WO2018051956A1 - 液晶配向剤、液晶配向膜、及び液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜、及び液晶表示素子 Download PDFInfo
- Publication number
- WO2018051956A1 WO2018051956A1 PCT/JP2017/032729 JP2017032729W WO2018051956A1 WO 2018051956 A1 WO2018051956 A1 WO 2018051956A1 JP 2017032729 W JP2017032729 W JP 2017032729W WO 2018051956 A1 WO2018051956 A1 WO 2018051956A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- group
- component
- diamine
- aligning agent
- Prior art date
Links
- UJOBWOGCFQCDNV-UHFFFAOYSA-N c(cc1)cc2c1[nH]c1c2cccc1 Chemical compound c(cc1)cc2c1[nH]c1c2cccc1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Definitions
- the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the same, which are used when forming a liquid crystal alignment film.
- a liquid crystal alignment film which is a constituent member of a liquid crystal display element, is a film that uniformly arranges liquid crystals.
- Various quality improvements are required as the quality of liquid crystal display elements in recent years has been improved.
- the liquid crystal alignment film obtained by the above method has an advantage that it is difficult to cause an afterimage of the liquid crystal display element.
- the manufacturing process of the liquid crystal display element in the cleaning process after rubbing, Water droplets are generated at the time of drying, and the film surface is locally and unevenly cleaned. In the obtained liquid crystal display element, linear display unevenness along the air knife direction occurs.
- the present invention has been made in view of the above circumstances, and is excellent in various afterimage characteristics such as liquid crystal alignment properties, alignment regulating power, rubbing resistance, charge storage characteristics, and the like, and unevenness is caused when cleaning a substrate with a liquid crystal alignment film.
- An object of the present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device using the same for obtaining a liquid crystal alignment film that is not generated.
- the present inventor conducted extensive research to achieve the above object, and found that the above object can be achieved by a liquid crystal aligning agent containing an alkoxysilane compound having a specific group at the terminal.
- the present invention is proposed in view of the above-mentioned problems of the prior art, and has the following gist.
- (A) component a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride containing an aromatic structure, a diamine having any one of the following formulas (1) to (3) in the structure, and Polyamic acid obtained by reacting a diamine component containing at least one diamine selected from paraphenylenediamine
- m 1 is an integer of 2 to 18, and when m 1 is an integer of 3 to 18, —O— may exist between carbon-carbon bonds.
- one or more arbitrary hydrogen atoms on the benzene ring may be substituted with a monovalent organic group other than a primary amino group, and m 2 is an integer of 1 to 8. is there.
- one or more arbitrary hydrogen atoms on the benzene ring may be substituted with a monovalent organic group other than a primary amino group, and m 3 is an integer of 1 to 4. is there.
- the diamine component used in the component (A) further contains a diamine having a structure of the following formula (4).
- the liquid crystal alignment agent In the liquid crystal alignment agent.
- X 1 is an oxygen atom or a sulfur atom
- a 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9
- * represents a bond with another atom.
- the third aspect of the present invention for solving the above problem is the liquid crystal aligning agent according to the first aspect or the second aspect, further comprising the following component (C).
- (C) component polyamic which is a reaction product of a tetracarboxylic dianhydride component and a diamine component containing at least one of diamines having a structure represented by the following formula (13) or the following formula (14) acid
- the tetracarboxylic dianhydride component in the component (C) contains a tetracarboxylic dianhydride represented by the following formula (16).
- a tetracarboxylic dianhydride represented by the following formula (16) In the liquid crystal aligning agent of the third aspect.
- the tetracarboxylic dianhydride component in the component (C) is further a tetracarboxylic acid represented by the following formulas (17) to (19).
- the liquid crystal aligning agent according to the third aspect contains at least one dianhydride of a compound selected from:
- R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the tetracarboxylic dianhydride having an aromatic structure is 20 mol% to the total tetracarboxylic dianhydride component. It is in the liquid crystal aligning agent of the 1st aspect which is 100 mol%.
- the tetracarboxylic dianhydride having an aromatic structure is pyromellitic dianhydride and 3,3 ′, 4,
- the liquid crystal aligning agent of the first aspect which is at least one selected from 4′-biphenyltetracarboxylic dianhydride.
- the eighth aspect of the present invention for solving the above-mentioned problem is the liquid crystal aligning agent according to the first aspect, wherein the component (B) contains an alkoxysilane compound in which the substituent on Si is a trialkoxy group. It is in.
- a ninth aspect of the present invention for solving the above problem is the liquid crystal aligning agent according to the eighth aspect, wherein the trialkoxy group contains an alkoxysilane compound in which the triethoxy group is a triethoxy group.
- a tenth aspect of the present invention for solving the above problem is a liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of the first to ninth aspects.
- An eleventh aspect of the present invention for solving the above problem is a liquid crystal display device comprising the liquid crystal alignment film of the tenth aspect.
- the liquid crystal aligning agent of the present invention is excellent in various properties such as liquid crystal alignment properties, alignment regulating power, rubbing resistance, voltage holding properties, charge storage properties, etc., and does not cause unevenness when cleaning a substrate with a liquid crystal alignment film. It is possible to provide a liquid crystal alignment agent for obtaining a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element using the same.
- the liquid crystal aligning agent of this invention is a composition used for forming a liquid crystal aligning film,
- the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride containing an aromatic structure and following (1) A polyamic acid obtained by reacting a diamine component containing at least one diamine selected from a diamine having any one of the following (3) in the structure and paraphenylenediamine (hereinafter also referred to as a specific polymer (A)): And an alkoxysilane compound having a terminal selected from the group consisting of an epoxy group, a vinyl group, a styryl group, a methacryl group, an acrylic group, a ureido group, a mercaptooxy group, and an isocyanate group (hereinafter also referred to as a specific compound (B)) Say).
- a polyamic acid obtained by reacting a diamine component containing at least one diamine selected from a diamine having any one of
- the specific polymer (A) is a highly oriented component polyamic acid, a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride containing an aromatic structure, and the following (1) to (3): It is obtained by reacting with a diamine component containing at least one diamine selected from a diamine having any of them in the structure and paraphenylenediamine (hereinafter also referred to as a specific diamine).
- a liquid crystal alignment film including these structures is excellent in liquid crystal alignment and alignment regulating power.
