WO2010053128A1 - 液晶配向処理剤 - Google Patents
液晶配向処理剤 Download PDFInfo
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- WO2010053128A1 WO2010053128A1 PCT/JP2009/068915 JP2009068915W WO2010053128A1 WO 2010053128 A1 WO2010053128 A1 WO 2010053128A1 JP 2009068915 W JP2009068915 W JP 2009068915W WO 2010053128 A1 WO2010053128 A1 WO 2010053128A1
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- liquid crystal
- formula
- aligning agent
- crystal aligning
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- HKKGIHCPNBYMFD-UHFFFAOYSA-N C1=CC=[I]C=C1 Chemical compound C1=CC=[I]C=C1 HKKGIHCPNBYMFD-UHFFFAOYSA-N 0.000 description 2
- IOXOZOPLBFXYLM-UHFFFAOYSA-N NCCc(cc1)ccc1[N+]([O-])=O Chemical compound NCCc(cc1)ccc1[N+]([O-])=O IOXOZOPLBFXYLM-UHFFFAOYSA-N 0.000 description 2
- DSNNRAUMHHQIRG-UHFFFAOYSA-N CC(C)(C1(C)C=CC(C)=CC1)c1ccc(C)cc1 Chemical compound CC(C)(C1(C)C=CC(C)=CC1)c1ccc(C)cc1 DSNNRAUMHHQIRG-UHFFFAOYSA-N 0.000 description 1
- VHYYZJXSXQXKTA-UHFFFAOYSA-N CC(C1)C=C(C)C(C(c2cccc(C)c22)=O)=C1C2=O Chemical compound CC(C1)C=C(C)C(C(c2cccc(C)c22)=O)=C1C2=O VHYYZJXSXQXKTA-UHFFFAOYSA-N 0.000 description 1
- SXQQBXZLKMTRAB-UHFFFAOYSA-N CC(CC(C)(C)C1)c2c1c1cc(C)ccc1[nH]2 Chemical compound CC(CC(C)(C)C1)c2c1c1cc(C)ccc1[nH]2 SXQQBXZLKMTRAB-UHFFFAOYSA-N 0.000 description 1
- CPVIKPUMCBQGJV-UHFFFAOYSA-N CC(CC1C)C(C)C=C1C(Oc1ccc(C)cc1)=O Chemical compound CC(CC1C)C(C)C=C1C(Oc1ccc(C)cc1)=O CPVIKPUMCBQGJV-UHFFFAOYSA-N 0.000 description 1
- LJADCIDQNZGGHV-UHFFFAOYSA-N CC1(C)C(C)=CC(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)=CC1 Chemical compound CC1(C)C(C)=CC(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)=CC1 LJADCIDQNZGGHV-UHFFFAOYSA-N 0.000 description 1
- HRXZRAXKKNUKRF-UHFFFAOYSA-N CCc(cc1)ccc1N Chemical compound CCc(cc1)ccc1N HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 1
- RESTWAHJFMZUIZ-UHFFFAOYSA-N CCc(cc1)ccc1[N+]([O-])=O Chemical compound CCc(cc1)ccc1[N+]([O-])=O RESTWAHJFMZUIZ-UHFFFAOYSA-N 0.000 description 1
- 0 CO*NC(N*)=O Chemical compound CO*NC(N*)=O 0.000 description 1
- IYSZSRMLCQIVAJ-UHFFFAOYSA-N Cc(cc1)ccc1C(Nc1ccc(C)cc1)=O Chemical compound Cc(cc1)ccc1C(Nc1ccc(C)cc1)=O IYSZSRMLCQIVAJ-UHFFFAOYSA-N 0.000 description 1
- OWEIAGSMFHSSES-UHFFFAOYSA-N Cc1ccc(C(C(F)(F)F)(C(F)(F)F)c2ccc(C)cc2)cc1 Chemical compound Cc1ccc(C(C(F)(F)F)(C(F)(F)F)c2ccc(C)cc2)cc1 OWEIAGSMFHSSES-UHFFFAOYSA-N 0.000 description 1
- XCCQFUHBIRHLQT-UHFFFAOYSA-N Cc1ccc(CCc2ccc(C)cc2)cc1 Chemical compound Cc1ccc(CCc2ccc(C)cc2)cc1 XCCQFUHBIRHLQT-UHFFFAOYSA-N 0.000 description 1
- LNPMZQXEPNWCMG-UHFFFAOYSA-N NCCc(cc1)ccc1N Chemical compound NCCc(cc1)ccc1N LNPMZQXEPNWCMG-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1O)=O Chemical compound [O-][N+](c(cc1)ccc1O)=O BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- IEXRKQFZXJSHOB-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1OC=O)=O Chemical compound [O-][N+](c(cc1)ccc1OC=O)=O IEXRKQFZXJSHOB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C275/10—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- 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 treatment agent for producing a liquid crystal alignment film.
- the present invention relates to a liquid crystal alignment treatment agent for use in a liquid crystal alignment film produced through a rubbing process.
- the liquid crystal alignment film is a film for controlling the alignment direction of liquid crystal molecules to be constant in a liquid crystal display element or a retardation plate using a polymerizable liquid crystal.
- a method for easily producing a liquid crystal alignment film there is a method of forming a polymer film such as polyimide on a substrate and rubbing the surface with a cloth, so-called rubbing treatment, which is still widely used industrially today. Yes.
- the rubbing treatment has a problem that dust generated by scraping the liquid crystal alignment film or scratches on the liquid crystal alignment film deteriorates display quality. Therefore, one of the characteristics required for the liquid crystal alignment film is rubbing resistance. It was.
- a method for obtaining a liquid crystal alignment film in which rubbing scraping and rubbing scratches are unlikely to occur a method of adding various additives to polyimide or a polyimide precursor is known (see, for example, Patent Documents 1 and 2).
- a polyimide structure with good rubbing resistance has been proposed (see, for example, Patent Documents 3 and 4).
- An object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film excellent in rubbing resistance, in which rubbing scraping and rubbing scratches are unlikely to occur.
- liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having excellent rubbing resistance
- the present invention is based on such knowledge. Yes, with the following gist. 1. It is a liquid crystal aligning agent containing either a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid derivative, and the diamine component contains a diamine represented by the following formula (1). Liquid crystal aligning agent characterized by the above.
- X is an oxygen atom or a sulfur atom
- Y 1 and Y 2 are each independently a single bond, —O—, —S—, —OCO—, or —COO—.
- R 1 and R 2 are each independently an alkylene group having 1 to 3 carbon atoms.
- 9. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of 1 to 8 above.
- 10. A liquid crystal display device having the liquid crystal alignment film as described in 9 above. 11.
- R 12 and R 22 each represent an alkylene group having 1 to 3 carbon atoms different from each other, and in the formula (1-c), R 13 and R 23 are each independently carbon atoms.
- R 13 and R 23 are each independently carbon atoms.
- It is an alkylene group of the number 1 to 3.
- liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film in which the surface of the film at the time of rubbing is less scratched or scraped and the liquid crystal orientation is good. Moreover, since the liquid crystal aligning film obtained using the liquid crystal aligning agent of this invention has the high voltage holding rate of a liquid crystal cell and low ion density, it can produce a high quality liquid crystal display element.
- the liquid-crystal aligning agent of this invention contains polyimide precursors, such as a polyamic acid and polyamic acid ester, or a polyimide, and uses the specific diamine represented by following formula (1) as a diamine component which is the synthetic raw material. It is characterized by that.
- X is an oxygen atom or a sulfur atom
- Y 1 and Y 2 are each independently a single bond, —O—, —S—, —OCO—, or —COO—
- R 1 and R 2 are each independently an alkylene group having 1 to 3 carbon atoms.
- X is an oxygen atom
- it is a urea group
- sulfur atom it is a thiourea group
- the urea group and the thiourea group may be collectively referred to as (thio) urea group).
- Both oxygen and sulfur atoms have high electronegativity.
- two hydrogen atoms with high donor properties exist on the nitrogen atom. Therefore, in the (thio) urea group, an oxygen or sulfur atom is relatively strongly self-assembled by two non-covalent bonds with two hydrogen atoms of another (thio) urea group.
- X in the formula (1) is preferably an oxygen atom. This is probably because the oxygen atom has a higher electronegativity compared to the oxygen atom and the sulfur atom, so the urea structure is stronger and more likely to self-assemble than the thiourea structure.
- the liquid crystal aligning agent of this invention has the (thio) urea group derived from the specific diamine which has a specific structure of the said Formula (1) in a polymer chain.
- the rubbing resistance is improved by electrostatic interaction between (thio) urea groups present in a polymer chain having a specific structure.
- the present invention is different from a method of improving rubbing resistance by connecting polymer chains generally used in the field of liquid crystal alignment films with a crosslinking agent.
- R 1 and R 2 each independently represents an alkylene group having 1 to 3 carbon atoms, and the structure thereof may be either linear or branched.
- methylene, ethylene, trimethylene, 1-methylethylene and 2-methylethylene groups examples thereof include methylene, ethylene, trimethylene, 1-methylethylene and 2-methylethylene groups.
- methylene, ethylene, and trimethylene are preferable.
- Y 1 and Y 2 are each independently a single bond, —O—, —S—, —OCO—, or —COO—.
- the structures of Y 1 and Y 2 are preferably as flexible as possible and have as little steric hindrance as possible from the viewpoint of liquid crystal orientation and rubbing resistance, and are preferably a single bond, —O—, or —S—.
- the structure between the (thio) urea group and the benzene ring is symmetrical about the (thio) urea group in the sense of forming a film with a high film density and forming a stronger liquid crystal alignment film.
- —R 1 —Y 1 — and —R 2 —Y 2 — have the same structure.
- R 11 and R 21 are both C 1-3 alkylene groups having the same carbon number.
- R 12 and R 22 are alkylene groups having 1 to 3 carbon atoms different from each other.
- R 13 and R 23 are each independently an alkylene group having 1 to 3 carbon atoms.
