WO2016043230A1 - 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
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- WO2016043230A1 WO2016043230A1 PCT/JP2015/076339 JP2015076339W WO2016043230A1 WO 2016043230 A1 WO2016043230 A1 WO 2016043230A1 JP 2015076339 W JP2015076339 W JP 2015076339W WO 2016043230 A1 WO2016043230 A1 WO 2016043230A1
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- liquid crystal
- diamine
- formula
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- aligning agent
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- WLTKKHQHJVNQNY-UHFFFAOYSA-N CC(C)(C)OC(N(CCc1cccc(N)c1)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=N)=O Chemical compound CC(C)(C)OC(N(CCc1cccc(N)c1)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=N)=O WLTKKHQHJVNQNY-UHFFFAOYSA-N 0.000 description 1
- FWVCNPPIJKFBFW-UHFFFAOYSA-N CC(C)(C)OC(N(Cc(cc1)ccc1N)C(N(Cc(cc1)ccc1N)C(OC(C)(C)C)=O)=[U])=O Chemical compound CC(C)(C)OC(N(Cc(cc1)ccc1N)C(N(Cc(cc1)ccc1N)C(OC(C)(C)C)=O)=[U])=O FWVCNPPIJKFBFW-UHFFFAOYSA-N 0.000 description 1
- WIRPWEKFZMGXTC-UHFFFAOYSA-N CC(C)(C)OC(N(Cc(cc1)ccc1N)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=O)=O Chemical compound CC(C)(C)OC(N(Cc(cc1)ccc1N)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=O)=O WIRPWEKFZMGXTC-UHFFFAOYSA-N 0.000 description 1
- PWTWTUVWXWKLOQ-UHFFFAOYSA-N CC(C)(C)OC(N(Cc(cc1)ccc1N)C(NCc(cc1)ccc1N)=O)=O Chemical compound CC(C)(C)OC(N(Cc(cc1)ccc1N)C(NCc(cc1)ccc1N)=O)=O PWTWTUVWXWKLOQ-UHFFFAOYSA-N 0.000 description 1
- VIAKPLVDAFNTCX-UHFFFAOYSA-N CC(C)(C)OC(N(Cc(cc1)ccc1N)C(NCc1cccc(N)c1)=O)=O Chemical compound CC(C)(C)OC(N(Cc(cc1)ccc1N)C(NCc1cccc(N)c1)=O)=O VIAKPLVDAFNTCX-UHFFFAOYSA-N 0.000 description 1
- JCNOBRMIAVXEJQ-UHFFFAOYSA-N CC(C)(C)OC(N(Cc1cc(N)ccc1)C(NCc1cccc(N)c1)=[U])=O Chemical compound CC(C)(C)OC(N(Cc1cc(N)ccc1)C(NCc1cccc(N)c1)=[U])=O JCNOBRMIAVXEJQ-UHFFFAOYSA-N 0.000 description 1
- ZLCVBXGWXUIQMB-UHFFFAOYSA-N CC(C)(C)OC(N(Cc1cccc(N)c1)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=[U])=O Chemical compound CC(C)(C)OC(N(Cc1cccc(N)c1)C(N(Cc1cccc(N)c1)C(OC(C)(C)C)=O)=[U])=O ZLCVBXGWXUIQMB-UHFFFAOYSA-N 0.000 description 1
- YSUWBKZBKVOADK-UHFFFAOYSA-N CC(C)(C)OC(N(Cc1cccc(N)c1)C(NCc(cc1)ccc1N)=[U])=O Chemical compound CC(C)(C)OC(N(Cc1cccc(N)c1)C(NCc(cc1)ccc1N)=[U])=O YSUWBKZBKVOADK-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C1)=CC(C)=CC1C(OC(CC1)CC(CCC2C3CCC4(*)C2CCC4C(CCCC([Zn])[Zn])N)C13N)=O Chemical compound CC(C1)=CC(C)=CC1C(OC(CC1)CC(CCC2C3CCC4(*)C2CCC4C(CCCC([Zn])[Zn])N)C13N)=O 0.000 description 1
- DFHWSKKRTPRFGD-UHFFFAOYSA-N CCCNC(CCCC(N)[Zn])C(CCC1C(CCC2CC(CC3)OC(c4cc(C)cc(C)c4)=O)C(CC4)C23NC)C14NC Chemical compound CCCNC(CCCC(N)[Zn])C(CCC1C(CCC2CC(CC3)OC(c4cc(C)cc(C)c4)=O)C(CC4)C23NC)C14NC DFHWSKKRTPRFGD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Definitions
- the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element obtained by using a diamine having a specific structure.
- a liquid crystal alignment film of a liquid crystal display element is mainly a liquid crystal alignment film obtained by applying a liquid crystal alignment agent (also referred to as a liquid crystal alignment treatment agent) containing a polyimide polymer to a substrate and baking it.
- the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
- the liquid crystal alignment film is used for the liquid crystal alignment film due to demands for suppressing a decrease in contrast of the liquid crystal display element and reducing an afterimage phenomenon.
- the important characteristics are that the voltage holding ratio is high, the residual charge is small when a DC voltage is applied, and / or the relaxation of the residual charge accumulated by the DC voltage is fast.
- liquid crystal display element is known as a display device that is lightweight, thin, and has low power consumption.
- liquid crystal display devices such as mobile phones, smart phones, and tablet devices, which have rapidly expanded their share, have made remarkable developments that require high display quality.
- the width of the sealing agent used for bonding the substrates of the liquid crystal display elements is made narrower than before, so-called narrow frame. Is required.
- the application position of the sealant used for manufacturing the liquid crystal display element is applied to the position in contact with the end of the liquid crystal alignment film or on the liquid crystal alignment film.
- polyimide since polyimide has no or few polar groups, there is a problem that a covalent bond is not formed between the sealing agent and the liquid crystal alignment film surface, resulting in insufficient adhesion between the substrates.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment film that does not cause display unevenness in the vicinity of the frame of the liquid crystal display element and has good adhesion to a sealant and a substrate.
- An object of the present invention is to provide a liquid crystal aligning agent used for forming the liquid crystal, and to provide a novel diamine having a specific structure used for producing the liquid crystal aligning agent.
- the present inventors have found that a polyimide precursor using a diamine having a specific structure and / or a liquid crystal aligning agent containing a polyimide obtained from the polyimide precursor is provided. It has been found that it has excellent characteristics, and the present invention has been completed.
- the present invention is a liquid crystal aligning agent containing a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component and / or a polyimide obtained from the polyimide precursor, wherein the diamine component is represented by the following formula (
- a liquid crystal aligning agent comprising a diamine having a structure represented by 1).
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group represented by the following formula (2), at least one of which is represented by the formula (2).
- A is a divalent group which is a single bond or a hydrocarbon group having 1 to 4 carbon atoms.