- m 1 is an integer of 2 to 18, and is preferably 3 to 12 and more preferably 4 to 8 from the viewpoint of liquid crystal orientation and heat resistance.
- m 1 is an integer of 3 to 18, —O— may exist between carbon-carbon bonds.
- the divalent organic group having the above formula (1) in the structure preferably further contains an aromatic ring.
- Specific examples thereof include structures represented by the following formulas (5) to (10). Although it is mentioned, it is not limited to these. *
- m 1 is an integer of 2 to 18, preferably 3 to 12, and more preferably 4 to 8.
- m 1 is each independently an integer of 2 to 18, preferably 2 to 12, more preferably 2 to 8.
- m 2 is a single bond or an integer of 1 to 8, preferably 1 to 3, more preferably 1 or 2 from the viewpoint of voltage holding characteristics. It is.
- m 2 is an integer of 1 to 8, preferably 1 to 3, more preferably 1 or 2, from the viewpoint of voltage holding characteristics.
- m 2 is an integer of 1 to 4, and is preferably 1 or 2 from the viewpoint of the stability of the polyamic acid solution.
- one or more arbitrary hydrogen atoms on the benzene ring are monovalent other than the primary amino group. It may be substituted with an organic group.
- the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluorine-containing alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms.
- Alkyl group having 4 to 4, alkenyl group having 2 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, fluorine-containing alkyl group having 1 to 4 carbon atoms, fluorine-containing alkenyl group having 2 to 4 carbon atoms, carbon number 1 to A monovalent organic group selected from 4 fluorine-containing alkoxy groups is preferred.
- the hydrogen atom on the benzene ring is unsubstituted. *
- diamines having any one of the above formulas (1) to (3) in the structure are shown below, but are not limited thereto. *
- diamines having the above formula (1) in the structure 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, Examples include 8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
- 1,3-bis (4-aminophenoxy) propane 1,4 corresponding to the above formula (5), which is a more preferred structure as a divalent organic group formula having the above formula (1) in the structure, -Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, , 8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane and the like.
- Examples of the diamine having the above formula (3) in the structure include 4,4'-diaminobenzidine and 4,4'-diamino-p-terphenyl. *
- the diamine component used for the component (A) further contains a diamine having the structure of the following formula (4). *
- X 1 is an oxygen atom or a sulfur atom, an oxygen atom is preferable.
- a 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably 1 carbon atom. The total number of carbon atoms is 1 to 9, preferably 3 to 6. * Represents a bond with another atom.
- Examples of the diamine having the above formula (4) in the structure include diamines having the following structure.
- “Boc” is a tert-butoxycarbonyl group. *
- the diamines mentioned in the above specific examples are preferable as raw materials for synthesizing the specific polymer (A), and among the diamines used for the reaction with tetracarboxylic dianhydride, these diamines are preferably 10 Polyamic acid synthesized by using mol% to 100 mol%, more preferably 50 mol% to 100 mol%, is preferred as the specific polymer (A).
- a diamine other than the above diamine (hereinafter also referred to as other diamine) may be used to the extent that the effects of the present invention are exhibited.
- other diamine a diamine other than the above diamine
- the specific example of other diamine is shown below, it is not limited to these.
- alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, and isophorone diamine Etc. *
- carbocyclic aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 1,3-diamino-4-chlorobenzene, 4,4'-diaminodiphenyl-2,2'- Propane, 4,4'-diaminodiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 4,4'-diphenylthioether, 4,4'-diaminodiphenyl sulfone 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobenzoic acid phenyl ester, 2,2′-diaminobenzophenone, 4,4′-diaminobenzyl, bis (4-aminophenyl) phosphine oxide, bis (3 -
- diamines containing nitrogen atoms in addition to two amino groups include 2,4-diaminodiphenylamine, 2,4-diaminopyridine, 2,4-diamino-s-triazine, 2,7-diaminodibenzofuran, 3,7- Diaminophenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine, N, N′-bis (4-aminophenyl) -N-phenylamine, N , N′-bis (4-aminephenyl) -N-methylamine, 4,4′-diaminodiphenylurea and the like. *
- diamines for constituting A which increases the pretilt angle of liquid crystal 1-dodecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diamino Benzene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2-bis [4- (4-aminophenoxy) phenyl] octane, 4,4′-diamino-3-dodecyldiphenyl ether, 4- (4- Trans-n-heptylcyclohexylphenoxy) -1,3-diaminobenzene, 4- (4-trans-n-pentylcyclohexylphenoxy) -1,3-diaminobenzene, 4-trans-n-pentylbicyclohexyl-3,5 -Diaminobenzoate and the like
- the tetracarboxylic dianhydride component used in the production of the specific polymer (A) of the present invention is a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride containing an aromatic structure in the structure.
- the preferred ratio of the tetracarboxylic dianhydride containing an aromatic structure in the structure to the total tetracarboxylic dianhydride component is 20 mol% to 100 mol%, more preferably 50 mol% to 100 mol. %.
- tetracarboxylic dianhydrides containing an aromatic structure include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetra Preferred are carboxylic acid, bis (3,4-dicarboxyphenyl) ether, bis (3,4-dicarboxyphenyl) sulfone, 2,3,6,7-naphthalenetetracarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid is particularly preferred.
- Tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-dicarboxy-1,2 , 3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, etc.
- the voltage holding ratio is important, these may be mixed.
- the specific compound (B) contained in the liquid crystal aligning agent of the present invention is selected from the group consisting of an epoxy group, a vinyl group, a styryl group, a methacryl group, an acrylic group, a ureido group, a mercaptooxy group, an isocyanate group, and an isocyanurate group.
- An alkoxysilane compound having a terminal group is preferable, and an epoxy group, a ureido group, and an isocyanate group are particularly preferable.
- the alkoxysilane at the terminal is preferably a trialkoxy group or a dialkoxy group, and among them, a triethoxy group is particularly preferable.
- Specific polymer (C) As a polymer used for the liquid crystal aligning agent of this invention, it is preferable to contain the specific polymer (C) explained in full detail below besides the specific polymer (A).
- the specific polymer (C) is a low resistance component polyamic acid. *
- the diamine component used for the specific polymer (C) contains at least one of diamine compounds having a structure represented by the following formula (13) and the following formula (14). *
- the structure of the above formula (13) is preferably a 4,4′-bonded diphenylamine group from the viewpoint of liquid crystal alignment, and the structure of the above formula (14) is preferably 3, 6 from the viewpoint of liquid crystal alignment.