- the bonding position of the amino group on the benzene ring is not particularly limited, but is preferably a 3-aminophenyl structure or a 4-aminophenyl structure, particularly preferably a 4-aminophenyl structure from the viewpoint of liquid crystal orientation.
- Aminophenyl structure Specifically, examples of the formula (1) are preferably any of the following formulas (1-1), (1-2), and (1-3), and particularly preferably the formula (1) 1-1).
- the compounds of the formulas (1-7) to (1-11) are novel compounds provided for the first time in the present invention, and of course, a polyimide precursor or polyimide using the compounds is also a novel compound. Further, diamine compounds other than those represented by formulas (1-7) to (1-11) are known compounds, but polyimide precursors or polyimides using these diamine compounds are novel compounds.
- the diamine represented by the formula (1) can be synthesized, for example, as follows.
- the diamine compound represented by the formula (1) of the present invention is composed of an aniline skeleton, a spacer part (R 1 , R 2 ), a linking group (Y 1 , Y 2 ), and a (thio) urea group, and its synthesis method Is not particularly limited, but can be synthesized, for example, by the method described below.
- X is an oxygen atom or a sulfur atom
- Y 1 and Y 2 are each independently a single bond, —O—, —S—, —OCO—, or —COO—
- R 1 and R 2 are each independently an alkylene group having 1 to 3 carbon atoms.
- the bonding position of the amine group on the benzene ring is not particularly limited.
- the diamine compound represented by the formula (1) of the present invention is a dinitro compound represented by the corresponding formula (2) (in the above formula (2), R 1 , R 2 , Y 1 , Y 2 , and X are , which is synonymous with the case of formula (1), and further, the nitro group is reduced and converted to an amino group.
- the method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, or platinum sulfide carbon is used as a catalyst, and ethyl acetate, toluene
- the method for synthesizing the dinitro compound represented by the formula (2) is not particularly limited and can be synthesized by an arbitrary method. Specific examples thereof include, for example, a method as shown in the following scheme (3). Can be synthesized.
- the dinitro compound represented by the formula (2) includes a nitrobenzene compound ( ⁇ ), ( ⁇ ′), a (thio) carbonyl compound (which is a general term for a carbonyl compound and a thiocarbonyl compound) ( ⁇ ), Can be synthesized in an organic solvent in the presence of an alkali.
- R 1 , R 2 , Y 1 , and Y 2 are the same as those in the formula (1), and the amino group represented by NH 2 is a hydrochloride (NH 2 -A salt such as HCl) may be formed.
- NH 2 -A salt such as HCl
- Specific examples thereof include nitrobenzylamine or a hydrochloride thereof; 2- (nitrophenyl) ethylamine or a hydrochloride thereof; 3- (nitrophenyl) propylamine or a hydrochloride thereof;
- the substitution position of the nitro group on the benzene ring is appropriately selected from those at which the target diamine compound is obtained.
- the compound shown here is an example and is not specifically limited.
- X is the same as in formula (1), and Z is a monovalent or divalent organic group.
- Examples of the (thio) carbonyl compound ( ⁇ ) include phosgene, thiophosgene, diphenyl carbonate, diphenyl thiocarbonate, bis (nitrophenyl) carbonate, bis (nitrophenyl) thiocarbonate, dimethyl carbonate, dimethylthiocarbonate, diethyl carbonate, and diethyl. Examples thereof include thiocarbonate, ethylene carbonate, ethylene thiocarbonate, 1,1′-carbonylbis-1H-imidazole, 1,1′-thiocarbonylbis-1H-imidazole and the like. Further, carbon oxide (carbon monoxide or carbon dioxide) may be used instead of the carbonyl compound ( ⁇ ).
- the compound shown here is an example and is not specifically limited.
- the nitrobenzene compounds ( ⁇ ) and ( ⁇ ′) may be the same, and in order to obtain an asymmetric compound May be prepared by reacting the nitrobenzene compound ( ⁇ ) with the (thio) carbonyl compound ( ⁇ ) in an equimolar amount and then adding a nitrobenzene compound ( ⁇ ′) having a structure different from that of the nitrobenzene compound ( ⁇ ).
- alkali examples include basic organic compounds such as triethylamine, diisopropylethylamine and DMAP (4-N, N-dimethylaminopyridine); inorganic alkali compounds such as sodium hydroxide and potassium carbonate; metal hydrides such as sodium hydride And the like.
- basic organic compounds such as triethylamine, diisopropylethylamine and DMAP (4-N, N-dimethylaminopyridine
- inorganic alkali compounds such as sodium hydroxide and potassium carbonate
- metal hydrides such as sodium hydride And the like.
- the compound shown here is an example and is not specifically limited.
- Organic solvents include solvents that do not affect the reaction, specifically, aromatic solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and heptane; halogens such as dichloromethane and 1,2 dichloroethane Solvents; ether solvents such as tetrahydrofuran and 1,4-dioxane; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; It can also be used. Moreover, these usage-amounts are arbitrary.
- the diamine synthesized as described above can be used as a raw material for polyamide and polyurea in addition to polyimide precursors and polyimides such as polyamic acid and polyamic acid ester described later, and these polymers are used for various electronic materials. It can be used as a material.
- the polyimide precursor contained in the liquid-crystal aligning agent of this invention is obtained by reaction with the diamine component which essentially contains said specific diamine, and a tetracarboxylic acid derivative. Only the specific diamine represented by Formula (1) may be sufficient as the diamine component for obtaining a polyimide precursor, and you may use together with another diamine.
- the ratio of the specific diamine represented by formula (1) can be any value, but in order to obtain sufficient rubbing resistance, the total diamine component (100 mol%), It is preferably 10 mol% or more, more preferably 30 mol% or more, and further preferably 50 mol% or more.
- the ratio of the specific diamine component is preferably 90 mol% or less in the total diamine component.
- diamine used together with the specific diamine represented by the formula (1) is not particularly limited, it can be represented by the following formula (4).
- R 5 represents a divalent organic group
- R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group.
- Specific examples of R 5 include the following divalent organic groups.
- R 5 in the formula (4) used in combination has a structure of any one of formulas [B-80] to [B-101].
- the content of the diamine when such a diamine is used is preferably 5 to 90 mol%, more preferably 10 to 80 mol% in the total diamine.
- R 5 in the above formula (4) is any one of the structures of the formulas [B-1] to [B-79] and [B-102] to [B-118].
- R 3 and R 4 in Formula (4) is preferably a monovalent organic group, more preferably a methyl group.
- the tetracarboxylic acid derivative to be reacted with the specific diamine component represented by the formula (1) or the specific diamine component represented by the formula (1) containing the diamine represented by the formula (4) is not particularly limited.
- the tetracarboxylic acid derivative includes tetracarboxylic dianhydride, tetracarboxylic monoanhydride, tetracarboxylic acid, dicarboxylic acid dialkyl ester (represented by the following formula (5-d)), dicarboxylic acid chloride dialkyl Examples include esters (represented by the following formula (5-e)), but are not limited to these as long as the reaction with diamine proceeds.
- Tetracarboxylic acid derivatives are represented by the following formulas (5-a) to (5-e), and R 7 represents an alkyl group.
- R 6 include the following [A-1] to [A-47].
- R 6 represents formula [A-6], formula [A-16], formula [A-18] to formula [A-22], formula [A-25], formula [A-37], and
- the tetracarboxylic acid derivative represented by the formula [A-38] is preferable because it is highly soluble in an organic solvent even if it is a polyimide having a high imidization rate.
- 10 mol% or more, preferably 20 mol% or more of the tetracarboxylic acid derivative used is R 6 having an alicyclic structure or an aliphatic structure such as those represented by formulas [A-1] to [A-25]. This is preferable because the voltage holding ratio is improved.
- R 6 represents a tetracarboxylic acid derivative selected from the group consisting of the formula [A-1], the formula [A-16], and the formula [A-19] among these alicyclic structures or aliphatic structures.
- R 6 represents a tetracarboxylic acid derivative selected from the group consisting of the formula [A-1], the formula [A-16], and the formula [A-19] among these alicyclic structures or aliphatic structures.
- the aromatic tetracarboxylic acid derivative is 10 mol% or more, preferably 20 mol% or more, based on the total amount of the tetracarboxylic acid derivative to be used, it is preferable because liquid crystal alignment can be improved and accumulated charge can be reduced.
- a method for obtaining a polyimide precursor or polyimide by reacting the above diamine component (hereinafter also simply referred to as diamine) and a tetracarboxylic acid derivative component hereinafter also simply referred to as tetracarboxylic acid derivative
- it is obtained by a known method. be able to.
- tetracarboxylic dianhydride will be described below as an example.
- the polymerization reaction method of the tetracarboxylic acid derivative and diamine used for the production of the liquid crystal aligning agent of the present invention is not particularly limited. Generally, by mixing in an organic solvent, a polymerization reaction can be made into a polyamic acid. Moreover, polyamic acid ester can be obtained by esterifying a carboxylic acid group using a known esterifying agent. The polyamic acid and polyamic acid ester thus produced can be made into polyimide by dehydrating and ring-closing.
- a method of mixing a tetracarboxylic acid derivative and a diamine component in an organic solvent a solution in which the diamine is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid derivative component is dispersed or dissolved in the organic solvent as it is.
- a method of adding a diamine to a solution in which a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent a method of alternately adding a tetracarboxylic acid derivative and a diamine, and the like.
- the plurality of types of components may be preliminarily mixed and may be polymerized individually or sequentially.
- the temperature at which the tetracarboxylic acid derivative and diamine are subjected to a polymerization reaction in an organic solvent is usually 0 to 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C. When the temperature is higher, the polymerization reaction is completed earlier, but when it is too high, a high molecular weight polymer may not be obtained.
- the polymerization reaction can be carried out at any charge concentration, but if the charge concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the charge concentration is too high, the reaction solution will become too viscous and uniform. Therefore, the amount is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
- the initial stage of the polymerization reaction may be performed at a high concentration, and then an organic solvent may be added.
