WO2012029763A1 - ジアミン、ポリイミド前駆体、ポリイミド、液晶配向剤、液晶配向膜及び液晶表示素子 - Google Patents
ジアミン、ポリイミド前駆体、ポリイミド、液晶配向剤、液晶配向膜及び液晶表示素子 Download PDFInfo
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- WO2012029763A1 WO2012029763A1 PCT/JP2011/069576 JP2011069576W WO2012029763A1 WO 2012029763 A1 WO2012029763 A1 WO 2012029763A1 JP 2011069576 W JP2011069576 W JP 2011069576W WO 2012029763 A1 WO2012029763 A1 WO 2012029763A1
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- liquid crystal
- diamine
- acid
- polyimide
- polyamic acid
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- 0 C*(C*1C)Cc2ccccc2N1c1ccccc1 Chemical compound C*(C*1C)Cc2ccccc2N1c1ccccc1 0.000 description 3
- GPRYFSRFEWGUAU-UHFFFAOYSA-N CC(C(C)(C)C1)C2=CC=C(C)N=C=C2N1c1ccccc1 Chemical compound CC(C(C)(C)C1)C2=CC=C(C)N=C=C2N1c1ccccc1 GPRYFSRFEWGUAU-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
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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
Definitions
- the present invention relates to a novel diamine, a polyimide precursor and polyimide, a liquid crystal aligning agent used for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element.
- a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction.
- the main liquid crystal alignment films that are industrially used are polyimide precursors such as polyamic acid (also called polyamic acid), polyamic acid esters, and polyimide-based liquid crystal aligning agents composed of polyimide solutions. It is manufactured by applying and forming a film.
- a surface stretching process is further performed by rubbing after film formation.
- a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays has been proposed, and in recent years, studies for industrialization have been performed.
- Patent Document 2 See Patent Document 2
- Patent Document 3 Various techniques have been proposed, such as Document 3).
- liquid crystal display elements have increased, the area has been increased, and the power consumption of display devices has progressed.
- the liquid crystal display elements can be used in various environments, and the characteristics required for liquid crystal alignment films are severe. It has become a thing.
- problems such as occurrence of printing failure due to deposition and separation due to a long tact time, and burn-in due to accumulated charge (RDC) are problems. It is difficult to solve both of these simultaneously.
- An object of the present invention is to solve the above-mentioned problems of the prior art, whereby a liquid crystal aligning agent having good printability can be obtained, and the accumulated charge can be reduced and the accumulated charge can be relaxed quickly. It is to provide a diamine, a polyimide precursor and a polyimide, a liquid crystal aligning agent using them, a liquid crystal alignment film, and a liquid crystal display element.
- the present inventors have achieved that the polyimide precursor and the liquid crystal aligning agent containing polyimide using the specific diamine represented by the following formula [1] as the diamine component achieve the above object. It has been found that it is extremely effective, and the present invention has been completed.
- the diamine compound represented by the following formula [1] is a novel compound not described in any literature.
- R 1 to R 9 are primary amino groups and the rest are hydrogen atoms or monovalent organic groups other than amino groups, which may be the same or different. 1 or 2 and the hydrogen atom of the saturated hydrocarbon part forming the ring may be substituted with a monovalent organic group other than a halogen atom or an amino group.
- the diamine is preferably represented by the following formula [2].
- p represents an integer of 0 to 3
- R 10 represents a monovalent organic group other than an amino group
- — (R 10 ) p represents p substituents R 10.
- q represents an integer of 0 to 4
- R 11 represents a monovalent organic group other than an amino group
- — (R 11 ) q represents q substituents R 11.
- n may be the same or different, and n is 1 or 2, and the hydrogen atom of the saturated hydrocarbon portion forming the ring may be substituted with an organic group other than a halogen atom or an amino group.
- the diamine is preferably represented by the following formula [3].