- one or more of arbitrary hydrogen atoms on the benzene ring may be substituted with a monovalent organic group other than the primary amino group.
- the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluorine-containing alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms.
- Alkyl group having 4 to 4, alkenyl group having 2 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, fluorine-containing alkyl group having 1 to 4 carbon atoms, fluorine-containing alkenyl group having 2 to 4 carbon atoms, carbon number 1 to A monovalent organic group selected from 4 fluorine-containing alkoxy groups is preferred.
- More preferable structures of the above formula (13) and the above formula (14) are those in which a hydrogen atom on the benzene ring is unsubstituted. *
- the ratio of the diamine compound containing the structure represented by the above formula (13) or the above formula (14) to the total diamine component is preferably 10 mol% to 100 mol%, more preferably 60 mol%. Mol% to 100 mol%.
- 4,4′-diaminodiphenylamine is used from the viewpoint of the reactivity with tetracarboxylic dianhydride and the liquid crystal alignment property when used as a liquid crystal alignment film.
- 3,6-diaminocarbazole is particularly preferred.
- the following formula (15) may be used as long as the effects of the present invention are not impaired. It is also possible to contain other diamine compounds. Specific examples of other diamines are shown below, but are not limited thereto. *
- aliphatic diamines include diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Octane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,4-diamino-2,2-dimethylbutane, 1,6-diamino-2,5 -Dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane 2,11-diaminododecane
- alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, and isophoronediamine Etc. *
- carbocyclic aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminotoluenes (eg, 2,4-diaminotoluene), 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylenes, 1,3-diamino-4-chlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-4-isopropylbenzene, 4,4'-diaminodiphenyl- 2,2′-propane, 4,4′-diaminodiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4′-diaminodiphenyl ether, 4,4′-diphenylthioether, 4,4 '-Diaminodiphenylsulf
- diamines for constituting A which increases the pretilt angle of liquid crystal 1-dodecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diamino Benzene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2-bis [4- (4-aminophenoxy) phenyl] octane, 4,4′-diamino-3-dodecyldiphenyl ether, 4- (4- Trans-n-heptylcyclohexylphenoxy) -1,3-diaminobenzene, 4- (4-trans-n-pentylcyclohexylphenoxy) -1,3-diaminobenzene, 4-trans-n-pentylbicyclohexyl-3,5 -Diaminobenzoate and the like
- the tetracarboxylic dianhydride component used for the production of the specific polymer (C) contains a dianhydride of a tetracarboxylic acid compound represented by the following formula (16). *
- the tetracarboxylic dianhydride component is selected from a dianhydride of a tetracarboxylic acid compound represented by the following formula (16) and a tetracarboxylic acid represented by the following formula (17) to the following formula (19). Those consisting of at least one dianhydride of the compound are preferred. *
- R 1, R 2, R 3, R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the composition ratio of tetracarboxylic dianhydride is preferably 10 mol% to 100 mol% of the total tetracarboxylic dianhydride component, and the above formula (16).
- (17) to at least one tetracarboxylic acid compound dianhydride selected from the tetracarboxylic acid compounds represented by the formula (19) is 0 mol% to 90 mol% of the total tetracarboxylic dianhydride component. is there. More preferably, the tetracarboxylic dianhydride represented by the above formula (16) is 10 mol% to 90 mol% of the total tetracarboxylic dianhydride component, and the above formula (17) to the above formula (19).
- the dianhydride of at least one tetracarboxylic acid compound selected from the tetracarboxylic acid compounds represented by the formula is 10 mol% to 90 mol% of the total tetracarboxylic dianhydride component. More preferably, the dianhydride of the tetracarboxylic acid represented by the above formula (16) is 20 to 80 mol% of the total tetracarboxylic dianhydride component, and from the above formula (17) to the above formula (19). The dianhydride of at least one tetracarboxylic acid compound selected from the tetracarboxylic acid compounds represented by the formula is 20 to 80 mol% of the total tetracarboxylic dianhydride component.
- the dianhydride of tetracarboxylic acid represented by the above formula (16) is 25 mol% to 75 mol% of the total tetracarboxylic dianhydride component, and the above formula (17) to the above formula (19).
- the dianhydride of at least one tetracarboxylic acid compound selected from the tetracarboxylic acid compounds represented by the formula is 25 mol% to 75 mol% of the total tetracarboxylic dianhydride component.
- a preferable combination of tetracarboxylic dianhydride components is a dianhydride of tetracarboxylic acid of the above formula (16) and the above formula (18) from the viewpoint of liquid crystal alignment.
- the ratio of the specific polymer (A) to the specific polymer (C) is such that the specific polymer (A) is 10% by weight to 95% with respect to the total amount of the specific polymer (A) and the specific polymer (C). It is preferably% by weight, more preferably 10% by weight to 50% by weight. If the amount of the specific polymer (A) is too small, the charge accumulation characteristics and the rubbing resistance of the liquid crystal alignment film may be deteriorated. If the amount of the specific polymer (C) is too small, the alignment property and alignment regulating power of the liquid crystal are deteriorated. There are things to do.
- the specific polymer (A) and the specific polymer (C) contained in the liquid crystal aligning agent of the present invention may each be one type or two or more types.
- the organic solvent used in the above reaction is not particularly limited as long as the produced polyamic acid can be dissolved, but specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, and ⁇ -butyrolactone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible. *
- a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
- a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
- the method of adding alternately etc. are mentioned, In this invention, any of these methods may be sufficient.
- the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds
- the plurality of types of components may be reacted in a mixed state in advance or may be reacted individually and sequentially.
- the temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent is usually 0 ° C. to 150 ° C., preferably 5 ° C. to 100 ° C., more preferably 10 ° C. to 80 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, it is preferably 1% by weight to 50% by weight, and more preferably 5% by weight to 30% by weight.
- the initial reaction may be carried out at a high concentration, and then an organic solvent may be added. *
- the ratio of the tetracarboxylic dianhydride component and the diamine component used for the polyamic acid polymerization reaction is preferably 1: 0.8 to 1.2 in terms of molar ratio.
