented by the above formula (3) or a derivative thereof, a tetracarboxylic dianhydride represented by the above formula (3) wherein X is represented by the above formulae (X-1) to (X-7), (X-11) to (X-13) or a derivative thereof can be mentioned.
< Polymer (P), diamine component and tetracarboxylic acid component content >
The content of the polymer (P) used in the present invention is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, based on the total mass of the liquid crystal aligning agent.
The content of the specific diamine is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 30 to 60 mol% based on the total amount of the diamine component used for producing the polymer (P).
The diamine component used for producing the polymer (P) may be used alone or in combination of two or more kinds depending on the solubility of the polymer in a solvent, the coating property of a liquid crystal aligning agent, the liquid crystal aligning property in the case of being used as a liquid crystal alignment film, the voltage holding ratio, the accumulated charge, and other properties.
The content of the tetracarboxylic dianhydride represented by the formula (3) is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, based on the total amount of the diamine component used for producing the polymer (P).
The tetracarboxylic acid component used for producing the polymer (P) may be used alone or in combination of two or more depending on the solubility of the polymer in a solvent, the coatability of a liquid crystal aligning agent, the liquid crystal alignment properties in the case of forming a liquid crystal alignment film, the voltage holding ratio, the accumulated charge, and other properties.
< Polymer >
Also included in the present invention are polymers obtained from a diamine component comprising at least one diamine represented by the above formula (2-1) or (2-2). Examples of such polymers include: polyimide precursors, polyimides, polyamides, polyureas, and the like. The polymer is preferably at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.
< production of polyimide precursor (Polyamic acid) >
Examples of the polyimide precursor used in the present invention include polyamic acids and polyamic acid esters.
The polyamic acid as the polyimide precursor used in the present invention can be produced, for example, by the following method. Specifically, the diamine component and the tetracarboxylic acid component can be reacted in the presence of an organic solvent at-20 to 150 ℃, preferably 0 to 80 ℃ for 30 minutes to 24 hours, preferably 1 to 12 hours.
The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used in this case is not particularly limited as long as the polyimide precursor formed by dissolution is obtained. Specific examples of the organic solvent used in the reaction are given below, but the organic solvent is not limited to these examples. For example, there may be mentioned: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or 1, 3-dimethyl-2-imidazolidinone.
When the polyimide precursor has high solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or an organic solvent represented by the following formulae [ D-1 ] to [ D-3 ] may be used.
Formula [ D-1]In (D)1Represents an alkyl group having 1 to 3 carbon atoms, formula [ D-2 ]]In (D)2Represents an alkyl group having 1 to 3 carbon atoms, formula [ D-3 ]]In (D)3Represents an alkyl group having 1 to 4 carbon atoms.
These organic solvents may be used alone or in combination. Further, even if the solvent is a solvent that does not dissolve the polyimide precursor, the solvent may be used in combination with the polyimide precursor within a range in which the polyimide precursor to be produced does not precipitate.
The concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, in view of preventing precipitation of the polymer and facilitating production of a high molecular weight product.
The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring the reaction solution into a poor solvent while sufficiently stirring the solution. Further, the polyamic acid is precipitated several times, washed with a poor solvent, and dried at normal temperature or under heating to obtain a powder of the purified polyamic acid. The poor solvent is not particularly limited, and examples thereof include: water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.
< production of polyimide precursor (polyamic acid ester) >
The polyamic acid ester as the polyimide precursor used in the present invention can be produced, for example, by the production method of (1), (2), or (3) shown below.
(1) Case of production from Polyamic acid
The polyamic acid ester can be produced by esterifying the polyamic acid produced as described above. Specifically, the polyamic acid can be produced by reacting a polyamic acid with an esterifying agent in the presence of an organic solvent at-20 to 150 ℃, preferably 0 to 50 ℃ for 30 minutes to 24 hours, preferably 1 to 4 hours.
The esterification agent is preferably an esterification agent which can be easily removed by purification, and examples thereof include: n, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dineopentylbutyl acetal, N-dimethylformamide di-tert-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 amount of the esterifying agent added is preferably 2 to 6 molar equivalents based on 1 mole of the repeating unit of the polyamic acid.
Examples of the organic solvent include: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or 1, 3-dimethyl-2-imidazolidinone. When the polyimide precursor has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or an organic solvent represented by the above formulae [ D-1 ] to [ D-3 ] can be used.
These organic solvents may be used alone or in combination. Further, even if the solvent is a solvent that does not dissolve the polyimide precursor, the solvent may be used in combination with the polyimide precursor within a range in which the polyimide precursor to be produced does not precipitate. Further, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the polyimide precursor to be produced, it is preferable to use an organic solvent obtained by dehydration and drying.
The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ -butyrolactone, and one kind or two or more kinds may be used in combination, from the viewpoint of solubility of the polymer. The concentration during production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, in view of the difficulty in causing precipitation of the polymer and the easiness in obtaining a high molecular weight product.
(2) Produced by reaction of tetracarboxylic acid diester dichloride with diamine
The polyamic acid ester can be made from a tetracarboxylic acid diester dichloride and a diamine. Specifically, the reaction can be carried out by reacting a tetracarboxylic acid diester dichloride with a diamine at-20 to 150 ℃, preferably 0 to 50 ℃, for 30 minutes to 24 hours, preferably 1 to 4 hours, in the presence of a base and an organic solvent.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable in order to allow the reaction to proceed mildly. The amount of the base to be added is preferably 2 to 4 times by mol based on the tetracarboxylic acid diester dichloride, from the viewpoint of ease of removal and availability of a high molecular weight product.