- n 1 or 2
- m is an integer of 0 to 2 (n + 1)
- R 12 represents a monovalent organic group other than a fluorine atom or an amino group
- — (R 12 ) m may be the same as or different from each other indicates that the substituent R 12 is m-number.
- R 12 is a hydrocarbon group having 1 to 6 carbon atoms, more preferably, R 12 is a methyl group.
- n 1.
- diamines represented by the following formulas [4-a] to [4-d] may be used.
- the polyimide precursor of the present invention is obtained by reacting at least one selected from tetracarboxylic acid and derivatives thereof with a diamine component containing the above diamine.
- the diamine is preferably 5 to 95 mol% when the total molar amount of the tetracarboxylic acid and its derivative is 100 mol%.
- the polyimide of the present invention is obtained by imidizing the polyimide precursor.
- liquid crystal aligning agent of this invention contains at least 1 type selected from the said polyimide precursor and the said polyimide, It is characterized by the above-mentioned.
- the liquid crystal alignment film of the present invention is obtained by applying the above liquid crystal aligning agent to a substrate and baking it.
- the liquid crystal display element of the present invention is characterized by comprising the liquid crystal alignment film.
- the novel diamine which can obtain the liquid crystal aligning agent with favorable printability, and can obtain the liquid crystal aligning film with few accumulation charges and quick relaxation of the accumulation
- the diamine of the present invention is represented by the following formula [1].
- R 1 to R 9 are primary amino groups and the rest are hydrogen atoms or monovalent organic groups other than amino groups, which may be the same or different. 1 or 2 and the hydrogen atom of the saturated hydrocarbon part forming the ring may be substituted with a monovalent organic group other than a halogen atom or an amino group.
- examples of the halogen atom include a fluorine atom.
- the monovalent organic group other than the amino group includes a hydrocarbon group, a hydroxyl group, a carboxyl group, a hydroxyl group, a thiol group, or a hydrocarbon group containing a carboxyl group, an ether bond, and an ester bond.
- a hydrocarbon group linked by a linking group such as an amide bond, a hydrocarbon group containing a silicon atom, and a halogenated hydrocarbon group.
- examples of the monovalent organic group other than the amino group include an inactive group in which the amino group is protected by a carbamate-based protecting group such as a t-butoxycarbonyl group.
- the position of the amino group is not particularly limited, and is not particularly limited as long as it is a diamine, but is represented by the following formula [2] from the viewpoint of liquid crystal alignment and ease of synthesis. Position is preferred.
- p represents an integer of 0 to 3
- R 10 represents a monovalent organic group other than an amino group
- — (R 10 ) p represents p substituents R 10.
- q represents an integer of 0 to 4
- R 11 represents a monovalent organic group other than an amino group
- — (R 11 ) q represents q substituents R 11.
- n may be the same or different, and n is 1 or 2, and the hydrogen atom of the saturated hydrocarbon portion forming the ring may be substituted with an organic group other than a halogen atom or an amino group.
- the hydrogen atom of the benzene ring having an amino group may be substituted with R 10 or R 11 which is a monovalent organic group other than the amino group.
- R 10 and R 11 other than the amino group include a hydrocarbon group, a carboxyl group, a hydroxyl group, a thiol group, or a hydrocarbon group having them, an ether bond, and an ester. Examples thereof include a hydrocarbon group linked by a bonding group such as a bond or an amide bond, a hydrocarbon group containing a silicon atom, or a halogenated hydrocarbon group.
- examples of R 10 and R 11 include an inert group in which an amino group is protected by a carbamate-based protecting group such as a t-butoxycarbonyl group.
- a carbamate-based protecting group such as a t-butoxycarbonyl group.
- the hydrogen atom of the benzene ring having an amino group is preferably unsubstituted.
- a more specific structural example is shown in the following formula [3].
- n 1 or 2
- m is an integer of 0 to 2 (n + 1)
- R 12 represents a monovalent organic group other than a fluorine atom or an amino group
- — (R 12 ) m may be the same as or different from each other indicates that the substituent R 12 is m-number.