- the charged concentration here refers to the concentration of the total mass of the tetracarboxylic dianhydride component and the diamine component.
- the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid and polyamic acid ester (hereinafter sometimes referred to as polyamic acid (ester)) are soluble.
- Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, Examples thereof include ⁇ -butyrolactone. These may be used alone or in combination.
- the solvent does not dissolve the polyamic acid (ester), it may be used by mixing with the above solvent as long as the produced polyamic acid (ester) does not precipitate.
- the ratio of the tetracarboxylic acid derivative and the diamine used in the polymerization reaction for obtaining the polyamic acid is preferably 1: 0.8 to 1: 1.2 in terms of molar ratio, and the closer this molar ratio is to 1: 1.
- the molecular weight of the resulting polyamic acid is increased. If the molecular weight of the polyamic acid (ester) is too small, the strength of the coating film obtained therefrom may be insufficient.
- the weight average molecular weight of the polyamic acid (ester) used in the liquid crystal aligning agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.
- a tetracarboxylic acid derivative and a diamine are used.
- the diamine a specific diamine represented by the above formula (1) and, if necessary, the above formula (4).
- the diamine represented is used.
- the tetracarboxylic acid derivatives preferably used are those in which R 6 in the above formulas (5-a) to (5-e) is represented by the formula [A-1], the formula [A-2], Formula [A-16], Formula [A-18], Formula [A-19], Formula [A-25], Formula [A-26], Formula [A-27], Formula [A A-32], formula [A-35], formula [A-38], or formula [A-47], and the diamine of the above formula (4) used in combination with the specific diamine is preferably R 5 Are represented by formula [B-6], formula [B-7], formula [B-8], formula [B-16], formula [B-17], formula [B-20], formula [B-21].
- Formula [B-29], Formula [B-30], Formula [B-32], Formula [B-33], Formula [B-40], Formula [B-44], Formula [B-45], Formula [B-48], Formula [B-56], Formula [ -57], Formula [B-58], Formula [B-61], Formula [B-62], Formula [B-63], Formula [B-76], Formula [B-80], Formula [B- 82], formula [B-83], formula [B-84], formula [B-85], formula [B-86], formula [B-87], formula [B-93], formula [B-104] ], [B-114], [B-115], or [B-118] is used.
- R 6 in the above formula (5-a) is represented by the formula [A-1], the formula [A-2], the formula [A-16], the formula [A-18], the formula [A-19], formula [A-25], formula [A-26], formula [A-27], or formula [A-32] are preferred.
- R 5 is Formula [B-7], Formula [B-8], Formula [B-17], Formula [B-20], Formula [B-21], Formula [B-29], Formula [B-30], Formula [B-32], Formula [B-61], Formula [B-76], Formula [B-80], Formula [B-82], Formula [B-83], Formula [B-84], Formula [B B-85], Formula [B-104], Formula [B-114], Formula [B-115], or Formula [B-118] are preferable.
- the polyamic acid thus obtained can be represented by a repeating unit of the following formula (6), and the polyamic acid ester can also be represented by the following formula (7).
- R a , R b and R c are diamine-derived groups represented by the above formula (1) or formula (4), and the diamine represented by formula (1)
- R a and R b are hydrogen
- R c is -phenylene-Y 1 -NH-CX-HN-R 2 -Y 2 -phenylene-
- a diamine represented by the formula (4) is used
- R a is R 3
- R b is R 4
- R c is R 5 .
- R 6 has the same meaning as R 6 in the tetracarboxylic acid derivatives represented by the above formulas (5-a) to (5-e).
- R in the formula (7) is a group derived from the esterifying agent used.
- the polyamic acid or polyamic acid ester obtained as described above may be used as it is for the liquid crystal aligning agent of the present invention, but may also be used after dehydrating and ring-closing polyimide.
- it may be difficult to use it as a liquid crystal aligning agent by being insolubilized by an imidization reaction.
- all of the amic acid (ester) groups in the polyamic acid (ester) may not be imidized, and may be imidized within a range in which appropriate solubility can be maintained.
- the imidation reaction for dehydrating and cyclizing polyamic acid is generally thermal imidization in which the solution of polyamic acid is heated as it is, and chemical imidation in which a catalyst is added to the solution of polyamic acid (ester). Chemical imidation in which the imidization reaction proceeds at a low temperature is preferable because the molecular weight of the resulting polyimide is less likely to decrease.
- Chemical imidization can be performed by stirring polyamic acid (ester) in an organic solvent in the presence of a basic catalyst and an acid anhydride.
- the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C., and the reaction time can be 1 to 100 hours.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the polyamic acid (ester), and the amount of the acid anhydride is 1 to 50 mol times of the polyamic acid (ester), preferably 3 to 30 mole times. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction.
- Examples of basic catalysts used for imidization include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- an organic solvent the solvent used at the time of the polyamic acid polymerization reaction mentioned above can be used.
- the imidation rate by chemical imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- the added catalyst remains in the solution. Therefore, in order to use it for the liquid crystal aligning agent of the present invention, this polyimide solution is put into a poor solvent which is being stirred. However, it is preferable to use the polyimide by collecting it by precipitation. Although it does not specifically limit as a poor solvent used for precipitation collection
- recovery of a polyimide Methanol, acetone, hexane, a butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc. can be illustrated.
- the polyimide precipitated by adding it to a poor solvent can be recovered by filtration, washing and drying at room temperature or under reduced pressure at normal temperature or by heating. By further dissolving the powder in a good solvent and reprecipitating it 2 to 10 times, the polyimide can be purified. When impurities cannot be completely removed by a single precipitation recovery operation, it is preferable to repeat this purification step. Mixing or sequentially using, for example, three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent in the repeated purification step is preferable because the purification efficiency is further increased.
- poor solvents such as alcohols, ketones, and hydrocarbons
- polyamic acid can be collected and purified by the same operation. If it is not desired to include the solvent used for the polymerization of the polyamic acid in the liquid crystal aligning agent, or if unreacted monomer components or impurities are present in the reaction solution, this precipitation recovery and purification may be performed.
- the imidation ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited. What is necessary is just to set to arbitrary values in consideration of the solubility of a polyimide.
- the molecular weight of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but if the molecular weight of the polyimide is too small, the strength of the resulting coating film may be insufficient, and conversely the molecular weight of the polyimide is large. If it is too high, the viscosity of the liquid crystal aligning agent to be produced becomes too high, and the workability at the time of coating film formation and the uniformity of the coating film may deteriorate. Therefore, the weight average molecular weight of the polyimide used for the liquid crystal aligning agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.
- the liquid-crystal aligning agent of this invention contains either the polyimide precursor obtained as mentioned above or a polyimide, and it is usually set as the coating liquid which dissolved these polymers in the organic solvent.
- the polymer contained in the liquid-crystal aligning agent of this invention may contain the polymer which has another structure other than the said polyimide precursor or a polyimide.
- the organic solvent contained in the liquid-crystal aligning agent of this invention will not be specifically limited if the polymer to contain is dissolved.
- organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone.
- 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, 2- (2-ethoxy Propoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate N-propyl ester, lactate N-butyl ester, lactate
- a solvent having a low surface tension is also preferably used in the liquid crystal alignment treatment agent of the present invention, but the amount used is more preferably 5 to 80% by mass of the total solvent contained in the liquid crystal alignment treatment agent, Preferably, it is 20 to 60% by mass.
- the liquid-crystal aligning agent of this invention may contain various additives other than said polymer and an organic solvent. Examples of additives that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
- F-top EF301, EF303, EF352 manufactured by Tochem Products
- MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
- Florard FC430, FC431 manufactured by Sumitomo 3M
- Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.).
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. It is.
- the additive for improving the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound.
- a functional silane-containing compound and an epoxy group-containing compound For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-
- the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. . If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- the liquid crystal alignment treatment agent of the present invention changes the polymer components other than the polymer and the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired.
- a target dielectric or conductive material, or a crosslinkable compound for the purpose of increasing the hardness or density of the liquid crystal alignment film may be added.
- the concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal alignment film, but a film having no defect is formed, and the film thickness is suitable as a liquid crystal alignment film. Is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass.
- the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or without alignment treatment in vertical alignment applications.
- 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, a polycarbonate substrate, or the like can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a prepared substrate from the viewpoint of simplification of the process.
- an opaque substance such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used.
- the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
- the substrate coated with the liquid crystal aligning agent can be baked at any temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C. .
- the conversion rate to polyimide changes depending on the firing temperature, but the liquid crystal aligning agent of the present invention does not necessarily need to be 100% imidized.
- the firing time can be set to an arbitrary time, but if the firing time is too short, display failure may occur due to the influence of the residual solvent. Therefore, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. It is.
- 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.
- liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
- Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
- the thickness of the spacer at this time is preferably 1-30 ⁇ m, more preferably 2-10 ⁇ m.
- the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention is excellent in reliability and can be suitably used for a large-screen high-definition liquid crystal television.
- BABU 1,3-bis (4-aminobenzyl) urea
- BAPU 1,3-bis (4-aminophenethyl) urea
- DA-3 1,3-bis (3-aminobenzyl) urea
- DA-4 1- (4-Aminobenzyl) -3- (4-aminophenethyl) urea
- DA-5 1,3-bis (2- (4-aminophenoxy) ethyl) urea
- DA-6 1,3-bis (3- ( 4-Aminophenoxy) propyl) urea
- DA-7 1,5′-bis (4-aminophenoxy) pentane
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- BODA Bicyclo
- 4-nitrobenzylamine hydrochloride [F] (50.00 g, 265 mmol), pyridine (20.97 g, 265 mmol), and dichloromethane (750 g) were added to a nitrogen-substituted four-necked flask. Cooled to below. To this was added a solution of 4-nitrophenyl chloroformate [J] (53.43 g, 265 mmol) in dichloromethane (150 g), the reaction temperature was raised to 23 ° C., and the mixture was stirred for 1 hour, and then heated to reflux.