- the polyamic acid obtained by adding an excess of the diamine component may increase the coloration of the solution. If the coloration of the solution is a concern, the ratio may be 1: 0.8 to 1. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1: 1, the higher the molecular weight of the polyamic acid obtained. If the molecular weight of the polyamic acid is too small, the strength of the coating film obtained therefrom may be insufficient.
- the polyamic acid used in the liquid crystal aligning agent of the present invention is preferably 0.1 to 2.0, more preferably 0.2 to 1.5 in terms of reduced viscosity (concentration 0.5 dl / g, 30 ° C. in NMP). is there. *
- the solvent used for the polymerization of the polyamic acid is not desired to be contained in the liquid crystal aligning agent of the present invention, or if unreacted monomer components or impurities are present in the reaction solution, the precipitate is collected and purified.
- the polyamic acid solution is preferably added to a stirring poor solvent, and the precipitate is recovered.
- recovery of polyamic acid Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc. can be illustrated.
- the polyamic acid precipitated by introducing it into a poor solvent can be recovered by filtration, washing and drying at room temperature or under reduced pressure at normal temperature or under reduced pressure.
- the polyamic acid can be purified.
- liquid crystal aligning agent a coating liquid containing a specific polymer (A) and a specific compound (B), if a uniform thin film can be formed on a board
- Other forms may be possible.
- the reaction solution of polyamic acid may be mixed as it is, and the solid polyamic acid is dissolved in an organic solvent and then mixed. You may do it. *
- the organic solvent is not particularly limited as long as it can dissolve the resin component contained therein.
- Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, and the like. May be used alone or in combination.
- the organic solvent contained in the liquid crystal aligning agent uses a mixed solvent that is used in combination with a solvent that improves the coating properties and the surface smoothness of the coating film when the liquid crystal aligning agent is applied in addition to the above-described solvents.
- a mixed solvent is also preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent to be used in combination are given below, but the organic solvent is not limited to these examples.
- ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6- Zimechi -4-heptanol, 1,2-ethanedi
- D 1 represents an alkyl group having 1 to 3 carbon atoms.
- D 2 represents an alkyl group having 1 to 3 carbon atoms.
- D 3 represents an alkyl group having 1 to 4 carbon atoms.
- preferred solvent combinations include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, propylene glycol monobutyl ether, and N-ethyl-2-pyrrolidone.
- propylene glycol monobutyl ether N-methyl-2-pyrrolidone and ⁇ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and propylene glycol monobutyl ether 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and ⁇ -butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyro Examples thereof include lidone, ⁇ -butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and dipropylene glycol dimethyl ether.
- the kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent
- the solid content concentration can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed, but is preferably 1 wt% to 10 wt%. If it is less than 1% by weight, it is difficult to form a uniform and defect-free coating film, and if it exceeds 10% by weight, the storage stability of the solution may deteriorate.
- an additive such as a silane coupling agent may be added to the liquid crystal aligning agent of the present invention, and other resin components may be added.
- the liquid crystal aligning agent of the present invention obtained as described above can be filtered as necessary, applied to a substrate, dried and baked to form a coating film. By performing alignment treatment such as irradiation, it can be used as a liquid crystal alignment film.
- the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a new substrate from the viewpoint of simplification of the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
- liquid crystal aligning agent examples include spin coating, printing, and ink-jet methods, but from the viewpoint of productivity, the transfer printing method is widely used industrially. Are also preferably used. *
- the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred.
- the drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like.
- a method of drying on a hot plate at 50 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C. for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes is used. *
- the firing of the liquid crystal aligning agent can be performed at an arbitrary temperature of 100 ° C. to 350 ° C., preferably 150 ° C. to 300 ° C., more preferably 200 ° C. to 250 ° C.
- the liquid crystal aligning agent contains a polyamic acid
- the conversion rate from the polyamic acid to the polyimide changes depending on the baking temperature, but the liquid crystal aligning agent of the present invention does not necessarily need to be imidized 100%.
- baking is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell manufacturing process, such as sealing agent curing. *
- the thickness of the coating film after baking is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so 5 nm to 300 nm, preferably 10 nm to 100 nm. It is. *
- liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention as described above has excellent characteristics, liquid crystal display elements such as TN, STN, TFT, lateral electric field type, and further, ferroelectric It can be used as a liquid crystal alignment film for a liquid crystal display element having a property and antiferroelectric property. In particular, it can be suitably used as a liquid crystal alignment film for a horizontal electric field type liquid crystal display element in which seizure due to the alignment regulating force easily occurs.
- the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
- a pair of substrates on which a liquid crystal alignment film is formed are sandwiched by spacers of 1 ⁇ m to 30 ⁇ m, preferably 2 ⁇ m to 10 ⁇ m, and the rubbing direction is an arbitrary angle of 0 ° to 270 °.
- a method is generally used in which the surroundings are fixed with a sealant, and liquid crystal is injected and sealed.
- the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.
- the liquid crystal display element produced using the liquid crystal aligning agent of this invention is excellent in the orientation of a liquid crystal, alignment control power, and has the outstanding electrical property, it is a contrast fall or image sticking. It can be a liquid crystal display device that hardly occurs, and is suitably used for various types of display elements using nematic liquid crystal such as TN, STN, TFT, and lateral electric field type liquid crystal display elements. Further, by selecting a liquid crystal to be used, it can be used for a ferroelectric and antiferroelectric liquid crystal display element. Among these liquid crystal display elements, the liquid crystal display element is particularly preferably used for a horizontal electric field type liquid crystal display element in which seizure due to the alignment regulating force easily occurs.
- NMP N-methyl-2-pyrrolidone
- BCS Butyl cellosolve
- GBL ⁇ -butyrolactone
- ⁇ Viscosity> the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24), temperature 25 Measured at ° C.
- a substrate with electrodes was prepared.
- the substrate is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
- an IZO electrode having a solid pattern constituting a counter electrode as a first layer is formed on the substrate.
- a SiN (silicon nitride) film formed by the CVD method is formed as the second layer.
- the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
- a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing.
- the size of each pixel is 10 mm long and about 5 mm wide.
- the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
- the pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of electrode elements having a dogleg shape whose central portion is bent.
- the width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.
- Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. *
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel.
- the electrode elements of the electrode are formed so as to form an angle of ⁇ 10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
- the polyimide film is rubbed with a rayon cloth in a predetermined rubbing direction (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. And dried at 80 ° C. for 10 minutes.