- Each of them has a saturated hydrocarbon moiety that forms a ring, and the hydrogen atom of the carbon of the saturated hydrocarbon portion may be substituted with a halogen atom such as a fluorine atom or a monovalent organic group other than an amino group.
- the substituent that replaces the hydrogen atom of the saturated hydrocarbon portion is R 12 .
- the monovalent organic group other than the amino group that replaces the hydrogen atom of the saturated hydrocarbon portion include a hydrocarbon group, a hydroxyl group, and a carboxyl group.
- the hydrocarbon group herein may be linear, branched or cyclic, and may be a saturated hydrocarbon or an unsaturated hydrocarbon, and some of the hydrogen atoms of the hydrocarbon group may be a carboxyl group, a hydroxyl group or a thiol group. Alternatively, it may be replaced by a silicon atom, a halogen atom, or the like, and may be linked by a bonding group such as an ether bond, an ester bond, or an amide bond.
- R 12 is preferably a hydrocarbon group composed of only carbon atoms and hydrogen atoms.
- the substituent for substituting the hydrogen atom of the carbon in the saturated hydrocarbon portion is preferably a hydrocarbon group having 1 to 6 carbon atoms.
- Polyimide precursors such as polyamic acid and polyimide using the diamine of the present invention have good solubility in a solvent and thus have good printability.
- the hydrogen atom of the saturated hydrocarbon portion is a hydrocarbon group having 1 to 6 carbon atoms. This is because the solubility of the polyimide precursor such as polyamic acid and the polyimide in the organic solvent is further improved and the printability is further improved.
- the solubility of the polyimide precursor such as polyamic acid and the polyimide in the solvent is high, the compatibility with other polymers is excellent, and the polyimide precursor and polyimide and other polymers using the diamine of the present invention. Even in the case of using a mixture, separation and precipitation are less likely to occur, and the printability is excellent.
- hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, 1 -Propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group, hexenyl group, phenyl group and the like are exemplified, but not limited thereto.
- the substitution position and number are not particularly limited, and various selections can be made depending on the ease of synthesis and the availability of reagents.
- a particularly preferred structure is one in which a hydrogen atom in the saturated hydrocarbon portion is substituted with a methyl group. From the viewpoint of ease of synthesis, those in which the hydrogen atom of the saturated hydrocarbon portion is not substituted are preferred.
- the specific example of the diamine of this invention preferable below is shown, it is not limited to this.
- Particularly preferred diamines of the present invention are as follows.
- Polyimide precursors and polyimides such as polyamic acid and polyamic acid ester made from the diamine of the present invention represented by the above formula [1] as a raw material have good solubility in organic solvents, and thus form a liquid crystal alignment film.
- a liquid crystal aligning agent having good printability without forming pinholes or unevenness in the film thickness of the edge portion or the like.
- this liquid crystal aligning agent when used, it is possible to obtain a liquid crystal alignment film in which charge accumulation is unlikely to occur and the accumulated charge is quickly discharged. There is an effect that image sticking hardly occurs and display characteristics are excellent. In addition, an increase in ion density due to long-term use can be suppressed. Furthermore, the liquid crystal orientation is also good.
- the diamine of the present invention has a diphenylamine structure having a site that acts as a steric hindrance and a saturated hydrocarbon moiety, so that it is possible to improve solubility and polymer compatibility while maintaining the electrical properties of diphenylamine.
- the diamine of Patent Document 3 has a structure that has a double bond at the position of the saturated hydrocarbon portion in the diamine of the present invention and does not have a saturated hydrocarbon portion.
- the main synthesis method of the diamine of the present invention will be described.
- the method described below is a synthesis example and is not limited thereto.
- the diamine of the present invention can be obtained by reducing a dinitro compound and converting a nitro group to an amino group as shown in the following reaction formula.