The organic solvent is preferably N-methyl-2-pyrrolidone or γ -butyrolactone from the viewpoint of solubility of the monomer and the polymer, and these may be used alone or in combination of two or more.
The polymer concentration during production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, in view of the difficulty in causing precipitation of the polymer and the easiness in obtaining a high molecular weight product. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the organic solvent used in the production of the polyamic acid ester is preferably dehydrated as much as possible, and is preferably kept from being mixed with outside air in a nitrogen atmosphere.
(3) From tetracarboxylic diesters and diamines
The polyamic acid ester can be produced by polycondensing a tetracarboxylic acid diester with a diamine. Specifically, the reaction can be carried out by reacting a tetracarboxylic acid diester with a diamine in the presence of a condensing agent, a base and an organic solvent at 0 to 150 ℃, preferably 0 to 100 ℃, for 30 minutes to 24 hours, preferably 3 to 15 hours.
Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N ' -carbonyldiimidazole, dimethoxy-1, 3, 5-triazinylmethyl morpholinium, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium hexafluorophosphate, and diphenyl (2, 3-dihydro-2-thio-3-benzoxazolyl) phosphonate. The amount of the condensing agent to be added is preferably 2 to 3 times by mol based on the tetracarboxylic acid diester.
As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be added is preferably 2 to 4 times by mol based on the diamine component, from the viewpoint of ease of removal and availability of a high molecular weight product.
In addition, in the above reaction, the reaction proceeds efficiently by adding a lewis acid as an additive. As the lewis acid, lithium halide such as lithium chloride or lithium bromide is preferable. The amount of the Lewis acid added is preferably 0 to 1.0 mol per mol of the diamine component.
Among the above-mentioned three methods for producing polyamic acid esters, the method for producing (1) or (2) is particularly preferable in order to obtain a polyamic acid ester having a high molecular weight.
The solution of the polyamic acid ester obtained as described above can be poured into a poor solvent while sufficiently stirring to precipitate a polymer. The polyamic acid ester is precipitated several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyamic acid ester powder. The poor solvent is not particularly limited, and examples thereof include: water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.
< production of polyimide >
The polyimide used in the present invention can be produced by imidizing the polyamic acid described above.
The imidization can be carried out by stirring the polyamic acid to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the organic solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include: pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a suitable basicity for proceeding the reaction. Further, examples of the acid anhydride include: acetic anhydride, trimellitic anhydride, pyromellitic anhydride (pyroracemic anhydride), and the like, among them, acetic anhydride is preferable because purification after completion of the reaction becomes easy when acetic anhydride is used.
The imidization ratio in the present specification means a ratio of an imide group to a total amount of an imide group and a carboxyl group (or a derivative thereof) derived from a tetracarboxylic dianhydride or a derivative thereof. The imidization rate of the polyimide is not necessarily 100%, and the polyimide can be arbitrarily produced according to the use and purpose. The imidization ratio of the polyimide used in the present invention is preferably 20% to 100%, more preferably 50% to 99%.
The temperature for the imidization is-20 to 140 ℃, preferably 0 to 100 ℃, and the reaction time is 0.5 to 100 hours, preferably 1 to 80 hours. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the amount of the acid amide. The imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.
Since the catalyst and the like remain in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the obtained imidized polymer is preferably recovered by the following method and redissolved in an organic solvent to be used as the component (a) of the liquid crystal aligning agent of the present invention.
The solution of the polyimide obtained as described above can be poured into a poor solvent while sufficiently stirring to precipitate a polymer. The polyimide is precipitated several times, washed with a poor solvent, and dried at normal temperature or under heating to obtain a purified polyimide powder.
The poor solvent is not particularly limited, and examples thereof include: methanol, acetone, hexane, butyl cellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like.
< other ingredients >
The liquid crystal aligning agent of the present invention may contain components other than the polymer (P) as required. Examples of the component other than the polymer (P) include: a polymer other than the polymer (P), a crosslinkable compound, a functional silane compound, a surfactant, a compound having a photopolymerizable group, an organic solvent, and the like.
The polymer other than the polymer (P) may be used for the purpose of improving the solution characteristics of the liquid crystal aligning agent, the electrical characteristics of the liquid crystal alignment film, or imparting photo-alignment properties to the liquid crystal alignment film. Examples of the polymer include: polyamic acids, polyimides, polyamic acid esters, polyorganosiloxanes, polyesters, polyamides, polyureas, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.
When a polymer other than the polymer (P) is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 70 parts by mass or less, more preferably 0.1 to 60 parts by mass, and still more preferably 0.1 to 40 parts by mass, relative to 100 parts by mass of the total polymer components in the composition.
The crosslinkable compound can be used for the purpose of improving the strength of the liquid crystal alignment film. Examples of the crosslinkable compound include: a compound having an epoxy group, an isocyanate group, a glycidyl group or a cyclic carbonate group as described in paragraphs [0109] to [0113] of International patent publication WO 2016/047771; or a compound having at least one group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, and in addition, a blocked isocyanate group.
The blocked isocyanate compound is commercially available, and examples thereof include CORONATE AP STABLE M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (manufactured by NIPPON POLYURETHANE INDUSTRIAL CO., LTD.), TAKENATE B-830, B-815N, B-820 NSU, and B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Co., Ltd.).