- reaction solution was cooled to room temperature, and dichloromethane (500 g) and an aqueous hydrochloric acid solution (1000 g) diluted to 10% by mass were added to perform filtration.
- the filtrate was stirred at room temperature, and the precipitated solid was filtered. This solid was washed with methanol (200 g) and dried to obtain a white solid compound [K] (amount 33.26 g, yield 40%).
- a saturated aqueous sodium hydrogen carbonate solution 500 g was added to the filtrate, and after washing, the organic layer was further washed with saturated brine (500 g) and dried over magnesium sulfate.
- Example 1 In a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 0.60 g (2.0 mmol) of BAPU and 1.95 g (18.0 mmol) of p-PDA were added, and 30 g of N-methyl-2-pyrrolidone was added. In addition, it was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 3.70 g (18.9 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. Thus, a solution of polyamic acid (P1) was obtained.
- P1 polyamic acid
- the liquid crystal alignment treatment agent obtained above 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 5 minutes, and then baked at 230 ° C. for 30 minutes.
- a polyimide film having a thickness of 100 nm was obtained.
- This polyimide 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).
- the surface of the film was observed using a confocal laser microscope, and was scraped at a magnification of 10 to observe the presence of scraps and the presence of scratches.
- Table 2 The results are shown in Table 2.
- the liquid crystal alignment treatment agent obtained above 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 5 minutes, and then baked at 230 ° C. for 30 minutes.
- a polyimide film having a thickness of 100 nm was obtained.
- ultrasonic irradiation was performed in pure water for 1 minute, and 80 ° C. for 10 minutes. Dried.
- Two substrates with such a liquid crystal alignment film are prepared, and a 6 ⁇ m spacer is placed on the liquid crystal alignment film surface of one of the substrates, and then combined so that the rubbing directions of the two substrates are antiparallel to each other.
- the periphery was sealed, and an empty cell with a cell gap of 6 ⁇ 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. (Liquid crystal orientation) When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects.
- ion density Using a liquid crystal cell produced in the same manner as described above (production of a liquid crystal cell), ion density was measured using a 6254 type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. In the measurement, a triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. During the measurement, the temperature of the liquid crystal cell was measured at 60 ° C.
- Example 2 A 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube was charged with 2.39 g (8.0 mmol) of BAPU and 0.87 g (8.0 mmol) of p-PDA, and 30 g of N-methyl-2-pyrrolidone. In addition, it was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 2.92 g (14.9 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 2 hours in a nitrogen atmosphere. Thus, a polyamic acid (P2) solution was obtained.
- P2 polyamic acid
- BAPU 2.68 g (9.0 mmol) and N-methyl-2-pyrrolidone 30 g were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 1.69 g (8.6 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. Thus, a polyamic acid (P3) solution was obtained.
- P3 polyamic acid
- Example 4 To a stirrer and a 50 ml four-necked flask equipped with a nitrogen introduction tube, 2.62 g (9.7 mmol) of BABU and 25 g of N-methyl-2-pyrrolidone were added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 1.85 g (9.4 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 2 hours in a nitrogen atmosphere. Thus, a polyamic acid (P4) solution was obtained.
- P4 polyamic acid
- Example 5 To a 50 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 2.54 g (8.5 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone were added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 1.69 g (7.7 mmol) of PMDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, followed by stirring at room temperature for 4 hours under a nitrogen atmosphere. Thus, a polyamic acid (P5) solution was obtained.
- P5 polyamic acid
- Example 6 To a 50 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 2.43 g (9.0 mmol) of BABU and 30 g of N-methyl-2-pyrrolidone were added and dissolved while stirring while feeding nitrogen. While stirring this diamine solution, 1.88 g (8.6 mmol) of PMDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 3 hours in a nitrogen atmosphere. Thus, a polyamic acid (P6) solution was obtained.
- P6 polyamic acid
- Example 8 BABU (3.24 g, 12.0 mmol) and N-methyl-2-pyrrolidone (25 g) were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 2.99 g (11.9 mmol) of BODA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. Stirring to obtain a polyamic acid (P8) solution.
- P8 polyamic acid
- Example 9 To a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, add 2.31 g (8.54 mmol) of DA-3 and 24.3 g of N-methyl-2-pyrrolidone, and dissolve by stirring while feeding nitrogen. I let you. While stirring the diamine solution, 1.66 g (8.46 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. Thus, a polyamic acid (P9) solution was obtained.
- P9 polyamic acid
- Example 10 Add 2.84 g (9.98 mmol) of DA-4 and 29.5 g of N-methyl-2-pyrrolidone to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolve by stirring while feeding nitrogen. I let you. While stirring this diamine solution, 1.66 g (9.53 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. Thus, a polyamic acid (P10) solution was obtained.
- P10 polyamic acid
- Example 11 Add DA-40 (3.40 g, 9.48 mmol) and N-methyl-2-pyrrolidone (29.5 g) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolve by stirring while feeding nitrogen. I let you. While stirring this diamine solution, 1.76 g (8.97 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. Thus, a polyamic acid (P11) solution was obtained.
- Example 12 A 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube was charged with 0.53 g (1.6 mmol) of DA-5 and 1.56 g (14.4 mmol) of p-PDA, and N-methyl-2- 30.9 g of pyrrolidone was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 2.82 g (15.4 mmol) of CBDA was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. Thus, a solution of polyamic acid (P12) was obtained.
- Example 13 In a 1000 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 7.07 g (24.44 mmol) of DA-7 and 3.13 g (10.48 mmol) of BAPU were placed, and the inside of the flask was replaced with nitrogen. Next, 359.90 g of dehydrated N-methyl-2-pyrrolidone and 6.63 g of pyridine were charged with a syringe and stirred at 25 ° C. with a magnetic stirrer to completely dissolve BAPU and DA-7. Thereafter, the reaction solution was cooled with water, and 9.34 g (31.44 mmol) of CA-4 was added while stirring with a magnetic stirrer.
- the addition was performed using a funnel over 30 seconds. Thereafter, the funnel used for the addition was washed with 10.00 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling. Next, the reaction solution was poured little by little while stirring 5 times the weight of methanol of the reaction solution, and stirring was continued for 1 hour. Thereafter, the precipitate obtained by filtration was stirred with 5 times weight of methanol for 1 hour, and then filtered to collect the precipitate. Thereafter, the same operation was performed using 5 times the weight of methanol, and the obtained precipitate was dried at 100 ° C. under reduced pressure for 24 hours to obtain 14.59 g of polyamic acid ester (P13).
- Example 14 In a 300 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 4.07 g (13.97 mmol) of DA-7 and 1.78 g (5.99 mmol) of BAPU were placed, and the inside of the flask was replaced with nitrogen. Next, 202.93 g of dehydrated N-methyl-2-pyrrolidone and 3.79 g of pyridine were charged with a syringe and stirred with a magnetic stirrer at 25 ° C. to completely dissolve BAPU and DA-7.
- reaction solution was cooled with water, and 1.27 g (3.99 mmol) of CA-5 and 4.15 g (13.96 mmol) of CA-4 were added while stirring with a magnetic stirrer.
- the addition was performed using a funnel over 30 seconds. Thereafter, the funnel used for the addition was washed with 10.00 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling.
- the reaction solution was poured little by little while stirring 5 times the weight of methanol of the reaction solution, and stirring was continued for 1 hour. Thereafter, the precipitate obtained by filtration was stirred with 5 times weight of methanol for 1 hour, and then filtered to collect the precipitate.
- the funnel used for the addition was washed with 20 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling.
- the reaction solution was poured little by little while stirring distilled water of 5 times the weight of the reaction solution, and stirring was continued for 1 hour.
- the precipitate obtained by filtration was stirred with 5 times weight of distilled water for 1 hour, and then filtered to collect the precipitate.
- the same operation was further performed using 5-fold weight of ethanol, and the obtained precipitate was dried at 100 ° C. under reduced pressure for 24 hours to obtain 14.82 g of a solid.
- the addition was performed using a funnel over 30 seconds. Thereafter, the funnel used for the addition was washed with 10 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling. Next, the reaction solution was poured little by little while stirring 5 times the weight of methanol of the reaction solution, and stirring was continued for 1 hour. Thereafter, the precipitate obtained by filtration was stirred with 5 times weight of methanol for 1 hour, and then filtered to collect the precipitate. Thereafter, the same operation was further performed using 5 times the weight of methanol, and the obtained precipitate was dried at 100 ° C. under reduced pressure for 24 hours to obtain 11.15 g of a solid.
- Table 1 shows the amounts of raw materials (diamines and the like) used in Examples 1 to 14 and Comparative Examples 1 to 3, the abbreviations of the polyamic acids obtained (P1 and the like), and the N-methyl- The viscosity of the 2-pyrrolidone solution is shown together. Note that no abbreviations were given to the polyamic acids and polyamic acid esters of Comparative Examples 1 to 3 (indicated by blanks in Table 1). In Table 1, “-” indicates that the viscosity is not measured.
- Example 1 liquid crystal cells were prepared using the liquid crystal alignment film treating agents obtained in Examples 2 to 4, Example 7 to Example 13, Comparative Example 1 and Comparative Example 2, and rubbed. Resistance, liquid crystal orientation, pretilt angle, voltage holding ratio and ion density were measured. Moreover, about Example 5, Example 6, Example 14, and Comparative Example 3, it measured by the method similar to Example 1 about the rubbing tolerance and liquid crystal orientation. The obtained results are shown in Table 2.
- the liquid crystal aligning film which is excellent in rubbing tolerance, the orientation of a liquid crystal is favorable, and a strong rubbing process is required can be obtained.
- the liquid crystal alignment film of the present invention can be used as a liquid crystal display element of vertical alignment that does not require rubbing treatment and further photo alignment because the voltage holding ratio of the liquid crystal cell is high and the ion density is also low.