- the liquid crystal alignment film formed using the polyimide precursor which uses the novel diamine which has the specific structure of this invention, and / or the polyimide obtained from this polyimide precursor is a sealing agent in a liquid crystal display element
- the adhesiveness to the substrate is high, the occurrence of display unevenness near the frame can be suppressed even under high temperature and high humidity conditions, and the frame area around the element can be reduced. Therefore, since the display area can be increased, the display area can be advantageously used for a small-sized and high-definition liquid crystal display element such as a mobile phone, a smart phone, and a tablet type element.
- the residual charge is quickly relaxed, there is an advantage that the afterimage phenomenon of the liquid crystal display element disappears in a short time.
- the polyimide precursor using a diamine having a specific structure of the present invention and / or a polyimide obtained from the polyimide precursor has a high solubility in a solvent, and thus has an advantage that a liquid crystal aligning agent having a high polymer concentration can be obtained. .
- the diamine contained in the diamine component used for obtaining the liquid crystal aligning agent of the present invention is a diamine having in its molecule a structure represented by the following formula (1).
- R 1 , R 2 and A are as defined above.
- at least one of R 1 and R 2 or both are preferably a group represented by the formula (2), and only one of R 1 and R 2 is preferred from the viewpoint of the orientation film strength during rubbing.
- A is preferably a single bond.
- the group of the formula (2) is a t-butoxycarbonyl group (also referred to as a Boc group in the present invention).
- the diamine having the structure represented by the above formula (1) in the molecule may be any diamine as long as the requirement is satisfied.
- a preferred example thereof is a diamine represented by the following formula [1].
- R 1 and R 2 are the same as those in the formula (1) including each preferable one.
- m and n are each independently an integer of 0 to 3, and are preferably 0 or 1 and more preferably 1 from the viewpoint of availability of raw materials.
- the amino group (—NH 2 ) in each benzene ring may be in any position of ortho, meta, or para with respect to the bonding position of the alkylene group. From the viewpoint of polymerization reactivity, the meta or para position is preferred, and the para position is more preferred.
- Examples of the diamine represented by the formula [1] preferably include the following compounds.
- Boc is a group represented by the following.
- the synthesis method of the diamine represented by Formula [1] is not specifically limited, As a general synthesis method, it can manufacture by reducing the dinitro compound X1 of the diamine X as shown below.
- R 1, R 2, m, n are each in the above formula (1) is the same as R 1, R 2, m, n.
- the reduction reaction includes a hydrogenation reaction in the presence of a catalyst, a reduction reaction performed in the presence of protons, a reduction reaction using formic acid as a hydrogen source, a reduction reaction using hydrazine as a hydrogen source, and the like. But you can. In view of the structure of the dinitro compound X1 and the reactivity of the reduction reaction, a hydrogenation reaction is preferred.
- the catalyst used for the reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon and the like. Further, palladium catalyst, platinum oxide, Raney nickel or the like may not necessarily be an activated carbon supported metal catalyst. Palladium-activated carbon, which is generally widely used, is preferred because good results are obtained.
- the reaction may be carried out in the presence of activated carbon.
- the amount of the activated carbon to be used is not particularly limited, but is preferably 1 to 20% by mass, more preferably 5 to 10% by mass with respect to the dinitro compound X1.
- the reaction may be carried out under pressure. In this case, in order to avoid reduction of benzene nuclei, it is carried out in a pressure range up to 20 atm. The reaction is preferably carried out in the range up to 10 atm.
- aprotic polar organic solvents DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (dimethylacetamide), NMP (N-methyl-2-pyrrolidone), etc.
- ethers Et 2 O (Diethyl ether), i-Pr 2 O (diiso-propyl ether), TBME (methyl tert-butyl ether), CPME (cyclopentyl methyl ether), THF (tetrahydrofuran), dioxane, etc.); aliphatic hydrocarbons (pentane, Hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenz
- solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the amount of solvent used is not particularly limited, but is 0.1 to 100 times by mass with respect to dinitro compound X1.
- the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but it is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
- the synthesis method of the dinitro compound X1 is not particularly limited, and can be synthesized by any method. As a specific example thereof, compound X2 and di-tert-butyl dicarbonate are reacted in a solvent, optionally in the presence of a base.
- a base in the reaction is not necessarily required, but when a base is used, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonate Inorganic bases such as cesium; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, imidazole, quinoline, collidine; sodium hydride, potassium hydride, tert- Bases such as butoxy sodium and tert-butoxy potassium can be used.
- the solvent in such a reaction can be used as long as it does not react with each raw material, and is the same solvent as described in the synthesis of X1 from X above, aprotic polar organic solvent, ethers, fats Aromatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, lower fatty acid esters and the like can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent. The amount of the solvent used is not particularly limited, but 0.1 to 100 times by mass of solvent may be used with respect to dinitro compound X2.
- the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably in the range of ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
- the dinitro compound X1 can be synthesized by reacting a carbonyl compound ( ⁇ ) with amine compounds X2 and X2 ′ provided with a Boc group in a solvent as described below. Specific examples thereof are shown in the following scheme.
- R 1 and R 2 each independently represent hydrogen or a Boc group.
- Y and Z are monovalent to divalent organic groups.
- Examples of the carbonyl compound ( ⁇ ) include phosgene, triphosgene, diphenyl carbonate, bis (nitrophenyl) carbonate, dimethyl carbonate, diethyl Examples include carbonate, ethylene carbonate, 1.1′-carbonylbis-1H-imidazole, methyl chloroformate, benzyl chloroformate, 4-nitrophenyl chloroformate, and the like.
- Carbon oxide may be used in place of the carbonyl compound ( ⁇ ).
- the above-described compound is an example and is not particularly limited.
- the nitro compounds X2 and X2 ′ may be the same.
- the nitro compound X2 is converted to a carbonyl compound ( ⁇ ),
- the nitro compound X2 ′ having a structure different from that of the nitro compound X2 may be added and reacted.
- the order of introducing the amine to which the Boc group is added is not particularly limited.
- Inorganic bases trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, amines such as pyridine, imidazole, quinoline, collidine; sodium hydride, potassium hydride, sodium tert-butoxy, tert-butoxy Bases such as potassium; and the like can be used.
- the solvent in such a reaction can be used as long as it does not react with each raw material, and is the same solvent as described in the synthesis of X1 from X above, aprotic polar organic solvent, ethers, fats Aromatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, lower fatty acid esters and the like can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the amount of solvent used is not particularly limited, but 0.1 to 100 times by mass of solvent may be used with respect to nitro compound X2.
- the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably in the range of ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
- an asymmetric dinitro compound X1 having a different n it can be synthesized by reacting an isocyanate compound X4 and an amine compound X2 provided with a Boc group as described below.
- the following scheme is shown as a specific example.
- the amount of the amine compound X2 used may be 0.98 to 1.2 equivalent times the isocyanate compound X4. More preferably, it is 1.0 to 1.02 equivalent times.