Specific examples of preferable crosslinkable compounds include compounds represented by the following formulas (CL-1) to (CL-11).
The above is an example of the crosslinkable compound, but is not limited thereto. The liquid crystal aligning agent of the present invention may be used in combination with one or more kinds of crosslinkable compounds.
The content of the other crosslinkable compound in the liquid crystal aligning agent of the present invention is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass based on 100 parts by mass of the total polymer components.
The functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the lower substrate. Specific examples thereof include silane compounds described in paragraph [0019] of International patent publication No. 2014/119682. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total polymer components.
The surfactant can be used for the purpose of improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film. Examples of the surfactant include: fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like. Specific examples thereof include the surfactants described in paragraph [0117] of International publication WO 2016/047771. The amount of the surfactant used is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent.
Examples of the compound having a photopolymerizable group include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule, and examples thereof include compounds represented by the following formulae (M-1) to (M-7).
Further, as the compound which promotes charge transfer in the liquid crystal alignment film and promotes charge elution of the element, a nitrogen-containing heterocyclic amine compound represented by the formulae [ M1] to [ M156] described in paragraphs [0194] to [0200] of International publication No. WO2011/132751 (published 2011.10.27) may be added to the liquid crystal alignment agent of the present invention, and 3-aminomethylpyridine or 4-aminomethylpyridine is more preferably added. The amine compound may be added directly to the liquid crystal aligning agent, preferably after being prepared into a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as the specific polymer (P) is dissolved in the solvent.
When the liquid crystal aligning agent of the present invention contains a polyamic acid or a polyamic acid ester, an imidization accelerator or the like may be added for the purpose of efficiently imidizing a coating film by heating when the coating film is baked.
< organic solvent >
The liquid crystal aligning agent of the present invention may be prepared as a liquid composition in which the polymer (P) and other components used as needed are dispersed or dissolved in an appropriate organic solvent.
Examples of the organic solvent to be used include: lactone solvents such as γ -valerolactone and γ -butyrolactone; lactam solvents such as γ -butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- (N-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (N-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (N-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone, amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropane amide, 3-butoxy-N, N-dimethylpropane amide, and N, N-dimethyllactamide; 4-hydroxy-4-methyl-2-pentanone, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, Diisobutyl ketone (2, 6-dimethyl-4-heptanone), isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisoamyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1, 2-ethanediol, diisobutylcarbinol (2, 6-dimethyl-4-heptanol), propylene glycol diacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and the like. These may be used alone or in combination of two or more.
Preferred combinations of solvents include: n-methyl-2-pyrrolidone, gamma-butyrolactone, and ethylene glycol monobutyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone and propylene glycol monobutyl ether; n-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; n-methyl-2-pyrrolidone, γ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diethylene glycol diethyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisobutylcarbinol; n-methyl-2-pyrrolidone, gamma-butyrolactone and dipropylene glycol dimethyl ether; n-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; n-ethyl-2-pyrrolidone and propylene glycol diacetate; n-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; n-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; n-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate; n-ethyl-2-pyrrolidone and diethylene glycol diethyl ether; n-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; n-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; gamma-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; n-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone; n-ethyl-2-pyrrolidone, N-dimethyllactamide, diisobutyl ketone, and the like. The kind and content of such a solvent are appropriately selected depending on the coating apparatus, coating conditions, coating environment, and the like of the liquid crystal aligning agent.
The concentration of the solid component in the liquid crystal aligning agent (the ratio of the total mass of the components other than the organic 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, and the like, and is preferably in the range of 1 to 10 mass%.
The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 mass%. When the printing is performed by the printing method, it is particularly preferable that the solution viscosity is set to a range of 12 to 50mPa · s by setting the solid content concentration to a range of 3 to 9 mass%. In the case of the ink jet method, it is particularly preferable to set the solid content concentration to a range of 1 to 5 mass% and thereby set the solution viscosity to a range of 3 to 15 mPas.
< liquid crystal alignment film and liquid crystal display element >
The liquid crystal alignment film of the present invention is formed of the liquid crystal aligning agent prepared as described above. The liquid crystal display element of the present invention further includes a liquid crystal alignment film formed using the liquid crystal aligning agent. The driving mode of the liquid crystal display element is not particularly limited, and from the viewpoint of obtaining the effects of the present invention, a TN type, an STN type, and a VA type (including a VA-MVA (Multi-domain Vertical Alignment) type, a VA-PVA (Patterned Vertical Alignment) type, and the like) are preferable.
The liquid crystal display element can be manufactured by, for example, the following steps (1-1) to (1-3).
[ Process (1-1): formation of coating film ]
First, a liquid crystal aligning agent is applied to a substrate, and then the coated surface is heated, thereby forming a coating film on the substrate. First, a pair of two substrates each provided with a patterned transparent conductive film is coated with a liquid crystal aligning agent on each transparent conductive film formation surface by, preferably, an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method.
As the substrate, for example, a glass such as float glass (float glass) or soda glass (soda glass); and transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, tin oxide (SnO) can be used2) The NESA film (registered trademark of PPG corporation, USA) is composed of indium oxide-tin oxide (In)2O3－SnO2) And an ITO film formed therefrom.