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Abstract
Description
液晶配向膜を簡便に作製する手法としては、基板上にポリイミドなどの高分子膜を形成し、この表面を布で擦る、いわゆるラビング処理を行う方法があり、現在でも工業的に広く用いられている。
ラビング削れやラビング傷が起こりにくい液晶配向膜を得る方法としては、ポリイミドやポリイミド前駆体に種々の添加剤を加える方法が知られている(例えば特許文献1、2参照)。そのほか、ラビング耐性の良好なポリイミド構造も提案されている(例えば特許文献3、4参照)。
1.ジアミン成分とテトラカルボン酸誘導体を反応させて得られるポリイミド前駆体またはポリイミドのいずれかを含有する液晶配向処理剤であって、上記ジアミン成分が下記式(1)で表されるジアミンを含有することを特徴とする液晶配向処理剤。
2.式(1)において、-R1-Y1-と-R2-Y2-とが同一構造である上記1に記載の液晶配向処理剤。
3.式(1)において、Y1及びY2が単結合である上記1又は2に記載の液晶配向処理剤。
4.式(1)において、Xが酸素原子である上記1~3のいずれかに記載の液晶配向処理剤。
5.前記テトラカルボン酸誘導体が、テトラカルボン酸二無水物、テトラカルボン酸一無水物、テトラカルボン酸、ジカルボン酸ジアルキルエステル、又はジカルボン酸クロライドジアルキルエステルである上記1~4のいずれかに記載の液晶配向処理剤。
6.さらに、フッ素系界面活性剤、シリコーン系界面活性剤、又はノ二オン系界面活性剤を含有する上記1~5のいずれかに記載の液晶配向処理剤。
7.さらに、官能性シラン含有化合物、又はエポキシ基含有化合物を含有する上記1~6のいずれかに記載の液晶配向処理剤。
8.液晶配向処理剤中の固形分濃度が、液晶配向処理剤の全量(100質量%)に対して、1~20質量%である上記1~7のいずれかに記載の液晶配向処理剤。
9.上記1~8のいずれかに記載の液晶配向処理剤から得られる液晶配向膜。
10.上記9に記載の液晶配向膜を有する液晶表示素子。
11.下記式(1-7)、式(1-8)、式(1-b)又は式(1-b)で表されるビスアミノフェニル若しくはビスアミノフェノキシアルキルウレア。
12.下記式(1-9)~式(1-11)で表されるビスアミノフェニル若しくはビスアミノフェノキシアルキルウレア。
本発明の液晶配向処理剤は、ポリアミック酸、ポリアミック酸エステルなどのポリイミド前駆体、又はポリイミドを含有し、その合成原料であるジアミン成分として、下記式(1)で表される特定ジアミンを使用することを特徴とする。
式(1)において、Xが酸素原子の場合はウレア基であり、硫黄原子の場合はチオウレア基(以下、ウレア基及びチオウレア基を総称して(チオ)ウレア基ということがある。)である。
なお、式(1)において、R1及びR2はそれぞれ独立して、炭素数1~3のアルキレン基を示し、その構造は直鎖又は分岐鎖のいずれでも良い。
式(1)で表されるジアミンは、例えば以下のようにして合成することができる。本発明の式(1)で表されるジアミン化合物は、アニリン骨格、スペーサー部(R1、R2)、連結基(Y1、Y2)および(チオ)ウレア基より構成され、その合成方法は特に限定されるものではないが、例えば、以下に述べる方法によって合成することができる。
本発明の液晶配向処理剤に含有されるポリイミド前駆体は、上記の特定ジアミンを必須として含むジアミン成分と、テトラカルボン酸誘導体との反応で得られる。
ポリイミド前駆体を得るためのジアミン成分は、式(1)で表される特定ジアミンのみであってもよく、他のジアミンと併用しても構わない。
R5の具体例としては以下の2価の有機基を挙げることができる。
上記式(4)において、R5の一部又は全部が式[B-80]~式[B-101]などである場合は、液晶のプレチルト角を大きくすることができる。
上記したジアミン成分(以下、単にジアミンともいう)とテトラカルボン酸誘導体成分(以下、単にテトラカルボン酸誘導体ともいう)とを反応させてポリイミド前駆体またはポリイミドを得る方法としては、公知の方法で得ることができる。テトラカルボン酸二無水物を用いる場合を例にして、下記に説明する。
ポリアミック酸を得るための重合反応に用いるテトラカルボン酸誘導体とジアミンの比率は、モル比で1:0.8~1:1.2であることが好ましく、このモル比が1:1に近いほど得られるポリアミック酸の分子量は大きくなる。ポリアミック酸(エステル)の分子量は、小さすぎるとそこから得られる塗膜の強度が不十分となる場合があり、逆にポリアミック酸(エステル)の分子量が大きすぎると、そこから製造される液晶配向処理剤の粘度が高くなり過ぎて、塗膜形成時の作業性、塗膜の均一性が悪くなる場合がある。従って、本発明の液晶配向処理剤に用いるポリアミック酸(エステル)の重量平均分子量は2,000~500,000が好ましく、より好ましくは5,000~300,000である。
本発明の液晶配向処理剤は、以上のようにして得られたポリイミド前駆体またはポリイミドのいずれかを含有するものであり、通常はこれらの重合体を有機溶媒に溶解させた塗布液とする。本発明の液晶配向処理剤に含有される重合体は、前記のポリイミド前駆体またはポリイミド以外に、他の構造を有する重合体を含有していてもよい。本発明の液晶配向処理剤に含有される有機溶媒は、含有する重合体を溶解させるものであれば特に限定されない。
本発明の液晶配向処理剤には、上記の重合体及び有機溶媒の他に、各種の添加剤を含有していてもよい。
膜厚均一性や表面平滑性を向上させる添加剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2-ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6-テトラグリシジル-2,4-ヘキサンジオール、N,N,N’,N’,-テトラグリシジル-m-キシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’,-テトラグリシジル-4、4’-ジアミノジフェニルメタンなどが挙げられる。
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処理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。
以上のようにして、本発明の液晶配向処理剤を用いて作製された液晶表示素子は、信頼性に優れ、大画面で高精細の液晶テレビなどに好適に利用できる。
下記実施例および比較例で用いる略語は、以下のとおりである。
BABU: 1,3-ビス(4-アミノベンジル)ウレア
BAPU: 1,3-ビス(4-アミノフェネチル)ウレア
DA-3: 1,3-ビス(3-アミノベンジル)ウレア
DA-4: 1-(4-アミノベンジル)-3-(4-アミノフェネチル)ウレア
DA-5: 1,3-ビス(2-(4-アミノフェノキシ)エチル)ウレア
DA-6: 1,3-ビス(3-(4-アミノフェノキシ)プロピル)ウレア
DA-7: 1,5’-ビス(4-アミノフェノキシ)ペンタン
CBDA: 1,2,3,4-シクロブタンテトラカルボン酸二無水物
PMDA: ピロメリット酸二無水物
BODA: ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物
CA-4: 1,3-ジカルボメトキシ-2,4-ビス(クロロカルボニル)シクロブタン
CA-5: 2,5-ジカルボメトキシテレフタル酸ジクロライド
p-PDA: パラフェニレンジアミン
なお、合成例中、1H-NMRとは、分子内水素原子の核磁気共鳴スペクトルを意味する。
1,3-ビス(4-アミノフェネチル)ウレア[BAPU]の合成
1H-NMR(400MHz, DMSO-d6, δppm):8.11-8.08(4H, m), 7.43-7.40(4H, m), 5.89(2H, t), 3.24-3.19(4H, q), 2.76(4H, t).
1H-NMR(400MHz, DMSO-d6, δppm):6.85-6.82(4H, m), 6.51-6.48(4H, m), 5.78(2H, t), 4.83(4H, s), 3.14-3.09(4H, m), 2.50-2.45(4H, m).
1,3-ビス(4-アミノベンジル)ウレア[BABU]の合成
1H-NMR(400MHz, DMSO-d6, δppm):8.22-8.19(4H, m), 7.53-7.50(4H, m), 6.82(2H, t), 4.36(4H, d).
1H-NMR(400MHz, DMSO-d6, δppm):6.92-6.88(4H, m), 6.51-6.48(4H, m), 6.03(2H, t), 4.91(4H, s), 4.02(4H, d).
1,3-ビス(3-アミノベンジル)ウレア〔DA-3〕の合成
1H-NMR(400MHz, DMSO-d6, δppm):8.06-8.05(4H, m), 7.68(2H, d), 7.56-7.55(2H, m), 6.84(2H, t), 4.32(4H, d).
化合物[I](7.04g、21.3mmol)、5%パラジウムカーボン(5%Pd/C)(0.7g)、及び1,4-ジオキサン(350g)の混合物を、窒素で置換した後、水素で置換しなおし、水素存在下、室温にて攪拌した。反応をHPLCにて追跡し、反応終了後、セライトで触媒をろ過した。その後、ろ液を、減圧下、溶媒留去し、茶白色固体の粗物を得た。その粗物に2-プロパノール(60g)を加え、超音波装置にて分散洗浄を行った後、ろ過、乾燥を行い茶白色固体のジアミノ化合物〔DA-3〕を得た(得量4.04g、収率81%)。
1H-NMR(400MHz, DMSO-d6, δppm):6.93(2H, t), 6.46-6.45(2H, m), 6.42-6.34(4H, m), 6.20(2H, t), 5.01(4H, s), 4.07(4H, d).
〔合成例4〕
1-(4-アミノベンジル)-3-(4-アミノフェネチル)ウレア〔DA-4〕の合成
1H-NMR(400MHz, CDCl3, δppm):8.8.28-8.24(4H, m), 7.55-7.53(2H, m), 7.37-7.34(2H, m), 5.64(1H, t), 4.59(2H, d).