- the reaction solvent is not particularly limited as long as it is inert to the reaction.
- hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sul
- Sulfur aprotic polar solvent and the like are; pyridine, pyridine picoline, and the like. These solvents may be used alone or as a mixture of two or more thereof. Preferably it is toluene, acetonitrile, or ethyl acetate, More preferably, it is toluene or ethyl acetate.
- the amount of solvent used is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, it is 0.1 to 100 times by mass of isocyanate compound X4. Use solvent. The amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited but is, for example, ⁇ 90 to 150 ° C., preferably ⁇ 30 to 100 ° C., and more preferably 0 to 80 ° C.
- the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
- a catalyst may be added to shorten the reaction time.
- organotin compounds such as dibutyltin dilaurate, dioctyltin bis (isooctylthioglycolate), dibutyltinbis (isooctylthioglycolate), dibutyltin diacetate; triethylamine, trimethylamine, tripropylamine, tributylamine , Diisopropylethylamine, N, N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2.2.2-octane, 1,8-diazabicyclo [5.4.0] Amines such as undecene, 1,5-diazabicyclo [4.3.0] nonene-5; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, fluo
- Inorganic acids Tiger butyl titanate, tetraethyl titanate, titanium compounds such as tetraisopropyl titanate; bismuth tris (2-ethylhexanoate) bismuth compounds such as; quaternary ammonium salts; and the like.
- These catalysts may be used alone or in combination of two or more. These catalysts are preferably liquid or soluble in the reaction solvent.
- the catalyst When the catalyst is added, the catalyst is used in an amount of 0.005 to 100 wt% with respect to the total amount (mass) of the isocyanate compound X4. Preferably it is 0.05 to 10 wt%, more preferably 0.1 to 5 wt%. If an organotin compound, a titanium compound, or a bismuth compound is used as the catalyst, the amount is preferably 0.005 to 0.1 wt%.
- the liquid crystal aligning agent of this invention is a polyimide precursor obtained by making the diamine component containing either of the diamine represented by said Formula [1], and a tetracarboxylic acid component react, and / or this polyimide. Contains polyimide obtained from the precursor.
- Tetracarboxylic acid component Preferred examples of the tetracarboxylic acid component are represented by any of the following formulas [8] to [10].
- a polyamic acid is obtained by reacting a tetracarboxylic acid anhydride represented by the formula [8] with a diamine.
- polyamic acid ester is obtained by making the tetracarboxylic acid diester dichloride represented by Formula [9] or the tetracarboxylic acid diester represented by Formula [10] react with diamine.
- a polyimide is compoundable by imidating this polyamic acid or polyamic acid ester.
- R 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the alkyl group include methyl group, ethyl group, propyl group, 2-propyl group, butyl group, t-butyl group and the like.
- the polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms of its alkyl group increases.
- the alkyl group is preferably a methyl group or an ethyl group, particularly preferably a methyl group, from the viewpoint of ease of imidization by heat.
- X is preferably a tetravalent hydrocarbon group having a 4- to 6-membered alicyclic or aromatic ring structure.
- X include (X-1) to (X-46) shown below.
- Y is a divalent group consisting of hydrocarbon, preferably a group having a 6-membered alicyclic or aromatic ring structure. Specific preferred examples of Y include (Y-1) to (Y-97).
- Polyamic acid (hereinafter also referred to as polymer) can be synthesized by a polyaddition reaction of tetracarboxylic dianhydride and diamine (hereinafter also referred to as monomer). Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.
- the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of the solubility of the monomer and the resulting polymer. You may mix and use.
- the concentration of the polymer in the reaction system is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
- the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution.
- cleaning with a poor solvent, and normal temperature or heat-drying can be obtained.
- a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
- polyamic acid ester can be synthesized by any of the following methods (A) to (C).
- A) When synthesizing polyamic acid ester from polyamic acid Polyamic acid ester can be synthesized by esterifying polyamic acid obtained from tetracarboxylic dianhydride and diamine.
- the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours.
- an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours.
- the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene and the like.
- the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
- the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of polymer solubility, and these are used alone or in combination of two or more. May be.
- the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass because polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.
- tetracarboxylic acid diester dichloride and diamine are mixed in the presence of a base and an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
- a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
- the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
- the organic solvent used in the above reaction is preferably N-methyl-2-pyrrolidone, ⁇ -butyrolactone or the like in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
- the concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
- the solvent used for the synthesis of polyamic acid ester is preferably dehydrated as much as possible, and the reaction is preferably prevented from mixing outside air in a nitrogen atmosphere.
- a tetracarboxylic acid diester and a diamine are mixed in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C., preferably 0 to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can synthesize
- Condensation agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like can be used.
- the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic
- tertiary amines such as pyridine and triethylamine can be used.
- the amount of the base added is preferably 2 to 4 times the amount of the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
- the reaction proceeds efficiently by adding a Lewis acid as an additive.
- the Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
- the addition amount of the Lewis acid is preferably 0 to 1.0 times the mole of the diamine component.
- the synthesis methods (A) and (B) are particularly preferable.
- the solution of the polyamic acid ester obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid ester powder.
- a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
- the molecular weight of the polyimide precursor affects the viscosity of the varnish and the physical strength of the polyimide film.
- the weight average molecular weight is preferably 500,000 or less from the viewpoint of obtaining good application workability of the varnish and the coating film, and 2,000 or more is preferred from the viewpoint of obtaining a sufficiently strong polyimide film. More preferably, it is 2,000 to 300,000, and still more preferably 5,000 to 100,000.
- the molecular weight of the polyimide precursor can be controlled by adjusting the ratio of the diamine component used for the polymerization reaction and the tetracarboxylic acid derivative. As this ratio, a molar ratio of 1: 0.7 to 1.2 can be exemplified. The closer the molar ratio is to 1: 1, the higher the molecular weight of the resulting polyimide precursor.
- the polyimide of the present invention can be synthesized by imidizing the polyimide precursor.
- a simple and preferred method for synthesizing a polyimide from a polyimide precursor is chemical imidization in which a catalyst is added to the polyamic acid solution obtained by the reaction of a diamine component and tetracarboxylic dianhydride. This is preferable because the imidization reaction proceeds at a low temperature and the molecular weight of the polymer is hardly lowered during the imidization process.
- Chemical imidation can be performed by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
- a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has a basicity suitable for advancing the reaction.
- the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among these, use of acetic anhydride is preferable because purification after completion of the reaction is easy.
- the temperature for carrying out the imidization reaction is ⁇ 20 to 200 ° C., preferably 0 to 180 ° C., and the reaction time is 1 to 100 hours, preferably 1 to 8 hours.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amic acid group, preferably 3 to 30 mole times.
- the imidation rate of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, reaction time, and the like. Since the added catalyst remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
- the polymer solution can be precipitated by pouring the polyimide solution obtained by the above method into a poor solvent while stirring well.