- a diamine in which the hydrogen atom of the benzene ring and the saturated hydrocarbon portion is not substituted with a halogen atom such as a fluorine atom or a monovalent organic group other than an amino group is described as an example.
- the method for reducing the dinitro compound is not particularly limited, and palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum carbon sulfide, etc. are used as catalysts, and ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohols, etc.
- Examples of the method include reduction with hydrogen gas, hydrazine, hydrogen chloride and the like in a solvent. You may carry out under pressure using an autoclave etc. as needed.
- the use of palladium carbon, platinum carbon, etc. will reduce the unsaturated bond site and cause saturation. Since there exists a possibility that it may become a coupling
- a commercially available nitroindoline derivative or nitrotetrahydroquinoline derivative is reacted with nitrobenzene substituted with a leaving group X such as a halogen to thereby convert the dinitro compound.
- a leaving group X such as a halogen
- Preferred leaving groups X include fluorine atom, chlorine atom, bromine atom, iodine atom, tosylate (—OTs), mesylate (—OMs) and the like.
- the above reaction can be performed in the presence of a base.
- the base to be used is not particularly limited as long as it can be synthesized, but inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium hydride, pyridine, dimethylaminopyridine , Organic bases such as trimethylamine, triethylamine, and tributylamine.
- a palladium catalyst such as dibenzylideneacetone palladium or diphenylphosphinoferrocene palladium or a copper catalyst is used in combination, the yield can be improved.
- the —NH— hydrogen present in the nitroindoline derivative or nitrotetrahydroquinoline derivative is extracted using a base such as sodium hydride, and 4-nitro
- a method of reacting fluorobenzene is preferred, synthesis is not particularly limited because synthesis is possible by methods other than this method.
- the polyimide precursor such as polyamic acid or polyamic acid ester of the present invention can be obtained by reacting the diamine of the present invention with at least one selected from tetracarboxylic acid and tetracarboxylic acid derivatives.
- the ratio of reacting the diamine of the present invention with tetracarboxylic acid and its derivative is not particularly limited.
- the total molar amount of tetracarboxylic acid and its derivative is 100 mol%.
- the diamine of the present invention is preferably 5 to 95 mol%.
- tetracarboxylic acid derivatives include tetracarboxylic acid dihalide, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester.
- a polyamic acid can be obtained by reacting a tetracarboxylic acid or a derivative thereof such as tetracarboxylic acid dihalide or tetracarboxylic dianhydride with a diamine component containing the diamine of the present invention.
- a polyamic acid ester By reacting, a polyamic acid ester can be obtained.
- the diamine component is a diamine that is reacted with at least one selected from tetracarboxylic acid and a tetracarboxylic acid derivative in order to obtain a polyimide precursor or a polyimide.
- the diamine of the present invention may be used in combination with other diamines.
- the polyimide precursor of the present invention is obtained by imidizing this polyimide precursor, specifically, dehydrating and ring-closing the polyamic acid, or heating the polyamic acid ester at a high temperature to promote dealcoholization and ring-closing. Can do.
- the polyimide precursor and polyimide such as polyamic acid and polyamic acid ester of the present invention will be described in further detail below.
- the diamine component for obtaining a polyimide precursor such as polyamic acid by reaction with at least one selected from tetracarboxylic acid and tetracarboxylic acid derivatives such as tetracarboxylic dianhydride the content of the diamine of the present invention
- the liquid crystal alignment film obtained by using the polyimide precursor of the present invention or a polyimide obtained by imidizing the same is a liquid crystal with less accumulated charge and faster relaxation of the accumulated charge as the diamine content ratio of the present invention increases. An alignment film can be obtained.
- the diamine component is the diamine of the present invention.
- the content of the diamine component of the present invention in the diamine component used for polymerization is preferably 20 to 90 mol%, particularly preferably 30 to 80 mol. %.