室温下、窒素置換した4つ口フラスコ中に2-(4-ニトロフェニル)エチルアミン塩酸塩
[C](30.29g、150mmol)、化合物[K](45.18g、142mmol)及びTHF(2260g)を加え、そこにトリエチルアミン(43.23g、427mmol)及び4-N,Nジメチルアミノピリジン(1.74g、14.2mmol)を加え、反応を行った。反応をHPLCにて追跡し、反応終了後、純水(10L)中へ反応溶液を加え、30分撹拌を行った。その後、ろ過を行い、純水(2L)で洗浄し、白色固体の粗物を得た。この得られた白色固体を2-プロパノール(300g)で洗浄した後、ろ過、乾燥を行い、白色固体のジニトロ化合物[L]を得た(得量43.9g、収率90%)。
1H-NMR(400MHz, DMSO-d6, δppm):8.19-8.14(4H, m), 7.52-7.44(4H, m), 6.62(1H, t), 6.12(1H, t), 4.31(2H, d), 3.33(2H, m), 2.86(2H, t).
化合物[L](50.00g、145mmol)、5%パラジウムカーボン(5%Pd/C)(5.0g)、及び1,4-ジオキサン(1000g)の混合物を、窒素で置換した後、水素で置換しなおし、水素存在下、室温にて攪拌した。反応をHPLCにて追跡し、反応終了後、セライトで触媒をろ過した。その後、ろ液を、減圧下、溶媒留去し、茶白色固体の粗物を得た。その粗物に2-プロパノール(330g)を加え、超音波装置にて分散洗浄を行った後、ろ過、乾燥を行い桃白色固体のジアミノ化合物〔DA-4〕を得た(得量37.0g、収率90%)。
1H-NMR(400MHz, DMSO-d6, δppm):6.90-6.87(2H, m), 6.84-6.82(2H, m), 6.51-6.47(4H, m), 6.08(1H, t), 5.73(1H, t), 4.9 (2H, s), 4.84(2H, s), 3.99 (2H, d), 3.15-3.10 (2H, m), 2.51-2.46(2H, m).
〔合成例5〕
1,3-ビス(2-(4-アミノフェノキシ)エチル)ウレア〔DA-5〕の合成
室温、窒素雰囲気下、4つ口フラスコ中に4-ニトロフェノール(27.69g、199mmol)、炭酸カリウム(55.01g、398mmol)、及びN,N-ジメチルホルムアミド(以下DMFと記載)(140g)を加え、65℃に加熱した。そこへN-(2-ブロモエチル)フタルイミド(50.57g、199mmol)のDMF(140g)溶液を滴下し加えた。反応終了後、氷水(2240g)中へ反応溶液を加え、黄色の固体を得た。これをろ過、水洗後、乾燥させることにより黄白色固体として、化合物[O]を得た(得量44.2g、収率71%)。
1H-NMR(400MHz, CDCl3, δppm):8.19-8.16(2H, m), 7.90-7.87(2H, m), 7.77-7.74(2H, m), 6.96-6.94(2H, m), 4.33(2H, t), 4.14(2H, t).
室温、窒素雰囲気下、4つ口フラスコ中の化合物[O](40.00g、128mmol)のエタノール(930g)溶液にヒドラジン一水和物(81.00g、1.28mol)を加えた後、加熱還流を行った。反応終了後、析出した固体を蒸留水(930g)で溶解させた後、1,2-ジクロロエタン(500g)で4回抽出を行った。有機層を合わせた後、水洗(500g)を2回行い、硫酸マグネシウムで乾燥後、ろ過し、溶媒留去して、黄色固体として化合物[P]を得た(得量16.5g、収率51%)。
1H-NMR(400MHz, CDCl3, δppm):8.22-8.20(2H, m), 6.99-6.96(2H, m), 4.09(2H, t), 3.15(2H, t), 1.26(2H, brs).
反応工程 Bによる化合物[P]の合成
室温、窒素フローのもと、4つ口フラスコ中に1,2-ジメトキシエタン(以下DMEと記載)(150g)を入れ、そこへ60%水素化ナトリウム (16.24g、372mmol)を加えた。その後、2-エタノールアミン(22.73g、372mmol)のDME(50g)溶液を徐々に滴下して加えた。次に、1-フルオロー4-ニトロベンゼン(50.00g、354mmol)のDME(50g)溶液を滴下した。反応終了後、蒸留水(1250g)中へ反応溶液を加え、ジクロロメタン(400g)で3回抽出を行った。有機層を合わせ、硫酸マグネシウムで乾燥後、ろ過し、溶媒留去して、黄色固体として化合物[P]を得た(得量46.1g、収率71%)
1H-NMR(400MHz, CDCl3, δppm):8.22-8.20(2H, m), 6.99-6.96(2H, m), 4.09(2H, t), 3.15(2H, t), 1.26(2H, brs).
室温下、窒素置換した4つ口フラスコ中に炭酸 ビス(4-ニトロフェニル)[D](7.95g、26.1mmol)、トリエチルアミン(15.87g、157mmol)、4-N,N-ジメチルアミノピリジン(0.64g、5.23mmol)、及びTHF(280g)を加え撹拌した。そこに、化合物[P] (10.00g、54.9mmol)のTHF(40g)溶液を加え、さらに反応を行った。反応をHPLCにて追跡し、反応終了後、純水(1.9L)中へ反応溶液を加え、30分撹拌を行った。その後、ろ過を行い、純水(500mL)で洗浄し、黄色固体の粗物を得た。得られた粗物を2-プロパノール(60g)で洗浄した後、乾燥を行い、黄色固体のジニトロ化合物[Q]を得た(得量6.98g、収率68%)。
1H-NMR(400MHz, CDCl3, δppm):8.21-8.18(4H, m), 6.97-6.93(4H, m), 4.83(2H, t), 4.15(4H, q), 3.68(4H, q).
化合物[Q](6.73g、17.2mmol)、5%パラジウムカーボン(5%Pd/C)(0.67g)、及び1,4-ジオキサン(337g)の混合物の入った4つ口フラスコの中を、窒素で置換した後、水素で置換しなおし、水素存在下、室温にて攪拌した。反応をHPLCにて追跡し、反応終了後、セライトで触媒をろ過した。その後、ろ液を、減圧下、溶媒留去し、薄黄色固体の粗物を得た。その粗物に2-プロパノール(48g)を加え、超音波装置にて分散洗浄を行った後、ろ過、乾燥を行い桃白色固体のジアミノ化合物〔DA-5〕を得た(得量3.43g、収率60%)。
1H-NMR(400MHz, DMSO-d6, δppm):6.67-6.63(4H, m), 6.51-6.48(4H, m), 6.18(2H, t), 4.60(4H, brs), 3.79(4H, t), 3.30(4H, q).
〔合成例6〕
3-ビス(3-(4-アミノフェノキシ)プロピル)ウレア〔DA-6〕の合成
室温、窒素雰囲気下、4つ口フラスコ中に4-ニトロフェノール(25.79g、185mmol)、炭酸カリウム(49.70g、185mmol)、及びDMF(130g)を加え、65℃に加熱した。そこへN-(3-ブロモプロピル)フタルイミド(49.7g、185mmol)のDMF(130g)溶液を滴下し加えた。反応終了後、氷水(2080g)中へ反応溶液を加え、黄色の固体を得た。これをろ過、水洗後、乾燥させることにより黄白色固体として、化合物[S]を得た(得量59.5g、収率98%)。
1H-NMR(400MHz, CDCl3, δppm):8.8.17-8.15(2H, m), 7.89-7.84(2H, m), 7.76-7.73(2H, m), 6.86-6.84(2H, m), 4.13(2H, t), 3.93(2H, t), 2.27-2.20(2H, m).
室温、窒素雰囲気下、4つ口フラスコ中の化合物[S](60.50g、185mmol)のエタノール(908g)溶液にヒドラジン一水和物(116.0g、1.85mol)を加えた後、加熱還流を行った。反応終了後、析出した固体を蒸留水(908g)で溶解させた後、1,2-ジクロロエタン(500g)で4回抽出を行った。有機層を合わせた後、水洗(500g)を2回行い、硫酸マグネシウムで乾燥した。その後、ろ過し、溶媒留去して、透黄色オイルとして化合物[T]を得た(得量36.0g、収率99%)。
1H-NMR(400MHz, CDCl3, δppm):8.20-8.17(2H, m), 6.98-6.94(2H, m), 4.18-4.15(2H, m), 3.40-3.37(2H, m), 2.20-2.14(2H, m), 2.03-2.20(2H, m).
反応工程 Dによる化合物[T]の合成
室温、窒素フローのもと、4つ口フラスコ中に1,2-ジメトキシエタン(以下DMEと記載)(188g)を入れ、そこへ60%水素化ナトリウム (14.52g、333mmol)を加えた。その後、3-アミノ-1-プロパノール(25.00g、333mmol)のDME(94g)溶液を徐々に滴下して加えた。次に、1-フルオロー4-ニトロベンゼン(46.96g、333mmol)のDME(94g)溶液を滴下した。反応終了後、蒸留水(564g)中へ反応溶液を加え、ジクロロメタン(500g)で3回抽出を行った。有機層を合わせ硫酸マグネシウムで乾燥後、ろ過し、溶媒留去して、黄色オイルとして化合物[T]を得た(得量60.72g、収率93%)
1H-NMR(400MHz, CDCl3, δppm):8.20-8.17(2H, m), 6.98-6.94(2H, m), 4.18-4.15(2H, m), 3.40-3.37(2H, m), 2.20-2.14(2H, m), 2.03-2.20(2H, m).
室温下、窒素置換した4つ口フラスコ中に炭酸化合物[T] (60.72g、310mmol)、ビス(4-ニトロフェニル)[D](35.87g、118mmol)、トリエチルアミン(47.72g、472mmol)、4-N,N-ジメチルアミノピリジン(1.44g、11.8mmol)、及びTHF(720g)を加え撹拌した。反応をHPLCにて追跡し、反応終了後、純水(4.3L)中へ反応溶液を加え、30分撹拌を行った。その後、ろ過を行い、純水(1L)で洗浄し、黄色固体の粗物を得た。得られた粗物を2-プロパノール(400g)で洗浄した後、乾燥を行い、黄色固体のジニトロ化合物[U]を得た(得量38.1g、収率77%)。
1H-NMR(400MHz, DMSO-d6, δppm):8.18-8.14(4H, m), 7.11-7.08(4H, m), 5.96(2H, t), 4.07(4H, 5), 3.11(4H, q), 1.84-1.78(4H, m).