- the purified polyimide powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating.
- the poor solvent is not particularly limited as long as the polymer is precipitated, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
- the liquid crystal aligning agent of the present invention is a varnish-like solution containing the polyimide precursor and / or polyimide (hereinafter also referred to as a polymer component) obtained as described above.
- the liquid crystal aligning agent of this invention may contain 2 or more types of polyimide precursors, 2 or more types of polyimides, and may contain both a polyimide precursor and a polyimide. Furthermore, the liquid crystal aligning agent may contain a polymer other than the polyimide precursor of the present invention or the polyimide of the present invention.
- the simplest structural example of the liquid crystal aligning agent of the present invention includes a composition comprising the above polyimide precursor and / or a polymer component of polyimide and an organic solvent for dissolving it.
- This composition may be a polyimide precursor or a reaction solution when the polyimide is synthesized, or may be a solution obtained by diluting the reaction solution with a solvent described later.
- the polyimide precursor or polyimide is recovered as a powder, it may be dissolved in an organic solvent to form a polymer solution.
- the concentration of the polymer component is preferably 10 to 30% by mass, particularly preferably 10 to 15% by mass. Moreover, you may heat when dissolving these.
- the heating temperature is preferably 20 to 150 ° C, particularly preferably 20 to 80 ° C.
- the organic solvent for dissolving the polyimide precursor or polyimide is not particularly limited as long as the polymer component is uniformly dissolved.
- the solvent component of the liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer component, a solvent for improving the coating film uniformity when the liquid crystal aligning agent is applied to the substrate.
- a solvent for improving the coating film uniformity when the liquid crystal aligning agent is applied to the substrate.
- a solvent having a surface tension lower than that of the organic solvent is generally used.
- ethyl cellosolve examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, Examples include 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, and lactate isoamyl ester. It is. Two types of these solvents may be used in combination. Two types
- the polymer concentration in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal aligning film to be formed, but it is 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film. From the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. The polymer concentration is more preferably 2 to 8% by mass.
- the liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent.
- the silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is formed and the liquid crystal alignment film formed there. Specific examples of the silane coupling agent include those described in International Publication No. WO2010 / 050523 (1st line to the last line of paragraph 0164 of International Application PCT / JP2009 / 068523).
- the amount of the silane coupling agent to be used is preferably 0.01 to 5% by mass with respect to the polymer component from the viewpoint that the unreacted agent does not adversely affect the liquid crystal orientation and the effect of adhesion appears. More preferably, the content is 1 to 1% by mass.
- Liquid crystal alignment film It is a coating film obtained by applying the liquid crystal aligning agent of this invention to a board
- the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is preferable to use a substrate on which the ITO electrode or the like is formed from the viewpoint of simplification of the process.
- an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and a material that reflects light such as aluminum can be used for the electrode.
- Examples of the method for applying the liquid crystal aligning agent include a spin coating method, a printing method, and an ink jet method.
- Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent.
- it is dried at 50 to 120 ° C. for 1 to 10 minutes, and then baked at 150 to 300 ° C. for 5 to 120 minutes.
- the thickness of the coating film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is 5 to 300 nm, preferably 10 to 200 nm.
- the fired coating film is rubbed or photo-aligned.
- a liquid crystal cell is prepared by a known method to obtain a liquid crystal display element.
- the method for producing the liquid crystal cell is not particularly limited.
- a pair of substrates on which the liquid crystal alignment film is formed is preferably 1 to 30 ⁇ m, more preferably 2 to 2 with the liquid crystal alignment film surface inside.
- a method is generally employed in which a 10 ⁇ m spacer is placed and then the periphery is fixed with a sealant, liquid crystal is injected, and sealing is performed.
- the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method for sealing after dropping the liquid crystal.
- a liquid crystal alignment agent is applied on two substrates to form a liquid crystal alignment layer, and the two substrates are arranged so that the liquid crystal alignment layers face each other.
- a liquid crystal layer is sandwiched between sheets of a substrate, and an ultraviolet ray is irradiated while applying an electric field to the liquid crystal layer.
- the substrate used is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed on a substrate, and a substrate on which an electrode pattern or a protrusion pattern is provided. May be used.
- the liquid crystal alignment layer is a resin film for aligning liquid crystals, and the method for forming a liquid crystal alignment layer on a substrate using a liquid crystal aligning agent is the same as the coating method described in the liquid crystal alignment film. A later baking method can be applied.
- the step of irradiating ultraviolet rays while applying an electric field to the liquid crystal layer applies, for example, an electric field to the liquid crystal layer by applying a voltage between the electrodes installed on the substrate, and irradiates the ultraviolet rays while maintaining the electric field.
- the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, and preferably 5 to 20 Vp-p.
- the amount of ultraviolet irradiation is, for example, 1 to 60 J, preferably 40 J or less. It is preferable that the amount of ultraviolet rays is small because it is possible to suppress a decrease in reliability that causes damage to the members constituting the liquid crystal display element, and the production efficiency is increased by selecting the ultraviolet irradiation time.
- a mixture of A1-1 (100 g, 218 mmol), 5 mass% Pd / C (50% water-containing type), and toluene (1200 ml) was stirred at 60 ° C. for 5 hours in the presence of hydrogen. After completion of the reaction, the catalyst was filtered, and then the solution was cooled to 5 ° C. and further stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with toluene (200 g), and then dried to obtain powder crystals A1 (yield 70 g, yield 80%).
- Example 1 To 10.0 g of the polyamic acid solution obtained in Synthesis Example 1, 5.65 g of NMP, 1.0 g of NMP solution containing 1.0% by mass of 3-glycidoxypropyltriethoxysilane, and 5.55 g of BCS were added. In addition, a liquid crystal aligning agent (A-1) having a concentration of 4.5% by mass was obtained. In this liquid crystal aligning agent (A-1), no abnormality such as turbidity or generation of precipitates was observed, and it was confirmed that the liquid crystal aligning agent (A-1) was a uniform solution.
- Example 2 To 10.0 g of the polyamic acid solution obtained in Synthesis Example 2, 5.65 g of NMP, 1.0 g of NMP solution containing 1.0% by mass of 3-glycidoxypropyltriethoxysilane, and 5.55 g of BCS were added. In addition, a liquid crystal aligning agent (A-2) having a concentration of 4.5% by mass was obtained. In this liquid crystal aligning agent (A-2), no abnormality such as turbidity or precipitation was observed, and it was confirmed that the liquid crystal aligning agent (A-2) was a uniform solution.
- ⁇ Preparation of adhesive evaluation sample> The liquid crystal aligning agent is filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 2 minutes, and then baked at 230 ° C. for 20 minutes. A 100 nm coating was obtained. Two substrates thus obtained were prepared, and a bead spacer having a diameter of 4 ⁇ m was sprayed on the liquid crystal alignment film surface of one of the substrates, and then a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was applied. It was applied in the form of dots.