- the rubbing directions are combined so that they are antiparallel, the periphery is sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.8 ⁇ m is formed.
- a liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell.
- the obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation.
- the afterimage was evaluated using the following optical system and the like.
- the prepared liquid crystal cell is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the LED backlight is turned on with no voltage applied, so that the brightness of transmitted light is minimized.
- the arrangement angle of the liquid crystal cell was adjusted.
- VT curve voltage-transmittance curve
- the afterimage evaluation according to the above-described method was performed under a temperature condition in which the temperature of the liquid crystal cell was 23 ° C.
- the liquid crystal cell After leaving, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal, and the backlight is turned on with no voltage applied so that the brightness of the transmitted light is minimized.
- the arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ .
- the second area was compared with the first area, and a similar angle ⁇ was calculated. Then, the average value of the angle ⁇ values of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
- the value of the angle ⁇ of the liquid crystal cell exceeded 0.1 degree, it was defined as “defective” and evaluated.
- the value of the angle ⁇ of the liquid crystal cell did not exceed 0.1 degree, it was defined as “good” and evaluated.
- the polyimide film was rubbed once under the conditions of a roll diameter of 130 mm, a rotation speed of 1200 rpm, a moving speed of 20 mm / sec, an indentation amount of 0.4 mm, and a rayon cloth. Then, in a shower washer, clean with pure water for 1 minute with a pressure of 0.15 MPa and a flow rate of 7 liters / minute, and then drain and dry with an air knife so that the wind hits from the angle of 45 degrees with the rubbing direction. The plate was dried at 80 ° C. for 10 minutes.
- Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was applied very thinly on the substrate, and heated on a hot plate at 100 ° C. for 5 minutes. After standing at room temperature for 10 minutes, the alignment disorder of the liquid crystal was observed using a polarizing microscope.
- the polyamic acid solution (346.7 g) was added with NMP (339.3 g) and N2.0 solution (1.1% by weight of AD-2) (52.0 g) and BCS (262.0 g), and the polymer concentration of the polyamic acid solution (B2 )
- the liquid crystal alignment films of Examples 1 to 11 showed good results in any of the evaluation of stability of liquid crystal alignment, relaxation of accumulated charge, and evaluation of cleaning unevenness.
- the alignment films of Comparative Examples 1 to 3 could not achieve good results in all evaluations.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
Abstract
Description
特定重合体(A)は高配向成分のポリアミック酸であり、芳香族構造を含有するテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分と、下記(1)~下記(3)のいずれかを構造中に有するジアミン及びパラフェニレンジアミンから選ばれる少なくとも1種のジアミン(以下、特定ジアミンとも称する)を含有するジアミン成分とを反応させて得られることを特徴とするものである。これらの構造を含む液晶配向膜は液晶配向性、配向規制力に優れる。
本発明の特定重合体(A)に用いられるジアミン成分には、本発明の効果を奏する程度において、上記のジアミン以外のジアミン(以下、その他のジアミンとも称する)が用いられても良い。その他のジアミンの具体例を以下に示すが、これらに限定されるものではない。
本発明の特定重合体(A)の製造に用いられるテトラカルボン酸二無水物成分は、芳香族構造をその構造内に含有するテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分が好ましい。この場合、芳香族構造をその構造内に含有するテトラカルボン酸二無水物の、テトラカルボン酸二無水物成分全体における好ましい比率は20モル%~100モル%、より好ましくは50モル%~100モル%である。芳香族構造をその構造内に含有するテトラカルボン酸二無水物としては、ピロメリット酸、3,3’,4,4’-ビフェニルテトラカルボン酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、ビス(3,4-ジカルボキシフェニル)エーテル、ビス(3,4-ジカルボキシフェニル)スルホン、2,3,6,7-ナフタレンテトラカルボン酸などが好ましく、ピロメリット酸、3,3’,4,4’-ビフェニルテトラカルボン酸が特に好ましい。
本発明の液晶配向剤に含有される特定化合物(B)とは、エポキシ基、ビニル基、スチリル基、メタクリル基、アクリル基、ウレイド基、メルカプトキ基、イソシアネート基、イソシアヌレート基からなる群から選ばれる基を末端に有するアルコキシシラン化合物である。その中でも、エポキシ基、ウレイド基、イソシアネート基、イソシアヌレート基が好ましく、エポキシ基、ウレイド基、イソシアネート基が特に好ましい。
本発明の液晶配向剤に用いられる重合体としては、特定重合体(A)の他、下記に詳述する特定重合体(C)を含有していることが好ましい。
特定重合体(A)又は特定重合体(C)を、テトラカルボン酸二無水物とジアミンとの反応により得る場合には、有機溶媒中でテトラカルボン酸二無水物とジアミンとを混合して反応させる方法が簡便である。
以下に説明する本発明の液晶配向剤の形態は、特定重合体(A)及び特定化合物(B)を含有する塗布液であるが、基板上に均一な薄膜を形成することができるのであれば、他の形態であっても良い。
本発明の液晶表示素子は、上記した手法により本発明の液晶配向剤から液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製し、液晶表示素子としたものである。液晶セル作製の一例を挙げるならば、液晶配向膜の形成された1対の基板を、1μm~30μm、好ましくは2μm~10μmのスペーサーを挟んで、ラビング方向が0°~270°の任意の角度となるように設置して周囲をシール剤で固定し、液晶を注入して封止する方法が一般的である。液晶封入の方法については特に制限されず、作製した液晶セル内を減圧にした後液晶を注入する真空法、液晶を滴下した後封止を行う滴下法などが例示できる。
下記DA-6において「Boc」はtert-ブトキシカルボニル基である。
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
GBL:γ-ブチロラクトン
合成例において、重合体溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)、温度25℃で測定した。
初めに電極付きの基板を準備した。基板は、30mm×35mmの大きさで、厚さが0.7mmのガラス基板である。基板上には第1層目として対向電極を構成する、ベタ状のパターンを備えたIZO電極が形成されている。第1層目の対向電極の上には第2層目として、CVD法により成膜されたSiN(窒化珪素)膜が形成されている。第2層目のSiN膜の膜厚は500nmであり、層間絶縁膜として機能する。第2層目のSiN膜の上には、第3層目としてIZO膜をパターニングして形成された櫛歯状の画素電極が配置され、第1画素および第2画素の2つの画素を形成している。各画素のサイズは、縦10mmで横約5mmである。このとき、第1層目の対向電極と第3層目の画素電極とは、第2層目のSiN膜の作用により電気的に絶縁されている。