化合物[U](26.00g、62.1mmol)、5%パラジウムカーボン(5%Pd/C)(2.6g)、及び1,4-ジオキサン(160g)/エタノール(160g)の混合物の入った4つ口フラスコの中を、窒素で置換した後、水素で置換しなおし、水素存在下、室温にて攪拌した。反応をHPLCにて追跡し、反応終了後、析出している固体を溶解させるため、窒素置換した後、アセトニトリル(1500g)、及びDMF(150g)を加えて加熱し、完全に溶解した。その後、セライトで触媒をろ過した。その後、ろ液を、減圧下、溶媒留去し、茶白色固体の粗物を得た。この粗物に2-プロパノール(160g)を加え、超音波装置にて分散洗浄を行った。その後、ろ過、乾燥を行い、茶白色固体のジアミノ化合物〔DA-6〕を得た(得量17.7g、収率79%)。
1H-NMR(400MHz, DMSO-d6, δppm):6.65-6.61(4H, m), 6.51-6.47(4H, m), 5.90(2H, t), 4.58(4H, s), 3.81(4H, t), 3.13-3.08(4H, m), 1.77-1.70(4H, m).
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBAPUを0.60g(2.0mmol)、及びp-PDAを1.95g(18.0mmol)入れ、N-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA3.70g(18.9mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P1)の溶液を得た。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、316mPa・sであった。
このポリアミック酸溶液16.24gにN-メチル-2-ピロリドン9.94g、及びブチルセロソルブ6.54gを加え、P1の濃度が6.0質量%の液晶配向処理剤を得た。
上記で得られた液晶配向処理剤を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5分間乾燥後、230℃で30分間焼成して膜厚100nmのポリイミド膜を得た。このポリイミド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。この膜表面を、共焦点レーザー顕微鏡を用いて表面状態を観察し、倍率10倍で削れカスの有無と傷の有無を観察した。この結果は表2に示す。
(液晶セルの作製)
上記で得られた液晶配向処理剤を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5分間乾燥後、230℃で30分間焼成して膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ロール径120mm、回転数300rpm、移動速度20mm/sec、押し込み量0.2mm)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。このような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6μm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6μm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。
(液晶配向性)
上記の液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。
(プレチルト角)
上記の液晶セルについて、結晶回転法による測定装置(TBA107、autroNic-MELCHERS GmbH社製)を用い、110℃で30分間加熱後の液晶のプレチルト角を測定した。
(電圧保持率)
上記(液晶セルの作製)と同様にして作製した液晶セルに、4Vの電圧を60μs間印加し、16.67ms後の電圧を測定することで、初期値からの変動を電圧保持率として計算した。測定の際、液晶セルの温度は90℃とし、それぞれの温度で測定を行った。
(イオン密度)
上記(液晶セルの作製)と同様にして作製した液晶セルを用い、東陽テクニカ社製の6254型液晶物性評価装置を用いてイオン密度の測定を行った。測定は、10V、0.01Hzの三角波を印加し、得られた波形のイオン密度に相当する面積を三角形近似法により算出し、イオン密度とした。測定の際、液晶セルの温度は60℃として測定した。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBAPUを2.39g(8.0mmol)、及びp-PDAを0.87g(8.0mmol)入れ、N-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA2.92g(14.9mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で2時間撹拌してポリアミック酸(P2)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、281mPa・sであった。
このポリアミック酸溶液16.12gにN-メチル-2-ピロリドン9.61g、及びブチルセロソルブ6.43gを加え、P2の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBAPUを2.68g(9.0mmol)、及びN-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA1.69g(8.6mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で6時間撹拌してポリアミック酸(P3)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、206mPa・sであった。
このポリアミック酸溶液14.65gにN-メチル-2-ピロリドン5.10g、及びブチルセロソルブ4.94gを加え、P3の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBABUを2.62g(9.7mmol)、及びN-メチル-2-ピロリドン25gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA1.85g(9.4mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で2時間撹拌してポリアミック酸(P4)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、173mPa・sであった。
このポリアミック酸溶液13.90gにN-メチル-2-ピロリドン5.10g、及びブチルセロソルブ4.75gを加え、P4の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置付、及び窒素導入管付きの50ml四つ口フラスコにBAPUを2.54g(8.5mmol)、及びN-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらPMDA1.69g(7.7mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P5)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、138.6mPa・sであった。
このポリアミック酸溶液15.13gにN-メチル-2-ピロリドン5.64g、及びブチルセロソルブ4.94gを加え、P5の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBABUを2.43g(9.0mmol)、及びN-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらPMDA1.88g(8.6mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で3時間撹拌してポリアミック酸(P6)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、276mPa・sであった。
このポリアミック酸溶液10.75gにN-メチル-2-ピロリドン8.56g、及びブチルセロソルブ4.83gを加え、P6の濃度が4.5質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBAPUを3.58g(12.0mmol)、及びN-メチル-2-ピロリドン30gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらBODA2.86g(11.4mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、50℃で28時間撹拌してポリアミック酸(P7)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、630mPa・sであった。
このポリアミック酸溶液12.22gにN-メチル-2-ピロリドン12.80g、及びブチルセロソルブ6.32gを加え、P7の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにBABUを3.24g(12.0mmol)、及びN-メチル-2-ピロリドン25gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらBODA2.99g(11.9mmol)を添加し、更に固形分濃度が15質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、50℃で24時間撹拌してポリアミック酸(P8)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、498mPa・sであった。
このポリアミック酸溶液9.95gにN-メチル-2-ピロリドン12.0g、及びブチルセロソルブ5.50gを加え、P8の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにDA-3を2.31g(8.54mmol)、及びN-メチル-2-ピロリドン24.3gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA1.66g(8.46mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P9)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、155mPa・sであった。
このポリアミック酸溶液16.80gにN-メチル-2-ピロリドン7.57g、及びブチルセロソルブ6.09gを加え、P9の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにDA-4を2.84g(9.98mmol)、及びN-メチル-2-ピロリドン29.5gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA1.66g(9.53mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P10)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、206mPa・sであった。
このポリアミック酸溶液17.12gにN-メチル-2-ピロリドン7.75g、及びブチルセロソルブ6.22gを加え、P10の濃度が5.5質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにDA-6を3.40g(9.48mmol)、及びN-メチル-2-ピロリドン29.5gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA1.76g(8.97mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P11)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、150mPa・sであった。
このポリアミック酸溶液18.88gにN-メチル-2-ピロリドン5.26g、及びブチルセロソルブ6.03gを加え、P11の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにDA-5を0.53g(1.6mmol)、及びp-PDAを1.56g(14.4mmol)入れ、さらにN-メチル-2-ピロリドン30.9gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCBDA2.82g(15.4mmol)を添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4時間撹拌してポリアミック酸(P12)の溶液を得た。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、160mPa・sであった。