- bonding was performed so that the liquid crystal alignment film surface of the other substrate was inward, the overlapping width of the substrates was 1 cm, and the sealing agent was positioned at the center of the overlapping portion of the substrates. At that time, the amount of the sealant dropped was adjusted so that the diameter of the sealant after bonding was about 3 mm.
- the two bonded substrates were fixed with a clip and then thermally cured at 120 ° C. for 1 hour to prepare a sample for evaluating adhesiveness.
- the liquid crystal aligning agent is filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 2 minutes, and then baked at 230 ° C. for 20 minutes. A 100 nm coating was obtained.
- the imidized polymer film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing amount: 0.4 mm), and then subjected to ultrasonic irradiation for 1 minute in pure water at 80 ° C. For 10 minutes.
- Two substrates with a liquid crystal alignment film obtained in this way were prepared, and after placing a 4 ⁇ m spacer on the liquid crystal alignment film surface of one substrate, the rubbing directions of the two substrates were combined so that they were antiparallel.
- the periphery was sealed leaving the liquid crystal injection port, and an empty cell having a cell gap of 4 ⁇ m was produced.
- Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this cell at room temperature, and the inlet was sealed to obtain an anti-parallel liquid crystal cell.
- a liquid crystal cell having a configuration of an FFS (Fringe Field Switching) liquid crystal display element was manufactured.
- 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 (Indium Tin Oxide) having a solid pattern constituting a counter electrode as a first layer is provided.
- An electrode was formed.
- a SiN (silicon nitride) film formed by a CVD (Chemical Vapor Deposition) method was formed as a second layer on the counter electrode of the first 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. It was. 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 were 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 dog-shaped electrode elements whose central portion is bent.
- the width of each electrode element in the short direction was 3 ⁇ m, and the distance between the electrode elements was 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 had a shape that bends and resembles a bold-faced koji.
- Each pixel is vertically divided with the 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 to be described later is used as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise), and in the second region of the pixel The electrode elements of the pixel electrode are formed at 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 obtained liquid crystal aligning agent was filtered through a 1.0 ⁇ m filter, and then applied to the prepared substrate with electrodes by spin coating. After drying for 120 seconds on a hot plate at 80 ° C., baking was performed in a far-infrared oven at 230 ° C. for 20 minutes to obtain a polyimide film having a thickness of 60 nm.
- This polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm, rubbing direction: inclined by 10 ° with respect to the third layer IZO comb-teeth electrode. Then, the substrate was washed by irradiating with ultrasonic water for 1 minute with pure water to remove water droplets by air blow, and then dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
- a polyimide film is formed on a glass substrate having a columnar spacer with a height of 4 ⁇ m on which the ITO electrode is formed on the back surface, and an alignment treatment is performed in the same procedure as above.
- the obtained substrate with a liquid crystal alignment film was obtained.
- One set of these two substrates with a liquid crystal alignment film is printed, and the sealant is printed on the substrate leaving the liquid crystal injection port.
- the other substrate has the liquid crystal alignment film surface facing and the rubbing direction is antiparallel. Then, the sealing agent was cured to produce an empty cell having a cell gap of 4 ⁇ m.
- Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C. for 30 minutes and left at 23 ° C. overnight before being used for each evaluation.