以下の光学系等を用いて残像の評価を行った。作製した液晶セルを偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でLEDバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。
この液晶セルを用い、60℃の恒温環境下、周波数30Hzで10Vppの交流電圧を168時間印加した。その後、液晶セルの画素電極と対向電極との間を短絡させた状態にし、そのまま室温に一日放置した。
得られた液晶配向剤を、液晶配向膜印刷機(飯沼ゲージ製 ドクターブレード方式S-150)、アニロックスロール(仕様:深度17マイクロメートル、400メッシュ)に液晶配向剤を約1cc滴下し、8×8cmの塗布面を有する印刷版(コムラテック製 仕様:400メッシュ、開口率30%、角度75度)を用いて、アニロックスロール圧は、Nip幅5mm、印圧マイナス0.12mmの条件で、10×10cmのガラス基板の中心に塗膜を形成した。その後、60℃のホットプレート上で2分間乾燥後、IRオーブンにて230℃15分間焼成し、ガラス基板上にポリイミド膜を得た。このポリイミド膜上を、ロール径130mm、回転数1200rpm、移動速度20mm/sec、押し込み量0.4mm、レーヨン布の条件で1回ラビングした。その後、シャワー洗浄機にて、圧力0.15MPa、流量7リットル/分の純水で1分間洗浄を行い、ラビング方向と45度の角度から風があたるように、エアナイフで水切り乾燥を行い、ホットプレート上で80℃10分間乾燥させた。その基板上に液晶(MLC-2041、メルク社製)をごく薄く塗布し、100℃のホットプレートで5分間加熱した。室温で10分間放置した後、偏光顕微鏡を使って液晶の配向乱れを観察した。
[ポリアミック酸B1の製造]
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-1を27.8g(0.140モル)、DA-4を111.6g(0.560モル)入れ、NMP1194gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を30.2g(0.154モル)加え、さらにNMPを341g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を131.4g(0.525モル)とNMPを170.5g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1376mPa・sであった。このポリアミック酸溶液346.7gにNMPを339.3g、AD-1を1.1重量%含むNMP溶液を52.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B1)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-1を27.8g(0.140モル)、DA-4を111.6g(0.560モル)入れ、NMP1194gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を30.2g(0.154モル)加え、さらにNMPを341g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を131.4g(0.525モル)とNMPを170.5g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1376mPa・sであった。このポリアミック酸溶液346.7gにNMPを339.3g、AD-2を1.1重量%含むNMP溶液を52.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B2)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-1を27.8g(0.140モル)、DA-4を111.6g(0.560モル)入れ、NMP1194gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を30.2g(0.154モル)加え、さらにNMPを341g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を131.4g(0.525モル)とNMPを170.5g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1376mPa・sであった。このポリアミック酸溶液346.7gにNMPを339.3g、AD-3を1.1重量%含むNMP溶液を52.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B3)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-7を25.0g(0.164モル)、DA-4を130.7g(0.656モル)入れ、NMP1331gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を77.2g(0.394モル)加え、さらにNMPを380g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を102.6g(0.410モル)とNMPを190.0g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1336mPa・sであった。このポリアミック酸溶液360.0gにNMPを324.0g、AD-2を1.1重量%含むNMP溶液を54.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B4)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-7を25.0g(0.164モル)、DA-4を130.7g(0.656モル)入れ、NMP1331gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を77.2g(0.394モル)加え、さらにNMPを380g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を102.6g(0.410モル)とNMPを190.0g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1336mPa・sであった。このポリアミック酸溶液360.0gにNMPを324.0g、AD-4を1.1重量%含むNMP溶液を54.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B5)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-8を17.7g(0.164モル)、DA-4を130.7g(0.656モル)入れ、NMP1289gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を77.2g(0.377モル)加え、さらにNMPを368g加え、窒素雰囲気下で1時間撹拌した。その後、CA-4を102.6g(0.410モル)とNMPを184.2g入れ、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、1312mPa・sであった。このポリアミック酸溶液360.0gにNMPを324.0g、AD-2を1.1重量%含むNMP溶液を54.0gおよびBCS262.0g加え、ポリマー濃度が5.8重量%のポリアミック酸溶液(B6)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-1を21.8g(0.110モル)、DA-4を87.7g(0.440モル)入れ、NMP1288gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を77.7g(0.396モル)加え、さらにNMPを396g加え、窒素雰囲気下で1時間撹拌した。その後、CA-3を33.0g(0.110モル)とNMPを495g入れ、6時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、131mPa・sであった。このポリアミック酸溶液612.2gにNMPを127.8g、AD-2を1.0重量%含むNMP溶液を60.0gおよびBCS200.0g加え、ポリマー濃度が6.0重量%のポリアミック酸溶液(B7)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-5を156.1g(0.545モル)入れ、NMP1593gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-1を116.7g(0.535モル)加え、さらにNMPを398g加え、窒素雰囲気下、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、510mPa・sであった。このポリアミック酸溶液535.7gにNMPを264.3g、およびBCS200.0g加え、ポリマー濃度が6.0重量%のポリアミック酸溶液(A1)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-5を110.0g(0.384モル)、DA-6を38.3g(0.096モル)入れ、NMP1459gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-1を100.5g(0.461モル)加え、さらにNMPを365g加え、窒素雰囲気下、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、502mPa・sであった。このポリアミック酸溶液555.6gにNMPを244.4g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A2)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-5を82.5g(0.288モル)、DA-6を76.5g(0.192モル)入れ、NMP1529gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-1を101.5g(0.465モル)加え、さらにNMPを382g加え、窒素雰囲気下、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、529mPa・sであった。このポリアミック酸溶液582.5gにNMPを217.5g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A3)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-5を85.9g(0.300モル)、DA-6を79.7g(0.200モル)入れ、NMP1171gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を46.1g(0.235モル)加え、さらにNMPを390g加え、窒素雰囲気下で2時間撹拌した。