After the liquid crystal aligning agent is applied, it is preferable to perform preliminary heating (prebaking) for the purpose of preventing the liquid of the applied liquid crystal aligning agent from sagging. The pre-drying temperature is preferably 30-200 ℃, more preferably 40-150 ℃, and particularly preferably 40-100 ℃. Then, the solvent is completely removed; and, when the liquid crystal aligning agent contains polyamic acid or polyamic acid ester, a firing (post-baking) step is performed for the purpose of imidizing the polyamic acid or polyamic acid ester. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 ℃, more preferably 120 to 250 ℃. The post-baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 1 to 1000nm, more preferably 5 to 500 nm.
[ Process (1-2): orientation ability imparting treatment
In the case of producing TN-type or STN-type liquid crystal display elements, the coating film formed in the step (1-1) is subjected to a treatment for imparting liquid crystal alignment ability. Examples of the orientation ability imparting treatment include: for example, the coating film is rubbed in a certain direction by a roll wound with a fabric made of a fiber such as nylon, rayon, or cotton. On the other hand, in the case of producing a VA liquid crystal display device, the coating film formed in the step (1-1) may be used as it is as a liquid crystal alignment film, or the coating film may be subjected to an alignment ability imparting treatment.
The liquid crystal alignment film preferable for the VA-type liquid crystal display element can also be preferably used for a psa (polymer sustained alignment) -type liquid crystal display element. Examples of the method for producing a liquid crystal display element using the liquid crystal aligning agent of the present invention include the following methods: the liquid crystal aligning agent is applied to a pair of substrates having conductive films to form coating films, the coating films are arranged to face each other with a liquid crystal molecular layer interposed therebetween to form a liquid crystal cell, and the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
[ Process (1-3): construction of liquid Crystal cell
(1-3A) As described above, two substrates on which liquid crystal alignment films are formed are prepared, and liquid crystal is disposed between the two substrates disposed to face each other, thereby manufacturing a liquid crystal cell. For manufacturing a liquid crystal cell, the following two methods can be cited, for example. In the first method, a liquid crystal cell can be manufactured by arranging two substrates facing each other with a gap (cell gap) therebetween so that the liquid crystal alignment films face each other, bonding peripheral portions of the two substrates together with a sealant, filling a liquid crystal into the cell gap defined by the substrate surfaces and the sealant, and then sealing the filling hole. The second method is a method called an ODF (One Drop Fill) method. A liquid crystal cell can be manufactured by applying, for example, an ultraviolet-curable sealant to a predetermined position on one of two substrates on which a liquid crystal alignment film is formed, dropping liquid crystal onto predetermined portions on the surface of the liquid crystal alignment film, then bonding the other substrate so that the liquid crystal alignment film faces each other, spreading the liquid crystal over the entire surface of the substrate, and then irradiating ultraviolet light onto the entire surface of the substrate to cure the sealant. In the case of using any method, it is desirable that, for each liquid crystal cell manufactured as described above, the flow alignment at the time of filling the liquid crystal is removed by further heating the liquid crystal to be used to a temperature at which the liquid crystal becomes isotropic and then slowly cooling the liquid crystal to room temperature.
As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. The liquid crystal includes nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable.
(1-3B) in the case of producing a PSA type liquid crystal display element, a liquid crystal cell was constructed in the same manner as in (1-3A) except that the compound having the photopolymerizable group was injected or dropped together with a liquid crystal. In this case, the content of the compound having a photopolymerizable group is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the liquid crystal component. After the liquid crystal cell is produced, the polymerizable compound is polymerized by applying an ac/dc voltage to the liquid crystal cell and irradiating the liquid crystal cell with heat or ultraviolet light. Thereby, the alignment of the liquid crystal molecules can be controlled. Then, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The applied voltage may be, for example, 5 to 50V DC or AC. The light to be irradiated is preferably ultraviolet light having a wavelength of 300 to 400 nm. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The dose of light irradiation is preferably 1000J/m2More than and less than 200000J/m2More preferably 1000 to 100000J/m2。
(1-3C) in the case of forming a coating film on a substrate using a liquid crystal aligning agent containing a compound having a photopolymerizable group, the following method may be employed: a liquid crystal cell was constructed in the same manner as in (1-3A) above, and then, a liquid crystal display element was manufactured through a step of irradiating the liquid crystal cell with light while a voltage was applied between the conductive films of the pair of substrates. In this case, the content of the compound having a photopolymerizable group is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total polymer components. According to this method, the advantage of the PSA mode can be achieved with a small amount of light irradiation. The above-mentioned (1-3B) can be applied to the applied voltage and the conditions of the light to be irradiated.
Further, a polarizing plate is bonded to the outer surface of the liquid crystal cell, whereby a liquid crystal display element can be obtained. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include: a polarizing plate which is formed by sandwiching a polarizing film called "H film" which absorbs iodine while extending and orienting polyvinyl alcohol with a cellulose acetate protective film; or a polarizing plate composed of the H film itself.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto. The meanings of abbreviations for the compounds used in the examples are shown below.
(tetracarboxylic dianhydride)
BODA: bicyclo [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic dianhydride.
CBDA: 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride.
(diamine)
m-PDA: 1, 3-phenylene diamine.
(solvent)
NMP: n-methyl-2-pyrrolidone.
BCS: butyl cellosolve.
THF: tetrahydrofuran.
< determination of molecular weight of polyimide >
A measuring device: normal temperature Gel Permeation Chromatography (GPC) (SSC-7200) manufactured by SENSHU scientific Co.
A chromatographic column: column (KD-803, KD-805) manufactured by Shodex corporation, column temperature: at 50 ℃.