- the liquid crystal cell (usually liquid crystal is used) is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to have the same potential.
- the angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted light measured on the two polarizing plates was minimized by irradiating the LED backlight from the bottom of the polarizing plate.
- the VT characteristics voltage-transmittance characteristics
- an AC voltage with a relative transmittance of 23% is measured. Calculated. Since this AC voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is convenient for evaluating the residual charge via the luminance.
- the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having good adhesion to a sealing agent or a substrate in an element, has little display unevenness in the vicinity of the frame, and can secure a large display area. Especially, it is used for small high-definition liquid crystal display elements and the like such as phones and tablet terminals.
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Abstract
Description
液晶配向膜は、液晶の配向状態を制御する目的で使用されるが、液晶表示素子の高精細化に伴い、液晶表示素子のコントラスト低下の抑制や残像現象の低減といった要求から、液晶配向膜には、電圧保持率が高いことや、直流電圧を印加した際の残留電荷が少ないこと、及び/又は直流電圧により蓄積した残留電荷の緩和が速いという特性が重要となっている。
また、液晶表示素子は、軽量、薄型かつ低消費電力の表示デバイスとして知られている。近年では、急速にシェアを拡大してきた携帯電話、スマートホン、タブレット型素子などの小型、高精細の液晶表示素子でも、高い表示品位が求められるほどの目覚ましい発展を遂げている。
また、本発明の特定の構造を有するジアミンを使用するポリイミド前駆体及び/又は該ポリイミド前駆体から得られるポリイミドは、溶媒に対する溶解度も大きいため、高ポリマー濃度の液晶配向剤が得られる利点も有する。
本発明の液晶配向剤を得るために使用されるジアミン成分に含有されるジアミンは、下記式(1)で表される構造を分子中に有するジアミンである。
式(1)及び(2)中、R1、R2及びAは、上記で定義したとおりである。なかでも、R1及びR2は、その少なくとも一方、又は両方とも、式(2)で表される基が好ましく、ラビング時の配向膜強度の観点から、R1及びR2のどちらか一方のみが、式(2)で表される基であるのが好ましい。
Aは、好ましくは単結合である。ここで、Aが単結合の場合、式(2)の基は、t-ブトキシカルボニル基(本発明では、Boc基ともいう。)である。
また、式[1]中、それぞれのベンゼン環におけるアミノ基(-NH2)は、アルキレン基の結合位置に対して、オルト、メタ、又はパラのいずれの位置でもよいが、合成の容易性、及び重合反応性の点から、メタ、又はパラの位置が好ましく、パラの位置がより好ましい。
還元反応に用いられる触媒は、市販品として入手できる活性炭担持金属が好ましく、例えば、パラジウム-活性炭、白金-活性炭、ロジウム-活性炭などが挙げられる。また、水酸化パラジウム、酸化白金、ラネーニッケルなど、必ずしも活性炭担持型の金属触媒でなくてもよい。一般的に広く使用されているパラジウム-活性炭が、良好な結果が得られるので好ましい。
同様な理由により、加圧下で反応を実施する場合もある。この場合、ベンゼン核の還元を避けるため、20気圧までの加圧範囲で行う。好ましくは10気圧までの範囲で反応を実施する。
例えば、非プロトン性極性有機溶媒(DMF(N,N-ジメチルホルムアミド)、DMSO(ジメチルスルホキシド)、DMAc(ジメチルアセトアミド)、NMP(N-メチル-2-ピロリドン)など);エーテル類(Et2O(ジエチルエーテル)、i-Pr2O(ジiso-プロピルエーテル)、TBME(メチルtert-ブチルエーテル)、CPME(シクロペンチルメチルエーテル)、THF(テトラヒドロフラン)、ジオキサンなど);脂肪族炭化水素類(ペンタン、へキサン、ヘプタン、石油エーテルなど);芳香族炭化水素類(ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど);ハロゲン系炭化水素類(クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど);低級脂肪酸エステル類(酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等);ニトリル類(アセトニトリル、プロピオニトリル、ブチロニトリル等);などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、1種単独で又は2種以上混合して用いることができる。必要に応じて、適当な脱水剤や乾燥剤を用いて溶媒を乾燥し、非水溶媒として用いることもできる。
反応温度は特に限定されないが、-100℃から使用する溶媒の沸点までの範囲、好ましくは、-50~150℃である。反応時間は、通常0.05~350時間、好ましくは0.5~100時間である。
一方、ジニトロ化合物X1の合成方法は特に限定されず、任意の方法により合成することができる。その具体例としては、化合物X2と二炭酸ジ-tert-ブチルとを、溶媒中、場合により塩基の存在下で反応させる。
反応における塩基の存在は必ずしも必要ではないが、塩基を用いる場合、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸水素ナトリウム、炭酸水素カリウム、燐酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウムなどの無機塩基;トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、ジメチルアミノピリジン、イミダゾール、キノリン、コリジンなどのアミン類;水素化ナトリウム、水素化カリウム、tert-ブトキシナトリウム、tert-ブトキシカリウムなどの塩基;等を使用できる。
溶媒の使用量は特に限定されないが、ジニトロ化合物X2に対し、0.1~100質量倍の溶媒を用いてもよい。好ましくは0.5~30質量倍であり、さらに好ましくは1~10質量倍である。反応温度は特に限定されないが、-100℃から使用する溶媒の沸点までの範囲、好ましくは、-50~150℃の範囲である。反応時間は、通常0.05~200時間、好ましくは0.5~100時間である。
カルボニル化合物(α)において、Y及びZは、1~2価の有機基であり、カルボニル化合物(α)としては、例えば、ホスゲン、トリホスゲン、ジフェニルカーボネート、ビス(ニトロフェニル)カーボネート、ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート、1.1’-カルボニルビス-1H-イミダゾール、クロロギ酸メチル、クロロギ酸ベンジル、クロロギ酸4-ニトロフェニル等が挙げられる。また、カルボニル化合物(α)の代わりにカーボンオキサイドを使用してもよい。
なお、上記した化合物は一例であり、特に限定されるものではない。
塩基の添加は必ずしも必要ではないが、塩基を用いる場合、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸水素ナトリウム、炭酸水素カリウム、燐酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウムなどの無機塩基;トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、イミダゾール、キノリン、コリジンなどのアミン類;水素化ナトリウム、水素化カリウム、tert-ブトキシナトリウム、tert-ブトキシカリウムなどの塩基;等を使用できる。
イソシアネート化合物X4とアミン化合物X2との反応において、アミン化合物X2の使用量は、イソシアネート化合物X4に対し、0.98~1.2当量倍を反応させればよい。より好ましくは、1.0~1.02当量倍である。
反応温度は特に限定されないが、例えば-90~150℃、好ましくは-30~100℃で、さらに好ましくは0~80℃である。反応時間は、通常0.05~200時間、好ましくは0.5~100時間である。
本発明の液晶配向剤は、上記の式[1]で表されるジアミンのいずれかを含有するジアミン成分と、テトラカルボン酸成分と、を反応させて得られるポリイミド前駆体、及び/又は該ポリイミド前駆体から得られるポリイミドを含有する。
[テトラカルボン酸成分]
テトラカルボン酸成分の好ましい例は、下記の式[8]~[10]のいずれかで表される。
また、ポリイミドは、かかるポリアミック酸あるいはポリアミック酸エステルをイミド化することにより合成することができる。