その後、CA-1を54.5g(0.250モル)とNMP390.5gを加え、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、518mPa・sであった。このポリアミック酸溶液571.4gにNMPを228.6g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A4)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-3を77.5g(0.300モル)、DA-6を79.7g(0.200モル)入れ、NMP1536gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-1を104.7g(0.480モル)加え、さらにNMPを384g加え、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、508mPa・sであった。このポリアミック酸溶液582.5gにNMPを217.5g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A5)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-2を73.3g(0.300モル)、DA-6を79.7g(0.200モル)入れ、NMP1505gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-1を103.6g(0.475モル)加え、さらにNMPを376g加え、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、501mPa・sであった。このポリアミック酸溶液582.5gにNMPを217.5g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A6)を得た。
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA-3を129.2g(0.500モル)入れ、NMP1594gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA-2を92.2g(0.470モル)加え、さらにNMPを398g加え、50℃で加熱しながら20時間撹拌し、25℃における粘度をE型粘度計(東機産業社製)で確認したところ、135mPa・sであった。このポリアミック酸溶液606.1gにNMPを193.9g、およびBCS200.0g加え、ポリマーの濃度が6.0重量%のポリアミック酸溶液(A7)を得た。
ポリアミック酸溶液A1を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A1:B2=2:8となるポリマー溶液(D1)を100g得た。
ポリアミック酸溶液A1を29.3g、B2を70.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A1:B2=3:7となるポリマー溶液(D2)を100g得た。
ポリアミック酸溶液A1を19.3g、B3を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A1:B3=2:8となるポリマー溶液(D3)を100g得た。
ポリアミック酸溶液A2を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A2:B2=2:8となるポリマー溶液(D4)を100g得た。
ポリアミック酸溶液A3を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A3:B2=2:8となるポリマー溶液(D5)を100g得た。
ポリアミック酸溶液A4を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A4:B2=2:8となるポリマー溶液(D6)を100g得た。
ポリアミック酸溶液A5を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A5:B2=2:8となるポリマー溶液(D7)を100g得た。
ポリアミック酸溶液A6を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A6:B2=2:8となるポリマー溶液(D8)を100g得た。
ポリアミック酸溶液A2を19.3g、B4を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A2:B4=2:8となるポリマー溶液(D9)を100g得た。
ポリアミック酸溶液A2を19.3g、B6を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A2:B6=2:8となるポリマー溶液(D10)を100g得た。
ポリアミック酸溶液A2を19.3g、B5を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A2:B5=2:8となるポリマー溶液(D11)を100g得た。
ポリアミック酸溶液A1を19.3g、B1を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A1:B1=2:8となるポリマー溶液(E1)を100g得た。
ポリアミック酸溶液A1を19.3g、B7を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A1:B7=2:8となるポリマー溶液(E2)を100g得た。
ポリアミック酸溶液A7を19.3g、B2を80.7g混合して、室温で2時間撹拌することで、ポリマー固形分の重量比が、A7:B2=2:8となるポリマー溶液(E3)を100g得た。
Claims (11)
- 下記(A)成分及び下記(B)成分を含有する液晶配向剤。
(A)成分:芳香族構造を含有するテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分と、下記式(1)~下記式(3)のいずれかを構造中に有するジアミン及びパラフェニレンジアミンから選ばれる少なくとも1種のジアミンを含有するジアミン成分とを反応させて得られるポリアミック酸
(B)成分:エポキシ基、ビニル基、スチリル基、メタクリル基、アクリル基、ウレイド基、メルカプトキ基、イソシアネート基からなる群から選ばれる基を末端に有するアルコキシシラン化合物 - 上記(A)成分において、芳香族構造を有するテトラカルボン酸二無水物が、全テトラカルボン酸二無水物成分に対し20モル%~100モル%である、請求項1に記載の液晶配向剤。
- 上記(A)成分において、芳香族構造を有するテトラカルボン酸二無水物が、ピロメリット酸二無水物及び3,3’,4,4’-ビフェニルテトラカルボン酸二無水物から選ばれる少なくとも1種である、請求項1に記載の液晶配向剤。
- 上記(B)成分において、Si上の置換基が、トリアルコキシ基であるアルコキシシラン化合物を含有する、請求項1に記載の液晶配向剤。
- 上記トリアルコキシ基が、トリエトキシ基であるアルコキシシラン化合物を含有する、請求項8に記載の液晶配向剤。
- 請求項1から請求項9のいずれか1項に記載の液晶配向剤から得られる液晶配向膜。
- 請求項10に記載の液晶配向膜を具備する液晶表示素子。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020197010128A KR102482054B1 (ko) | 2016-09-13 | 2017-09-11 | 액정 배향제, 액정 배향막, 및 액정 표시 소자 |
JP2018539712A JP7299557B2 (ja) | 2016-09-13 | 2017-09-11 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
CN201780069530.3A CN109937380B (zh) | 2016-09-13 | 2017-09-11 | 液晶取向剂、液晶取向膜及液晶表示元件 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016178850 | 2016-09-13 | ||
JP2016-178850 | 2016-09-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018051956A1 true WO2018051956A1 (ja) | 2018-03-22 |
Family
ID=61620061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/032729 WO2018051956A1 (ja) | 2016-09-13 | 2017-09-11 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7299557B2 (ja) |
KR (1) | KR102482054B1 (ja) |
CN (1) | CN109937380B (ja) |
TW (1) | TWI762508B (ja) |
WO (1) | WO2018051956A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022014470A1 (ja) * | 2020-07-17 | 2022-01-20 | 日産化学株式会社 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW202146524A (zh) * | 2020-06-10 | 2021-12-16 | 奇美實業股份有限公司 | 液晶配向劑、液晶配向膜及液晶顯示元件 |
JP2022027466A (ja) * | 2020-07-29 | 2022-02-10 | Jsr株式会社 | 液晶配向剤、液晶配向膜及び液晶素子 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5872924A (ja) * | 1981-10-28 | 1983-05-02 | Hitachi Ltd | 液晶表示素子 |
JPH11119226A (ja) * | 1997-10-09 | 1999-04-30 | Jsr Corp | 液晶配向剤 |
JP2001288447A (ja) * | 2000-02-03 | 2001-10-16 | Nippon Polyurethane Ind Co Ltd | 非水系ラミネート接着剤用ポリウレタン樹脂組成物及びこれを用いた非水系ラミネート接着剤 |
JP2002322240A (ja) * | 2001-04-26 | 2002-11-08 | Dainippon Ink & Chem Inc | 湿気硬化性ウレタン組成物 |