Eluent: n, N' -dimethylformamide (as additive, lithium bromide-hydrate (LiBr. H)2O) 30mmol/L, phosphoric acid/anhydrous crystals (O-phosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10 ml/L).
Flow rate: 1.0 ml/min.
Calibration curve preparation standard sample: TSK Standard polyethylene oxide manufactured by Tosoh corporation (molecular weight: 9000000, 150000, 100000, 30000); and polyethylene glycol (molecular weight about 12000, 4000, 1000) manufactured by Polymer Laboratory.
< measurement of chemical imidization Rate >
20mg of polyimide powder and 1.0ml of deuterated dimethyl sulfoxide (DMSO-d 6, 0.05% TMS mixture) were added to an NMR sample tube (NMR Standard tube. phi.5 manufactured by Softysciences corporation), and ultrasonic waves were applied thereto to completely dissolve the polyimide powder. The proton NMR of the solution at 500MHz was measured by using an NMR measuring instrument (JNW-ECA 500) manufactured by electronic DATUM of Japan. The imidization ratio was determined as follows: the proton derived from the structure which has not changed before and after imidization is determined as a reference proton, and the peak integral value of the proton derived from the NH group of amic acid appearing in the vicinity of 9.5 to 10.0ppm are used to obtain the following formula. In the formula, x is a peak integrated value of a proton derived from an NH group of amic acid, y is a peak integrated value of a reference proton, and α is a ratio of the number of protons of the reference proton to the protons of one NH group of amic acid in the case of polyamic acid (imidization ratio of 0%).
Chemical imidization ratio (%) - (1-. alpha.x/y). times.100
DA-S1 is a novel compound, and the synthesis method is described in detail below.
The product described in monomer Synthesis example 1 below was identified by 1H-NMR analysis. The analysis conditions are as follows.
The device comprises the following steps: a Varian NMR System 400NB (400 MHz).
And (3) determination of a solvent: CDCl 3.
Reference substance: tetramethylsilane (TMS) (. delta.0.0 ppm for 1H).
< Synthesis of monomer Synthesis example DA-S1 >
Synthesis of Compound 3(3a, 3b mixture)
Magnesium (15.39g, 63.3mmol, 1.5eq.) was added to a four-necked flask, vacuum-dried for 1 hour in a vacuum pump, and then THF (100g) was added thereto by a syringe and stirred at room temperature. Then, a solution of Compound 1(100g, 42.2mmol) in THF (300g) was slowly added dropwise at a rate of about constant reflux and added. Then, the reaction solution was cooled to 0 ℃, and a solution of compound 2(105.60g, 42.2mmol, 1.0eq.) in THF (200g) was added dropwise. After completion of the dropwise addition, the temperature of the reaction mixture was returned to room temperature, and the mixture was stirred at room temperature for 3 hours. Then, toluene (1L) was added to dilute the reaction solution, and the reaction solution was cooled to 0 ℃ again, and a 10% acetic acid solution (500g) was slowly added dropwise.
Then, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with saturated saline (1L), saturated sodium bicarbonate solution (1L), and saturated saline (1L), respectively, and dried over anhydrous magnesium sulfate. Then, the mixture was filtered and distilled off by an evaporator to obtain 172g of crude crystals of Compound 3. The obtained crude crystals were used directly in the following reaction.
Synthesis of Compound 4
A mixture of compound 3(172g, 422mmol) as crude crystals and p-toluenesulfonic acid monohydrate (4.82g, 25.3mmol, 0.06eq.) in dehydrated toluene (MS4A dehydrate, 2L) was reacted under reflux for 2 hours with removal of water. After completion of the reaction, about half of the amount of toluene used was distilled off in an evaporator, and then the solution was stirred at room temperature to precipitate a solid. The obtained solid was filtered to obtain crystals of Compound 4 (specialty 150g, specialty 91%).
Synthesis of Compound 5(5a, 5b mixture)
A mixture of compound 4(108g, 276mmol), 5% palladium on carbon powder (water, 11g, 10 wt%), ethyl acetate (1L), and ethanol (1L) was stirred at room temperature in the presence of hydrogen. After completion of the reaction, toluene (2L) was added to dissolve the crystals, and then the reaction mixture was filtered through celite (celite), and the celite was washed with 1L of toluene. The filtrate was concentrated under reduced pressure, whereby the desired compound 5 was obtained (yield: 103.3g, 95%).
Synthesis of Compound 6
To a solution of 5(95.4g, 243mmol) in dichloromethane (800mL) at 0 ℃ under nitrogen substitution, BBr was added dropwise3(1.0M－CH2Cl2243mL, 1.01 mol). After the dropwise addition, the mixture was stirred at 0 ℃ for 2 hours. After the reaction, the reaction solution was added to distilled water in small amounts. The extract was extracted with ethyl acetate (1L), and the extract was washed twice with 500mL of distilled water. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized from ethanol, filtered, and washed with ethanol, whereby the target compound 6 was obtained (yield 18.6g, 21%).
Synthesis of Compound 8
To a mixture of compound 6(10.0g, 26.4mmol), potassium carbonate (11.0g, 79.2mmol, 3eq.), toluene (50g), a solution of compound 7(5.35g, 26.4mmol) in toluene (20g) was added dropwise under reflux. After the addition, stir at reflux-evening-out. After completion of the reaction, the reaction mixture was cooled to about 60 ℃ and then ethyl acetate (500g) was added thereto, followed by washing with distilled water three times. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized from acetonitrile/ethanol (2: 1) solution, filtered, and the filtered crystals were washed with ethanol to obtain crude crystals of compound 8. Purification of the crude crystals by column chromatography (SiO2, CHCl3) gave the crystals of Compound 8 (7.1 g, 49% yield).