本発明の液晶配向剤に含有されるポリイミド前駆体を得る場合、本発明の効果を損なわない限りにおいて、ジアミン成分として、上記特定のジアミン以外に、下記式[11]で表される、その他のジアミンを併用することができる。
ポリアミック酸(以下、ポリマーともいう)は、テトラカルボン酸二無水物とジアミン(以下、モノマーともいう)との重付加反応により合成できる。
上記のようにして得られたポリアミック酸は、反応溶液をよく撹拌させながら貧溶媒に注入することで、ポリマーを析出させて回収することができる。また、析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥することで精製されたポリアミック酸の粉末を得ることができる。貧溶媒は、特に限定されないが、水、メタノール、エタノール、ヘキサン、ブチルセロソルブ、アセトン、トルエンなどが挙げられる。
ポリアミック酸エステルは、以下の(A)~(C)のいずれかの方法で合成できる。
(A)ポリアミック酸からポリアミック酸エステルを合成する場合
ポリアミック酸エステルは、テトラカルボン酸二無水物とジアミンから得られるポリアミック酸をエステル化することによって合成できる。
塩基には、ピリジン、トリエチルアミン、4-ジメチルアミノピリジン等が使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、除去が容易な量で、かつ高分子量体が得やすいという点から、テトラカルボン酸ジエステルジクロリドに対して、2~4倍モルであることが好ましい。
また、テトラカルボン酸ジエステルジクロリドの加水分解を防ぐため、ポリアミック酸エステルの合成に用いる溶媒は、できるだけ脱水されていることが良く、反応は窒素雰囲気中で、外気の混入を防ぐのが好ましい。
(C)テトラカルボン酸ジエステルとジアミンからポリアミック酸を合成する場合
ポリアミック酸エステルは、テトラカルボン酸ジエステルとジアミンを、縮合剤により重縮合することにより合成できる。
また、上記反応において、ルイス酸を添加剤として加えることで、反応が効率的に進行する。ルイス酸としては、塩化リチウム、臭化リチウムなどのハロゲン化リチウムが好ましい。ルイス酸の添加量は、ジアミン成分に対して、0~1.0倍モルであることが好ましい。
上記3つのポリアミック酸エステルの合成方法の中でも、高分子量のポリアミック酸エステルが得られるため、(A)及び(B)の合成法が特に好ましい。
ポリイミド前駆体の分子量は、ワニスの粘度や、ポリイミド膜の物理的な強度に影響を与える。ワニスの良好な塗布作業性や塗膜の良好な均一性を得るという点からは、重量平均分子量で500,000以下が好ましく、十分な強度のポリイミド膜を得るという点からは2,000以上が好ましく、より好ましくは2,000~300,000であり、さらに好ましくは、5,000~100,000である。ポリイミド前駆体の分子量は、前記重合反応に用いるジアミン成分とテトラカルボン酸誘導体の比率を調整することで制御できる。この比率としては、モル比で1:0.7~1.2を例示することができる。このモル比が1:1に近いほど得られるポリイミド前駆体の分子量は大きくなる。
本発明のポリイミドは、前記ポリイミド前駆体をイミド化することにより合成することができる。ポリイミド前駆体からポリイミドを合成する簡便で好ましい方法としては、ジアミン成分とテトラカルボン酸二無水物との反応で得られた前記ポリアミック酸の溶液に、触媒を添加する化学的イミド化であり、比較的低温でイミド化反応が進行し、イミド化の過程で、重合体の分子量低下が起こりにくいので好ましい。
本発明の液晶配向剤は、上記のようにして得られたポリイミド前駆体及び/又はポリイミド(以下、これらをポリマー成分ともいう。)を含有するワニス状の溶液である。本発明の液晶配向剤は、2種類以上のポリイミド前駆体や2種類以上のポリイミドを含有していてもよく、ポリイミド前駆体とポリイミドの両方を含有していてもよい。更には、液晶配向剤は、本発明のポリイミド前駆体又は本発明のポリイミド以外のポリマーを含有してもよい。
ポリイミド前駆体又はポリイミドを溶解させるための有機溶媒としては、ポリマー成分が均一に溶解するものであれは特に限定されない。具体的には、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-ビニル-2-ピロリドン、ジメチルスルホキシド、ジメチルスルホン、γ-ブチロラクトン、1,3-ジメチル-イミダゾリジノン、3-メトキシ-N,N-ジメチルプロパンアミドなどを挙げることができる。これらは1種又は2種以上を混合して用いてもよい。また、単独ではポリマー成分を均一に溶解できない溶媒であっても、重合体が析出しない範囲であれば、上記の有機溶媒に混合してもよい。
本発明の液晶配向剤は、その他に、シランカップリング剤や架橋剤などの各種添加剤を含有してもよい。
シランカップリング剤は、液晶配向剤が形成される基板と、そこに形成される液晶配向膜との密着性を向上させる目的で添加される。シランカップリング剤の具体例は、国際公開公報WO2010/050523号(国際出願PCT/JP2009/068523)の段落0164の1行~末行)に記載されるものが挙げられる。
本発明の液晶配向剤を基板に塗布し、乾燥し、焼成して得られた塗膜であり、必要に応じて、この塗膜面に既知の配向処理を実施する。液晶配向剤を塗布する基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板、アクリル基板やポリカーボネート基板などのプラスチック基板などを用いることができ、液晶駆動のためのITO電極などが形成された基板を用いることが、プロセスの簡素化の点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならば、シリコンウエハーなどの不透明な物でも使用でき、電極はアルミニウムなどの光を反射する材料も使用できる。
焼成後の塗膜の厚みは、特に限定されないが、薄すぎると液晶表示素子の信頼性が低下する場合があるので、5~300nm、好ましくは10~200nmである。液晶を水平配向、又は傾斜配向させる場合は、焼成後の塗膜はラビング、又は光配向処理される。
本発明の液晶配向剤から液晶配向膜付き基板を得た後、既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。
液晶セルの製造方法は特に限定されないが、一例を挙げるならば、液晶配向膜が形成された1対の基板を、液晶配向膜面を内側にして、好ましくは1~30μm、より好ましくは2~10μmのスペーサーを挟んで設置した後、周囲をシール剤で固定し、液晶を注入し、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。
上記の液晶配向層とは、液晶を配向させるための樹脂膜であり、液晶配向剤を用いて基板上に液晶配向層を形成する方法は、前記の液晶配向膜で記載した塗布方法及び塗布した後の焼成方法が適用できる。
NMP:N-メチル-2-ピロリドン BCS:ブチルセロソルブ
DMAP:ジメチルアミノピリジン
Boc2O:二炭酸ジ-tert-ブチル
DMAP:ジメチルアミノピリジン Pd/C:パラジウムカーボン
DIEPA:ジイソプロピルエチルアミン
DMF:ジメチルホルムアミド
THF:テトラヒドロフラン
装置:Varian NMR system 400NB(400MHz)(Varian社製)、及びJMTC-500/54/SS(500MHz)(JEOL社製)
測定溶媒:CDCl3(重水素化クロロホルム),DMSO-d6(重水素化ジメチルスルホキシド)
基準物質:TMS(テトラメチルシラン)(δ:0.0ppm,1H)及びCDCl3(δ:77.0ppm,13C)
常温ゲル浸透クロマトグラフィー(GPC)装置(GPC-101)(昭和電工社製)、及びカラム(KD-803,KD-805)(Shodex社製)を用いて、以下のようにして測定した。
カラム温度:50℃
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L(リットル)、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:TSK 標準ポリエチレンオキサイド(分子量;約900,000、150,000、100,000、及び30,000)(東ソー社製)及びポリエチレングリコール(分子量;約12,000、4,000、及び1,000)(ポリマーラボラトリー社製)。
1H-NMR(500MHz, CDCl3); 8.76(1H, s), 8.17(4H, m), 7.39(4H, m), 3.93(2H, t), 3.57(2H, t), 2.97(4H, m), 1.49(9H, s)
1H-NMR(500MHz, CDCl3); 8.70(1H, s), 7.00(4H, m), 6.64(4H, m), 3.82(2H, t), 3.57(1H, br), 3.45(4H, m), 2.74(4H, m), 1.47(9H, s)
1H-NMR(CDCl3,δppm):8.19-8.15(m,2H),7.42-7.27(m,2H),3.86(br,4H),3,07(br,4H),1.50(s,18H)
1H-NMR(CDCl3,δppm):7.06-7.02(m,2H),6.65-6.62(m,2H),3.78(br,4H),3.56(s,4H),2.86(br,4H),1.48(s,18H)