- diamine component other diamines other than the diamine represented by the formula [1] used when the diamine represented by the formula [1] is less than 100 mol% are not particularly limited.
- a specific example is as follows.
- alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.
- aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
- aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methyl)
- heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino
- examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
- aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminoocta
- examples of other diamines include diamine compounds having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of these in the side chain.
- diamines represented by the following formulas [DA-1] to [DA-30] can be exemplified.
- R 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group
- S 5 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, — Represents O-, -CO-, or -NH-.
- R 14 represents an alkyl group having 1 to 22 carbon atoms, alkoxy Group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
- S 7 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2
- R 15 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
- R 16 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
- R 17 represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- a more stable pretilt can be obtained by using the diamine of the above formula [1] together with the diamines of the above [DA-1] to [DA-30].
- the diamine to be used in combination is preferably a formula [DA-10] to [DA-30], more preferably a diamine of [DA-10] to [DA-16].
- the preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol% with respect to the total amount of the diamine component, and is preferably 5 to 30 mol% from the viewpoint of printability.
- i is an integer of 0 to 3
- j is an integer of 1 to 5.
- VHR voltage holding ratio
- diaminosiloxanes represented by the following formula [DA-39] can also be mentioned.
- Such other diamine compounds may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
- tetracarboxylic acid such as tetracarboxylic dianhydride and the derivative thereof to be reacted with the diamine component in order to obtain a polyimide precursor such as the polyamic acid of the present invention
- a polyimide precursor such as the polyamic acid of the present invention
- Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
- Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclo
- the liquid crystal alignment is improved and the accumulated charge of the liquid crystal cell is reduced. Since it can reduce, it is preferable.
- Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.
- the tetracarboxylic acid dialkyl ester that is reacted with the diamine component to obtain the polyamic acid ester of the present invention is not particularly limited. Specific examples are given below.
- aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy- , 2,3,4-Tetrahydro-1-na
- aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalenetetracarboxylic acid dialkyl
- a polyamide can also be synthesized by reacting a diamine component such as the diamine of the present invention with a dicarboxylic acid.
- the dicarboxylic acid to be reacted with the diamine component in order to obtain polyamide is not particularly limited. Specific examples are given below.
- dicarboxylic acid or its aliphatic dicarboxylic acid include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimeline Mention may be made of dicarboxylic acids such as acids, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
- Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid.
- aromatic dicarboxylic acids o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic
- dicarboxylic acid containing a heterocyclic ring examples include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
- dicarboxylic acids may be acid dihalides or anhydrous structures. These dicarboxylic acids are preferably dicarboxylic acids capable of giving a polyamide having a linear structure in order to maintain the orientation of liquid crystal molecules.
- terephthalic acid isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4 caster-phenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid or these acid dihalides are preferred. Some of these compounds have isomers, but may be a mixture containing them. Two or more compounds may be used in combination.
- the dicarboxylic acids used in the present invention are not limited to the above exemplary compounds.
- Tetracarboxylic acid such as tetracarboxylic dianhydride and derivatives thereof may be used alone or in combination of two or more depending on properties such as liquid crystal alignment properties, voltage holding characteristics, and accumulated charges when formed into a liquid crystal alignment film. be able to.
- a method of obtaining a polyimide precursor such as polyamic acid by reacting a diamine component with at least one selected from tetracarboxylic acid and tetracarboxylic acid derivatives a known synthesis method can be used.
- a method of obtaining the polyamic acid of the present invention by reaction of tetracarboxylic dianhydride and a diamine component a method of reacting tetracarboxylic dianhydride and diamine component in an organic solvent can be mentioned.
- the reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
- the organic solvent used for the reaction between tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid can be dissolved.
- Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Sulfone, hexamethylsulfoxide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, Ethyl cell
- the solvent may be used alone or in combination.
- it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
- water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
- a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
- tetracarboxylic dianhydride or diamine component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed to form a high molecular weight product.