Synthesis of DA-S1
A mixture of compound 8(12.2g, 22.4mmol), 5% palladium on carbon powder (aqueous 1.22g, 10 wt%), dioxane (120g) was stirred in the presence of hydrogen at 60 ℃ for 4 hours. After completion of the reaction, nitrogen substitution was performed, and then filtration was performed with celite while maintaining the temperature at 60 ℃. The solvent was distilled off from the filtrate under reduced pressure, and as a result, a crude product was obtained. The crude product was recrystallized from 2-propanol/ethyl acetate (2: 1), whereby the desired DA-S1 was obtained (yield 8.0g, yield 74%).
1H NMR(CDCl3，δppm)：7.725(1H，d)，7.577(2H，m)，7.272(2H，m)，7.102(1H，s)，6.791(1H，d)，6.207(1H，d)，6.117(1H，dd)，3.621(4H，broad)，2.553(1H，m)，2.067－0.863(31H，m)。
< Synthesis example 1 >
BODA (1.50g, 6.00mmol), m-PDA (0.78g, 7.20mmol) and DA-S1 (2.33g, 4.80mmol) were dissolved in NMP (18.4g), reacted at 60 ℃ for 3 hours, then CBDA (1.15g, 5.88mmol) and NMP (4.60g) were added, and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution. To the polyamic acid solution (23.0g) was added NMP to dilute the solution to 6.5 mass%, and then acetic anhydride (4.87g) and pyridine (1.51g) were added as imidization catalysts to react at 80 ℃ for 2.5 hours. The reaction solution was poured into methanol (270g), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ℃ to obtain polyimide powder. The polyimide had a chemical imidization rate of 82%, Mn of 14100 and Mw of 51800.
NMP (24.3g) was added to the obtained polyimide powder (2.7g), and the mixture was stirred at 70 ℃ for 12 hours to dissolve the NMP. BCS (18.0g) was added to the solution, and stirred at room temperature for 2 hours to thereby obtain a liquid crystal aligning agent SPI-1.
< Synthesis example 2 >
BODA (2.75g, 11.0mmol), m-PDA (1.43g, 13.2mmol) and DA-S2 (3.83g, 8.80mmol) were dissolved in NMP (32.0g), and after reaction at 60 ℃ for 3 hours, CBDA (2.11g, 10.8mmol) and NMP (8.50g) were added and reaction at 40 ℃ for 6 hours gave a polyamic acid solution. To the polyamic acid solution (44.6g) was added NMP to dilute the solution to 6.5 mass%, and acetic anhydride (9.86g) and pyridine (3.06g) were added as imidization catalysts to react at 80 ℃ for 2.5 hours. The reaction solution was poured into methanol (526g), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ℃ to obtain polyimide powder. The polyimide had a chemical imidization ratio of 78%, Mn of 13700 and Mw of 47400.
NMP (24.3g) was added to the obtained polyimide powder (2.7g), and the mixture was stirred at 70 ℃ for 12 hours to dissolve the NMP. BCS (18.0g) was added to the solution, and stirred at room temperature for 2 hours to thereby obtain a liquid crystal aligning agent SPI-2.
< Synthesis example 3 >
BODA (2.75g, 11.0mmol), m-PDA (1.43g, 13.2mmol) and DA-S3 (3.35g, 8.80mmol) were dissolved in NMP (30.1g), reacted at 60 ℃ for 3 hours, then CBDA (2.11g, 10.8mmol) and NMP (8.50g) were added, and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (42g) to dilute the solution to 6.5 mass%, and acetic anhydride (9.74g) and pyridine (3.02g) were added as imidization catalysts to react at 80 ℃ for 2.5 hours. The reaction solution was poured into methanol (497g), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ℃ to obtain polyimide powder. The polyimide had a chemical imidization ratio of 70%, Mn of 15400 and Mw of 51200.
NMP (24.3g) was added to the obtained polyimide powder (2.7g), and the mixture was stirred at 70 ℃ for 12 hours to dissolve the NMP. BCS (18.0g) was added to the solution, and stirred at room temperature for 2 hours to thereby obtain a liquid crystal aligning agent SPI-3.
[ Table 1]
< example 1 >
Using the liquid crystal alignment agent SPI-1 obtained in synthesis example 1, a liquid crystal cell was produced in the following procedure.
The liquid crystal aligning agent SPI-1 obtained in synthesis example 1 was spin-coated on a glass substrate with an ITO electrode and a substrate on which an ITO electrode pattern having a line width/line pitch (line/space) of 500 μm was formed, dried on a hot plate at 80 ℃ for 90 seconds, and then baked in a hot air circulation oven at 230 ℃ for 30 minutes or under severe conditions for 90 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. A bead spacer of 4 μm was spread on one of the liquid crystal alignment films, and a thermosetting sealing agent (XN-1500T, Co., Ltd.) was further printed thereon. Next, the other substrate was bonded to the former substrate with the surface of the other substrate on which the liquid crystal alignment film was formed as the inner side, and then the sealant was cured to prepare an empty cell. The empty cell was filled with liquid crystal MLC-3023 (trade name, manufactured by MERCK) containing a polymerizable compound for PSA by a reduced pressure injection method to prepare a liquid crystal cell. Then, the obtained liquid crystal cell was subjected to PSA treatment, and the pretilt angle was measured.