このポリアミック酸溶液18.41gにN-メチル-2-ピロリドン6.03g、及びブチルセロソルブ6.11g加え、P12の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの1000ml四つ口フラスコにDA-7を7.00g (24.44mmol)、BAPUを3.13g(10.48mmol)入れ、フラスコ内を窒素で置換した。次に、脱水N-メチル-2-ピロリドン359.90g、及びピリジン6.63gをシリンジで仕込み、25℃でマグネチックスターラーにて攪拌し、BAPU及びDA-7を完全に溶解させた。その後、反応液を水冷し、マグネチックスターラーにて攪拌しながらCA-4を9.34g(31.44mmol)添加した。添加は、ロートを使用して30秒かけて行った。その後、添加に使用したロートを脱水N-メチル-2-ピロリドン10.00gで洗浄し、反応容器内を窒素置換して、水冷下で3時間撹拌を続けた。次に、反応溶液の5倍重量のメタノールを攪拌しているところに、反応溶液を少しずつ注ぎ1時間攪拌を続けた。その後、ろ過によって得られた析出物を、5倍重量のメタノールとともに1時間攪拌を行った後、ろ過して析出物を回収した。その後、5倍重量のメタノールを用いて同様の操作を行い、得られた析出物を100℃、減圧下で24時間乾燥させて、14.59gのポリアミック酸エステル(P13)を得た。得られた固形物のうち2.26gを、N-メチル-2-ピロリドン20.36gで完全に溶解させた。次に、その溶液にN-メチル-2-ピロリドン2.12g、及びブチルセロソルブ10.60gを加え、P13の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの300ml四つ口フラスコにDA-7を4.00g (13.97mmol)、BAPUを1.78g(5.99mmol)入れ、フラスコ内を窒素で置換した。次に、脱水N-メチル-2-ピロリドン202.93g、及びピリジン3.79gをシリンジで仕込み、25℃でマグネチックスターラーにて攪拌し、BAPU及びDA-7を完全に溶解させた。その後、反応液を水冷し、マグネチックスターラーにて攪拌しながらCA-5を1.27g(3.99mmol)、CA-4を4.15g(13.96mmol)添加した。添加は、ロートを使用して30秒かけて行った。その後、添加に使用したロートを脱水N-メチル-2-ピロリドン10.00gで洗浄し、反応容器内を窒素置換して、水冷下で3時間撹拌を続けた。次に、反応溶液の5倍重量のメタノールを攪拌しているところに、反応溶液を少しずつ注ぎ1時間攪拌を続けた。その後、ろ過によって得られた析出物を、5倍重量のメタノールとともに1時間攪拌を行った後、ろ過して析出物を回収した。その後、さらに5倍重量のメタノールを用いて同様の操作を行い、得られた析出物を100℃、減圧下で24時間乾燥させて8.87gのポリアミック酸エステル(P14)を得た。得られた固形物のうち2.27gを、N-メチル-2-ピロリドン20.45gで完全に溶解させた。次に、その溶液にN-メチル-2-ピロリドン2.13g、及びブチルセロソルブ10.65gを加え、P14の濃度が6.0質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの50ml四つ口フラスコにp-PDA2.17g(20.0mmol)を入れ、さらにN-メチル-2-ピロリドン25gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながら1,2,3,4-シクロブタンテトラカルボン酸二無水物3.77g(19.2mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、室温で4時間撹拌して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、602.3mPa・sであった。
得られたポリアミック酸溶液7.89gを撹拌子の入った50ml三角フラスコに分取し、N-メチル-2-ピロリドン6.29g、及びブチルセロソルブ3.55gを加え、マグネチックスターラーで30分間撹拌してポリアミック酸濃度5.5質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの1000ml四つ口フラスコにDA-7を10.00g (34.92mmol)入れ、フラスコ内を窒素で置換した。次に脱水N-メチル-2-ピロリドン304g、及びピリジン6.1gをシリンジで仕込み、25℃でマグネチックスターラーにて攪拌し、DA-7を完全に溶解させた。その後、反応液を水冷し、マグネチックスターラーにて攪拌しながらCA-4を9.34g(31.43mmol)添加した。添加は、ロートを使用して30秒かけて行った。その後、添加に使用したロートを脱水N-メチル-2-ピロリドン20gで洗浄し、反応容器内を窒素置換して、水冷下で3時間撹拌を続けた。次に、反応溶液の5倍重量の蒸留水を攪拌しているところに、反応溶液を少しずつ注ぎ1時間攪拌を続けた。その後、ろ過によって得られた析出物を、5倍重量の蒸留水とともに1時間攪拌を行った後、ろ過して析出物を回収した。その後、さらに5倍重量のエタノールを用いて同様の操作を行い、得られた析出物を100℃、減圧下で24時間乾燥させて14.82gの固形物を得た。得られた固形物のうち3.99gを、N-メチル-2-ピロリドン35.90gで完全に溶解させた。次に、その溶液にN-メチル-2-ピロリドン6.91g、及びブチルセロソルブ19.36gを加え、ポリアミック酸エステルの濃度が5.5質量%の液晶配向処理剤を得た。
撹拌装置、及び窒素導入管付きの1000ml四つ口フラスコにDA-7を7.00g (24.44mmol)入れ、フラスコ内を窒素で置換した。次に、脱水N-メチル-2-ピロリドン249.3g、及びピリジン4.6gをシリンジで仕込み、25℃でマグネチックスターラーにて攪拌し、DA-7を完全に溶解させた。その後、反応液を水冷し、マグネチックスターラーにて攪拌しながらCA-5を1.56g(4.88mmol)、及びCA-4を6.08g(17.12mmol)添加した。添加は、ロートを使用して30秒かけて行った。その後、添加に使用したロートを脱水N-メチル-2-ピロリドン10gで洗浄し、反応容器内を窒素置換して、水冷下で3時間撹拌を続けた。次に、反応溶液の5倍重量のメタノールを攪拌しているところに、反応溶液を少しずつ注ぎ1時間攪拌を続けた。その後、ろ過によって得られた析出物を、5倍重量のメタノールとともに1時間攪拌を行った後、ろ過して析出物を回収した。その後、さらに5倍重量のメタノールを用いて同様の操作を行い、得られた析出物を100℃、減圧下で24時間乾燥させて11.15gの固形物を得た。得られた固形物のうち10.06gを、N-メチル-2-ピロリドン90.54gで完全に溶解させた。次に、その溶液にN-メチル-2-ピロリドン5.63g、及びブチルセロソルブ44.97gを加え、ポリアミック酸エステルの濃度が6.0質量%の液晶配向処理剤を得た。
また、表1中、「-」は、粘度が未測定であることを示す。
なお、2008年11月6日に出願された日本特許出願2008-285860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 (12)
- 式(1)において、-R1-Y1-と-R2-Y2-とが同一構造である請求項1に記載の液晶配向処理剤。
- 式(1)において、Y1及びY2が単結合である請求項1又は請求項2に記載の液晶配向処理剤。
- 式(1)において、Xが酸素原子である請求項1から請求項3のいずれかに記載の液晶配向処理剤。
- 前記テトラカルボン酸誘導体が、テトラカルボン酸二無水物、テトラカルボン酸一無水物、テトラカルボン酸、ジカルボン酸ジアルキルエステル、又はジカルボン酸クロライドジアルキルエステルである請求項1から請求項4のいずれかに記載の液晶配向処理剤。
- さらに、フッ素系界面活性剤、シリコーン系界面活性剤、又はノ二オン系界面活性剤を含有する請求項1から請求項5のいずれかに記載の液晶配向処理剤。
- さらに、官能性シラン含有化合物、又はエポキシ基含有化合物を含有する請求項1から請求項6のいずれかに記載の液晶配向処理剤。
- 液晶配向処理剤中の固形分濃度が、液晶配向処理剤の全量(100質量%)に対して、1~20質量%である請求項1から請求項7のいずれかに記載の液晶配向処理剤。
- 請求項1から請求項8のいずれかに記載の液晶配向処理剤から得られる液晶配向膜。
- 請求項9に記載の液晶配向膜を有する液晶表示素子。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2635400A1 (de) * | 1976-08-06 | 1978-02-09 | Bayer Ag | Verfahren zur herstellung von polyurethankunststoffen |
JPS5490147A (en) * | 1977-12-09 | 1979-07-17 | Ciba Geigy Ag | Bisanthranilic acid derivative*its manufacture and use |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5011753A (en) * | 1987-11-24 | 1991-04-30 | Hoechst Celanese Corporation | Photoresist compositions containing polyamides polybenzoxa from bis((aminohydroxyphenyl)hexafluoroisopropyl)diphenyl ethers |
JP3191535B2 (ja) | 1993-10-21 | 2001-07-23 | ジェイエスアール株式会社 | 液晶配向剤および液晶表示素子 |
FR2731223A1 (fr) * | 1995-03-02 | 1996-09-06 | Pf Medicament | Nouveaux derives bi-tryptaminiques, leur procede de preparation et leur utilisation a titre de medicaments |
JP3206401B2 (ja) | 1995-11-20 | 2001-09-10 | ジェイエスアール株式会社 | 液晶配向剤および液晶表示素子 |
JP3603460B2 (ja) | 1996-03-25 | 2004-12-22 | Jsr株式会社 | 液晶配向剤および液晶表示素子 |
KR100645616B1 (ko) * | 1998-08-26 | 2006-11-13 | 닛산 가가쿠 고교 가부시키 가이샤 | 액정배향 처리제 및 그것을 사용한 액정소자와 액정의배향방법 |
CN101633621A (zh) * | 2004-04-28 | 2010-01-27 | 日产化学工业株式会社 | 液晶定向剂、使用了该定向剂的液晶定向膜及液晶显示元件 |
JP5122980B2 (ja) * | 2005-02-09 | 2013-01-16 | スリーエム イノベイティブ プロパティズ カンパニー | アルキルオキシ置換チアゾロキノリン類およびアルキルオキシ置換チアゾロナフチリデン類 |
CU23431B6 (es) * | 2005-05-12 | 2009-10-16 | Ct Ingenieria Genetica Biotech | Método para la inhibición de la proliferación de células tumorales y el tratamiento del cáncer |
CN101421257A (zh) * | 2006-03-21 | 2009-04-29 | 欧洲分子生物学实验室 | 阻断细胞复制的试剂以及它们在抑制病理状态中的用途 |
CN101495915B (zh) * | 2006-07-28 | 2010-12-15 | 日产化学工业株式会社 | 液晶定向处理剂及使用了该处理剂的液晶显示元件 |
CN100529919C (zh) * | 2006-09-08 | 2009-08-19 | Jsr株式会社 | 液晶取向剂和液晶显示元件 |
JP2008090297A (ja) | 2006-09-08 | 2008-04-17 | Jsr Corp | 液晶配向剤および液晶表示素子 |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2635400A1 (de) * | 1976-08-06 | 1978-02-09 | Bayer Ag | Verfahren zur herstellung von polyurethankunststoffen |
JPS5490147A (en) * | 1977-12-09 | 1979-07-17 | Ciba Geigy Ag | Bisanthranilic acid derivative*its manufacture and use |
Non-Patent Citations (2)
Title |
---|
LEUNG, MAN-KIT ET AL.: "S,S-Dimethyl Dithiocarbonate: A Convenient Reagent for the Synthesis of Symmetrical and Unsymmetrical Ureas", JOURNAL OF ORGANIC CHEMISTRY, vol. 61, no. 12, 1996, pages 4175 - 4179 * |
TOHRU YOSHIDA ET AL.: "A new synthesis of cyclic ureas, cyclic urethanes, and a quinazolinedione. Selenium-assisted carbonylation of aromatic amines with carbon monoxide", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 60, no. 5, 1987, pages 1793 - 1799 * |
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KR101671659B1 (ko) | 2016-11-01 |
JPWO2010053128A1 (ja) | 2012-04-05 |
CN104761471B (zh) | 2017-01-04 |
JP5733340B2 (ja) | 2015-06-10 |
TWI477533B (zh) | 2015-03-21 |
JP2013241412A (ja) | 2013-12-05 |
CN102203662B (zh) | 2014-04-16 |
CN103739523B (zh) | 2015-08-05 |
CN102203662A (zh) | 2011-09-28 |
KR101613757B1 (ko) | 2016-04-19 |
CN104761471A (zh) | 2015-07-08 |
CN103739523A (zh) | 2014-04-23 |
KR20150138410A (ko) | 2015-12-09 |
KR20110082589A (ko) | 2011-07-19 |
JP5333454B2 (ja) | 2013-11-06 |
TW201030059A (en) | 2010-08-16 |
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