- the polycondensation temperature can be selected from -20 ° C to 150 ° C, but it is preferably in the range of -5 ° C to 100 ° C.
- the polycondensation reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
- the initial stage of the reaction may be performed at a high concentration, and then an organic solvent may be added.
- the ratio of the total number of moles of tetracarboxylic dianhydride and the total number of moles of diamine component is 0. It is preferably 8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
- the polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component as described above, or reacting the tetracarboxylic acid diester with the diamine component in the presence of an appropriate condensing agent or base. it can. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction.
- tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 hour.
- a polyamic acid ester By reacting for ⁇ 4 hours, a polyamic acid ester can be synthesized.
- pyridine triethylamine, 4-dimethylaminopyridine 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 reaction proceeds efficiently by adding Lewis acid as an additive.
- Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
- the addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester to be reacted.
- the solvent used in the above reaction can be the same solvent as that used in the synthesis of the polyamic acid shown above.
- N-methyl-2-pyrrolidone, ⁇ -Butyrolactone is preferred, and these may be used alone or in combination of two or more.
- the concentration at the time of synthesis is such that in the reaction solution of a tetracarboxylic acid derivative such as tetracarboxylic acid diester dichloride or tetracarboxylic acid diester and a diamine component, from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
- the total concentration is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
- the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
- the polyimide of the present invention can be obtained by dehydrating and ring-closing the polyamic acid.
- the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
- Examples of the method of imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
- the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the outside of the system.
- the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, 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, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- polyimide can also be obtained by heating a polyamic acid ester at a high temperature to promote dealcoholization and ring closure.
- the reaction solution is poured into a poor solvent and precipitated. That's fine.
- the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
- the polyimide precursor and polyimide which have been deposited in a poor solvent and precipitated are collected by filtration, they can be dried at room temperature or under normal pressure or reduced pressure.
- the impurities in the polymer can be reduced by repeating the steps of re-dissolving the precipitated and recovered polyimide precursor and polyimide in an organic solvent and repeating the reprecipitation and recovery 2 to 10 times.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the polyimide precursor and polyimide such as polyamic acid and polyamic acid ester to be contained in the liquid crystal aligning agent of the present invention takes into consideration the strength of the obtained coating film, workability at the time of coating film formation, and uniformity of the coating film.
- the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
- the polyimide precursor and polyimide such as the polyamic acid and polyamic acid ester of the present invention can be used together with a solvent to form a liquid crystal aligning agent.
- a liquid crystal aligning agent is a solution for forming a liquid crystal aligning film, and is a solution in which a polymer component for forming a liquid crystal aligning film is dispersed or dissolved in an organic solvent.
- the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.
- the polymer component contains at least one selected from polyimide precursors such as the polyamic acid and polyamic acid ester of the present invention and polyimide.
- all of the polymer components contained may be polyimide precursors or polyimides such as the polyamic acid or polyamic acid ester of the present invention, or the polyamic acid or polyamic of the present invention.
- Other polymers may be mixed with a polyimide precursor such as acid ester or polyimide.
- the content of the other polymer in the total amount of the polymer component is 0.5% by mass to 50% by mass, preferably 1% by mass to 30% by mass.
- Examples of such other polymers include polyamic acid obtained by using a diamine other than the diamine represented by the above formula [1] of the present invention as a diamine component to be reacted with a tetracarboxylic dianhydride component. And polyamic acid ester and polyimide.
- liquid crystal aligning agent at least one selected from polyimide precursors such as the polyamic acid and polyamic acid ester of the present invention and polyimide, and the content of other polymers mixed as necessary is the total amount of polymer components
- the content is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- the solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the polymer component.
- Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetra Methylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropane Amides, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone,
- the liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
- These poor solvents may be used alone or in combination.
- the above solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
- Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, 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 resin component contained in the liquid crystal aligning agent.