撹拌装置及び窒素導入管付きの50ml四つ口フラスコに、DA-1(0.42g,2.8mmol)、及びDA-3(1.67g、4.2mmol)を計量した後、NMP21.7g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撹拌しながら、CA-1(0.534g,2.45mmol)及びCA-2(0.837g、4.27mmol)を加え、さらにNMPを5.4g加えた。その後、3時間攪拌し、樹脂固形分濃度12質量%のポリアミック酸溶液を得た。このポリアミック酸溶液の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、320mPa・sであった。このポリアミック酸の分子量はMn=10,550、Mw=32,000であった。
撹拌装置及び窒素導入管付きの50ml四つ口フラスコに、DA-1(0.42g,2.8mmol)、及びDA-4(2.09g、4.2mmol)を計量した後、NMP21.7g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撹拌しながら、CA-1(0.534g,2.45mmol)及びCA-2(0.837g、4.27mmol)を加え、さらにNMPを5.4g加えた。その後、3時間攪拌し、樹脂固形分濃度12質量%のポリアミック酸溶液を得た。このポリアミック酸溶液の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、370mPa・sであった。このポリアミック酸のMnは19,000、Mwは50,500であった。
撹拌装置及び窒素導入管付きの50ml四つ口フラスコに、DA-1(0.42g,2.8mmol)、及びDA-2(1.25g、4.2mmol)を計量した後、NMP21.7g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撹拌しながら、CA-1(0.534g,2.45mmol)及びCA-2(0.837g、4.27mmol)を加え、さらにNMPを5.4g加えた。その後、3時間攪拌し、樹脂固形分濃度12質量%のポリアミック酸溶液を得た。このポリアミック酸溶液の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、330mPa・sであった。このポリアミック酸の分子量はMn=9,900、Mw=21,800であった。
合成例1で得られたポリアミック酸溶液10.0gに、NMPを5.65g、3-グリシドキシプロピルトリエトキシシランが1.0質量%入ったNMP溶液を1.0g、及びBCS5.55gを加え、濃度が4.5質量%の液晶配向剤(A-1)を得た。この液晶配向剤(A-1)に、濁りや析出物の発生などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られたポリアミック酸溶液10.0gに、NMPを5.65g、3-グリシドキシプロピルトリエトキシシランが1.0質量%入ったNMP溶液を1.0g、及びBCS5.55gを加え、濃度が4.5質量%の液晶配向剤(A-2)を得た。この液晶配向剤(A-2)に、濁りや析出物の発生などの異常は見られず、均一な溶液であることが確認された。
比較合成例1で得られたポリアミック酸溶液10.0gに、NMPを5.65g、3-グリシドキシプロピルトリエトキシシランが1.0質量%入ったNMP溶液を1.0g、及びBCS5.55g加え、濃度が4.5質量%の液晶配向剤(B-1)を得た。この液晶配向剤(B-1)に、濁りや析出物の発生などの異常は見られず、均一な溶液であることが確認された。
得られた液晶配向剤5.0gの攪拌溶液中に、γ-ブチルラクトン(GBL)を加えながら、固体が析出するまでの溶媒量を記録することで溶解性の評価を実施した。
液晶配向剤A-1、A-2、及びB-1に関して実施したGBLの添加量の結果を表1に示す。
液晶配向剤を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、80℃のホットプレート上で2分間乾燥した後、230℃で20分間焼成して、膜厚が100nmの塗膜を得た。このようにして得られた2枚の基板を用意し、一方の基板の液晶配向膜面上に、直径が4μmのビーズスペーサーを散布した後、シール剤(協立化学社製XN-1500T)を点状に塗布した。次いで、他方の基板の液晶配向膜面を内側にし、基板の重なり幅が1cmになるようにして、基板が重なっている部分の中心にシール剤が位置するように貼り合わせを行った。その際、貼り合わせ後のシール剤の直径が約3mmとなるようにシール剤滴下量を調整した。貼り合わせた2枚の基板をクリップにて固定した後、120℃で1時間熱硬化させて、接着性評価用のサンプルを作製した。
作製したサンプルを島津製作所社製の卓上形精密万能試験機(AGS-X 500N)にて、上下基板の端の部分を固定した後、基板重なり部分の上部から押し込みを行い、剥離する際の圧力(N)を測定した。
計測したシール剤の直径より見積もった面積(mm2)で圧力(N)を割り算して規格化した値を接着力の指標とした。
液晶配向剤A-1、及びB-1の接着力の結果を表1に示す。
液晶配向剤を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、80℃のホットプレート上で2分間乾燥した後、230℃で20分間焼成して、膜厚が100nmの塗膜を得た。このイミド化重合体膜をレーヨン布でラビング(ロール径120mm、回転数1000rpm、移動速度20mm/sec、押し込み量0.4mm)した後、純水中にて1分間超音波照射を行い、80℃で10分間乾燥した。このようにして得られた液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に4μmのスペーサーを設置した後、2枚の基板のラビング方向が逆平行になるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが4μmの空セルを作製した。このセルに液晶(MLC-2041、メルク社製)を常温で真空注入し、注入口を封止してアンチパラレル液晶セルとした。
この液晶セルの配向状態を偏光顕微鏡にて観察し、配向欠陥がないものを「良好」、配向欠陥があるものは「不良」とした。液晶配向剤A-1、A-2及びB-1の配向性の評価結果を表3に示す。
FFS(Fringe Field Switching)方式の液晶表示素子の構成を備えた液晶セルを作製した。
始めに、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のガラス基板であり、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(Indium Tin Oxide)電極が形成されていた。第1層目の対向電極の上には第2層目として、CVD(Chemical Vapor Deposition)法により成膜されたSiN(窒化珪素)膜が形成されていた。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画素及び第2画素の2つの画素を形成されていた。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た。
各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっている。すなわち、後述する液晶配向膜のラビング方向を基準とした場合、画素の第1領域では、画素電極の電極要素が+10°の角度(時計回り)をなすように形成され、画素の第2領域では、画素電極の電極要素が-10°の角度(時計回り)をなすように形成されている。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されている。
上記液晶セル(通常液晶を使用)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、画素電極と対向電極とを短絡して同電位にした状態で、2枚の偏光板の下からLEDバックライトを照射しておき、2枚の偏光板の上で測定するLEDバックライト透過光の輝度が最小となるように、液晶セルの角度を調節した。
次に、この液晶セルに周波数30Hzの矩形波を印加しながら、23℃の温度下でのV-T特性(電圧-透過率特性)を測定し、相対透過率が23%となる交流電圧を算出した。この交流電圧は電圧に対する輝度の変化が大きい領域に相当するため、輝度を介して残留電荷を評価するのに都合がよい。
蓄積した電荷の緩和が速いほど、直流電圧を重畳したときの液晶セルへの電荷蓄積も速いことから、蓄積電荷の緩和特性は、直流電圧を重畳した直後の相対透過率が40%以上の状態から35%に低下するまでに要した時間で評価した。この時間が短いほど蓄積電荷の緩和特性が良好であると定義し、評価を行なった。液晶配向剤A-1、及びB-1の緩和特性を表4に示す。
なお、2014年9月18日に出願された日本特許出願2014-190292号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (11)
- 前記式[1]で表されるジアミンを、前記ジアミン成分中、5~100モル%含有する請求項1又は2に記載の液晶配向剤。
- ポリイミド前駆体及びポリイミドの合計含有量が、1~20重量%である請求項1~3のいずれかに記載の液晶配向剤。
- 式[1]で表されるジアミンのベンゼン環におけるアミノ基の置換位置が、アルキレン基の結合位置に対して、メタ位、又はパラ位である、請求項2~4のいずれかに記載の液晶配向剤。
- ベンゼン環におけるNH2基が、アルキレン基の結合位置に対して、メタ位、又はパラ位にある請求項6に記載のジアミン。
- 前記1~5のいずれかに記載の液晶配向剤から形成される液晶配向膜。
- 膜の厚さが、5~500nmである、請求項9に記載の液晶配向膜。
- 請求項9又は10に記載の液晶配向膜を有する基板が、ガラス基板又はプラスチック基板である液晶表示素子。
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