[ PSA treatment ]
UV of 10J/cm2 passed through a cut-off filter of 325nm or less was irradiated from the outside of the cell in a state where a DC voltage of 15V was applied. In terms of the illuminance of UV, a UV-35 photodetector was used in conjunction with UV-MO 3A, manufactured by ORC. Then, the residual unreacted polymerizable compound in the liquid crystal cell was irradiated with UV light for 30 minutes (UV lamp: FLR40SUV 32/A-1) using a UV-FL irradiation apparatus manufactured by Toshiba Lighting & Technology, Inc. in a state where no voltage was applied thereto, for the purpose of inactivating the residual polymerizable compound.
[ measurement of pretilt Angle ]
The pretilt angle of the cell prepared in the above was measured by using an LCD analyzer (LCA-LUV 42A manufactured by Ci Technica).
< comparative examples 1 and 2 >
Each liquid crystal cell was produced in the same manner as in example 1 except that SPI-2 and SPI-3 were used instead of SPI-1, respectively, and the pretilt angle was measured after PSA treatment. The results are shown in Table 2.
[ Table 2]
As shown in table 2, it was confirmed that: in comparative examples 1 and 2 in which liquid crystal aligning agents SPI-2 and SPI-3 containing diamines having no vertically aligning side chain of naphthylene were used, the difference between the pretilt angle under the severe conditions and the pretilt angle under the standard conditions was large, while in example 1 in which liquid crystal aligning agent SPI-1 containing diamine DA-S1 having a vertically aligning side chain of naphthylene was used, the difference between the pretilt angle under the severe conditions and the pretilt angle under the standard conditions was very small. From these results, it is found that a liquid crystal alignment film having a high liquid crystal alignment ability can be obtained even when a liquid crystal alignment agent containing a vertically aligned side chain diamine having a naphthylene group is exposed to excessive heating.
The entire contents of the specification, claims and abstract of japanese patent application No. 2019-173214, filed 24.9.9.2019, are incorporated herein by reference as disclosure of the specification of the present invention.
Claims (15)
1. A liquid crystal aligning agent comprising at least one polymer (P) selected from the group consisting of a polyimide precursor having a group represented by the following formula (1) and a polyimide,
*-X1-Q-X2-Y-R (1)
in the formula (1), X1An alkylene group having 1 to 14 carbon atoms, wherein one or two non-adjacent methylene groups in the alkylene group are optionally substituted by-O-or-COO-; x2Represents a single bond, -OCO-, -COO-, or CONR2-, said CONR2In (A) R2Represents a hydrogen atom or a methyl group; q represents a naphthylene group, Y represents a group containing at least one cyclohexylene group; optionally, any hydrogen atom of the naphthylene group or the cyclohexylene group is substituted by at least one selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, and a fluorine atom; r represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoroalkoxy group having 1 to 12 carbon atoms, -CN, -F, -OH, -CO2H、－OCOR3or-CO2R3，R3Represents a methyl or ethyl group; denotes a bond.
2. The liquid crystal aligning agent according to claim 1,
the polymer (P) is a polymer obtained from a diamine component containing a diamine having a group represented by the formula (1).
3. The liquid crystal aligning agent according to claim 2,
the diamine having the group represented by the formula (1) is at least one diamine selected from the group consisting of diamines represented by the following formulae (2-1) and (2-2),
in the formulae (2-1) and (2-2), X11、X21a、X21bAnd X of the formula (1)1Synonymy, Q1、Q2a、Q2bSynonymous with Q of said formula (1), X12、X22a、X22bAnd X of the formula (1)2Synonymy, Y1、Y2a、Y2bSynonymous with Y of the formula (1), R1、R2a、R2bSynonymous with R of said formula (1); l represents a single bond, -O-, -C (CH)3)2－、－NR－、－CO－、－NHCO－、－COO－、－(CH2)m－、－SO2－、－O－(CH2)m－O－、－O－C(CH3)2－、－CO－(CH2)m－、－NH－(CH2)m－、－SO2－(CH2)m－、－CONH－(CH2)m－、－CONH－(CH2)m-NHCO-, or-COO- (CH)2)m-OCO-, wherein-NR-, R represents a hydrogen atom or a methyl group; m represents an integer of 1 to 8.
4. The liquid crystal aligning agent according to any one of claims 1 to 3,
in the formula (1), Y represents a group represented by the following formula (Z),
in the formula (Z), X3Represents a single bond, - (CH)2)a－、－CONH－、－NHCO－、－CON(CH3) -, -NH-, -O-, -COO-, -OCO-or- ((CH)2)a1－A1)m1-, said- (CH)2)aIn the formula, a is an integer of 1 to 15; wherein a1 each independently represents an integer of 1 to 15, A1Each independently represents an oxygen atom or-COO-, m1Represents an integer of 1 to 2; y is1Represents a cyclohexylidene group, any hydrogen atom of the cyclohexylidene group being optionally substituted by at least one member selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, and a fluorine atom; n represents an integer of 1 to 10.
5. The liquid crystal aligning agent according to any one of claims 2 to 4,
the diamine having a group represented by the formula (1) is at least one diamine selected from the group consisting of diamines represented by the following formulae (d-1) to (d-12),
wherein m represents 2; n represents 3, 5 or 7; c represents 1 to 6; d represents 0 or 1.