WO2014034792A1 (ja) * | 2012-08-30 | 2014-03-06 | 日産化学工業株式会社 | 液晶配向処理剤及びそれを用いた液晶表示素子 |
JP2015212807A (ja) * | 2014-04-14 | 2015-11-26 | Jnc株式会社 | 液晶配向剤、液晶配向膜および液晶表示素子 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4461564B2 (ja) * | 2000-04-13 | 2010-05-12 | チッソ株式会社 | ポリアミド酸、ポリアミド酸溶液、および該ポリアミド酸溶液を用いた液晶表示素子 |
AU2003289307A1 (en) | 2002-12-11 | 2004-06-30 | Nissan Chemical Industries, Ltd. | Liquid crystl orientating agent and liquid crystal display element using it |
WO2009148099A1 (ja) * | 2008-06-04 | 2009-12-10 | 日産化学工業株式会社 | ケイ素系液晶配向剤、液晶配向膜及び液晶表示素子 |
CN103261956B (zh) * | 2010-10-19 | 2016-03-16 | 日产化学工业株式会社 | 适用于光取向处理法的液晶取向剂及使用该液晶取向剂的液晶取向膜 |
KR101610558B1 (ko) * | 2011-07-12 | 2016-04-07 | 닛산 가가쿠 고교 가부시키 가이샤 | 액정 배향제, 액정 배향막 및 액정 표시 소자 |
US20130331482A1 (en) * | 2012-06-06 | 2013-12-12 | Jnc Petrochemical Corporation | Polymer composition having photoalignable group, liquid crystal alignment film formed of the polymer composition, and optical device having phase difference plate formed of the liquid crystal alignment film |
KR20170102041A (ko) * | 2012-10-18 | 2017-09-06 | 닛산 가가쿠 고교 가부시키 가이샤 | 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자 |
JP6398973B2 (ja) * | 2013-06-06 | 2018-10-03 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
CN110950781A (zh) * | 2013-10-23 | 2020-04-03 | 日产化学工业株式会社 | 新的二胺、聚酰胺酸和聚酰亚胺 |
JP2017106941A (ja) * | 2014-04-09 | 2017-06-15 | 日産化学工業株式会社 | アルコキシシリル基を有するウレア化合物及び液晶配向剤 |
CN105694912B (zh) * | 2014-12-11 | 2019-11-19 | 捷恩智株式会社 | 光取向用液晶取向剂、液晶取向膜及使用其的液晶显示元件 |
-
2017
- 2017-09-11 CN CN201780069530.3A patent/CN109937380B/zh active Active
- 2017-09-11 JP JP2018539712A patent/JP7299557B2/ja active Active
- 2017-09-11 WO PCT/JP2017/032729 patent/WO2018051956A1/ja active Application Filing
- 2017-09-11 KR KR1020197010128A patent/KR102482054B1/ko active IP Right Grant
- 2017-09-13 TW TW106131349A patent/TWI762508B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5872924A (ja) * | 1981-10-28 | 1983-05-02 | Hitachi Ltd | 液晶表示素子 |
JPH11119226A (ja) * | 1997-10-09 | 1999-04-30 | Jsr Corp | 液晶配向剤 |
JP2001288447A (ja) * | 2000-02-03 | 2001-10-16 | Nippon Polyurethane Ind Co Ltd | 非水系ラミネート接着剤用ポリウレタン樹脂組成物及びこれを用いた非水系ラミネート接着剤 |
JP2002322240A (ja) * | 2001-04-26 | 2002-11-08 | Dainippon Ink & Chem Inc | 湿気硬化性ウレタン組成物 |
WO2014034792A1 (ja) * | 2012-08-30 | 2014-03-06 | 日産化学工業株式会社 | 液晶配向処理剤及びそれを用いた液晶表示素子 |
JP2015212807A (ja) * | 2014-04-14 | 2015-11-26 | Jnc株式会社 | 液晶配向剤、液晶配向膜および液晶表示素子 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022014470A1 (ja) * | 2020-07-17 | 2022-01-20 | 日産化学株式会社 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
JPWO2022014470A1 (ja) * | 2020-07-17 | 2022-01-20 | ||
CN116234856A (zh) * | 2020-07-17 | 2023-06-06 | 日产化学株式会社 | 液晶取向剂、液晶取向膜以及液晶显示元件 |
JP7311047B2 (ja) | 2020-07-17 | 2023-07-19 | 日産化学株式会社 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
CN116234856B (zh) * | 2020-07-17 | 2024-04-09 | 日产化学株式会社 | 液晶取向剂、液晶取向膜以及液晶显示元件 |
Also Published As
Publication number | Publication date |
---|---|
TW201823308A (zh) | 2018-07-01 |
KR20190052052A (ko) | 2019-05-15 |
JPWO2018051956A1 (ja) | 2019-06-27 |
JP7299557B2 (ja) | 2023-06-28 |
CN109937380B (zh) | 2022-04-19 |
CN109937380A (zh) | 2019-06-25 |
TWI762508B (zh) | 2022-05-01 |
KR102482054B1 (ko) | 2022-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5773177B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7259328B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP6627772B2 (ja) | 液晶配向剤、液晶配向膜、及びそれを用いた液晶表示素子 | |
JP7107220B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2013157586A1 (ja) | 光配向法用の液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JPWO2020158818A1 (ja) | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 | |
JP7099327B2 (ja) | 液晶配向剤及び液晶配向膜の製造方法 | |
WO2020100918A1 (ja) | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 | |
JP7299557B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP7131538B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7196847B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2014148596A1 (ja) | 液晶配向剤、液晶配向膜およびそれを用いた液晶表示素子 | |
WO2022176680A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2020162462A1 (ja) | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 | |
WO2020184373A1 (ja) | 機能性高分子膜形成用塗布液及び機能性高分子膜 | |
JP7311047B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP7318826B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP7302744B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
CN111868619B (zh) | 液晶取向剂、液晶取向膜及液晶表示元件 | |
JP7022350B2 (ja) | 液晶配向剤、液晶配向膜および液晶表示素子 | |
CN117126676A (zh) | 液晶取向剂、液晶取向膜及液晶元件 | |
WO2019181878A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
CN116917798A (zh) | 液晶取向剂、液晶取向膜以及液晶显示元件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17850858 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018539712 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197010128 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17850858 Country of ref document: EP Kind code of ref document: A1 |