6. The liquid crystal aligning agent according to any one of claims 2 to 5,
the polymer (P) is at least one polymer selected from the group consisting of a polyimide precursor obtained by polymerizing a diamine component containing a diamine having a group represented by the formula (1) with a tetracarboxylic acid component, and a polyimide obtained by imidizing the polyimide precursor.
7. The liquid crystal aligning agent according to claim 6,
the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula (3),
x represents any one structure selected from the following (X-1) to (X-13),
in the formulae (x-1) to (x-13), R1～R4Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring; r5And R6Each independently represents a hydrogen atom or a methyl group; j and k independently represent 0 or 1, A1And A2Each independently represents a single bond, an ether group, a carbonyl group, an ester group, a phenylene group, a sulfonyl group, or an amide group; [ 1] represents a bond to one acid anhydride group, and [ 2] represents a bond to the other acid anhydride group.
8. The liquid crystal aligning agent according to any one of claims 2 to 7,
the diamine having a group represented by the formula (1) is 10 to 80 mol% based on 100 mol% of the total diamine components.
9. The liquid crystal aligning agent according to any one of claims 1 to 8,
the content of the polymer (P) is 1-10% by mass relative to the total mass of the liquid crystal aligning agent.
10. A liquid crystal alignment film characterized in that,
is formed by using the liquid crystal aligning agent according to any one of claims 1 to 9.
11. A liquid crystal display element is characterized in that,
a liquid crystal alignment film according to claim 10.
12. A method for manufacturing a liquid crystal display element comprises the following steps:
a liquid crystal aligning agent according to any one of claims 1 to 9, which is applied to a pair of substrates having conductive films to form a coating film, wherein the coating films are arranged to face each other with a liquid crystal molecule layer interposed therebetween to form a liquid crystal cell, and wherein the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
13. A diamine represented by the following formula (2-1) or (2-2),
the definitions of the respective symbols are the same as those described in claim 3.
14. A polymer derived from a diamine component comprising at least one diamine as defined in claim 13.
15. The polymer of claim 14, wherein,
the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2019-173214 | 2019-09-24 | ||
| JP2019173214 | 2019-09-24 | ||
| PCT/JP2020/034324 WO2021059999A1 (en) | 2019-09-24 | 2020-09-15 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polymer, and diamine |
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| JP (1) | JPWO2021059999A1 (en) |
| KR (1) | KR20220068980A (en) |
| CN (1) | CN114466882A (en) |
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| WO (1) | WO2021059999A1 (en) |
Citations (6)
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|---|---|---|---|---|
| CN1246469A (en) * | 1998-04-22 | 2000-03-08 | 大日本油墨化学工业株式会社 | Naphthacridine derivative and liquid crystal composite containing it |
| JP2012159827A (en) * | 2011-01-12 | 2012-08-23 | Jsr Corp | Liquid crystal display element and alignment agent |
| JP2012208471A (en) * | 2011-03-17 | 2012-10-25 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| JP2013242526A (en) * | 2012-04-26 | 2013-12-05 | Jnc Corp | Liquid crystal alignment agent for forming liquid crystal alignment layer for optical alignment, liquid crystal alignment layer, and liquid crystal display element using the same |
| WO2015033921A1 (en) * | 2013-09-03 | 2015-03-12 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN109563409A (en) * | 2016-08-03 | 2019-04-02 | 捷恩智株式会社 | Liquid crystal display element, display device |
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|---|---|---|---|---|
| JP4175826B2 (en) | 2002-04-16 | 2008-11-05 | シャープ株式会社 | Liquid crystal display |
| CN101057178B (en) | 2004-12-28 | 2010-06-02 | 日产化学工业株式会社 | Liquid-crystal alignment material for vertical alignment, liquid-crystal alignment film, and liquid-crystal display element employing the same |
| US10465116B2 (en) * | 2010-12-23 | 2019-11-05 | Rolic Ag | Photoactive polymer materials |
-
2020
- 2020-09-15 CN CN202080066918.XA patent/CN114466882A/en active Pending
- 2020-09-15 JP JP2021548786A patent/JPWO2021059999A1/ja active Pending
- 2020-09-15 WO PCT/JP2020/034324 patent/WO2021059999A1/en active Application Filing
- 2020-09-15 KR KR1020227002806A patent/KR20220068980A/en unknown
- 2020-09-21 TW TW109132515A patent/TW202126794A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246469A (en) * | 1998-04-22 | 2000-03-08 | 大日本油墨化学工业株式会社 | Naphthacridine derivative and liquid crystal composite containing it |
| JP2012159827A (en) * | 2011-01-12 | 2012-08-23 | Jsr Corp | Liquid crystal display element and alignment agent |
| JP2012208471A (en) * | 2011-03-17 | 2012-10-25 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| JP2013242526A (en) * | 2012-04-26 | 2013-12-05 | Jnc Corp | Liquid crystal alignment agent for forming liquid crystal alignment layer for optical alignment, liquid crystal alignment layer, and liquid crystal display element using the same |
| WO2015033921A1 (en) * | 2013-09-03 | 2015-03-12 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN109563409A (en) * | 2016-08-03 | 2019-04-02 | 捷恩智株式会社 | Liquid crystal display element, display device |
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| WO2021059999A1 (en) | 2021-04-01 |
| JPWO2021059999A1 (en) | 2021-04-01 |
| KR20220068980A (en) | 2022-05-26 |
| TW202126794A (en) | 2021-07-16 |
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