- the compound that improves the adhesion between the liquid crystal alignment film and the substrate include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane.
- the following phenoplast type additives may be introduced for the purpose of preventing the deterioration of electrical characteristics due to the backlight.
- Specific phenoplast additives are shown below, but are not limited to this structure.
- the amount used is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Is 1 to 20 parts by mass. If the amount used 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 aligning agent of the present invention has a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired.
- a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
- the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation, or without alignment treatment in vertical alignment applications. Since the liquid crystal alignment film of the present invention contains a polyimide precursor or polyimide formed using the diamine of the present invention, there is no pinhole formation or unevenness in the film thickness of the edge portion, etc. Accumulation of charges is difficult to occur, and the accumulated charges are quickly discharged.
- the substrate is not particularly limited as long as it has high transparency, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
- a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
- an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate.
- a material that reflects light such as aluminum, can be used.
- a high-performance element such as a TFT-type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
- the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet 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.
- Firing after applying the liquid crystal aligning agent on the substrate is carried out at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a hot-air circulating furnace, an infrared furnace, etc. Can be formed.
- the thickness of the coating film formed after baking is disadvantageous in terms of power consumption of the liquid crystal display element if it is too thick, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
- the thickness is preferably 10 to 100 nm.
- the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
- 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 producing a liquid crystal cell by a known method.
- the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
- a liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film.
- the substrate used in the liquid crystal display element of the present invention 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.
- a substrate on which a transparent electrode for driving liquid crystal is formed.
- substrate described with the said liquid crystal aligning film can be mentioned.
- liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.
- the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and liquid crystal materials used in the conventional vertical alignment method, such as MLC-2003, MLC-6608, MLC-6609 manufactured by Merck Ltd., etc. Can be used.
- a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
- the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
- the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
- 1- (4-nitrophenyl) -6-amino-1,2,3,4-tetrahydroquinoline obtained in the third step was 10.0 (37.1 mmol), 10% by mass palladium carbon. 1.00 g was weighed out, 300 mL of ethanol was added, and the atmosphere was sufficiently purged with nitrogen. Then, the atmosphere was hydrogen gas and vigorously stirred at room temperature.
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- TDA 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride
- CBDE 1,2, 3,4-Cyclobutanetetracarboxylic acid dimethyl ester
- DMT-MM 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate ⁇ organic solvent>
- NMP N-methyl-2-pyrrolidone
- ⁇ -BL ⁇ -butyrolactone
- BC Butyl cellosolve
- DPM Dipropylene glycol monomethyl ether
- GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 mL / L) Flow rate: 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).
- the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard manufactured by Kusano Kagaku), add 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture), and apply ultrasonic waves. It was completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
- the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
- x is the proton peak integrated value derived from the NH group of the amic acid
- y is the peak integrated value of the reference proton
- ⁇ is the NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
- Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
- Example 1 Synthesis of polyamic acid using CBDA / Diamine-1
- a diamine component in a 50 mL four-necked flask 1.50 g (6.65 mmol) of Diamin-1 obtained in Synthesis Example 1 and 15 NMP were obtained. .3 g, cooled to about 10 ° C., added 1.22 g (6.20 mmol) of CBDA, returned to room temperature, reacted for 6 hours in a nitrogen atmosphere, and a polyamic acid (PAA-1) solution having a concentration of 15% by mass was obtained. Obtained.
- PAA-1 polyamic acid
- Example 2 Synthesis of polyamic acid using CBDA / Diamine-2
- a diamine component in a 50 mL four-necked flask 1.50 g (6.25 mmol) of Diamin-2 obtained in Synthesis Example 2 and 15 NMP were obtained.
- 0.04 g cooled to about 10 ° C., added 1.14 g (5.80 mmol) of CBDA, returned to room temperature, reacted for 6 hours in a nitrogen atmosphere, and a polyamic acid (PAA-2) solution having a concentration of 15% by mass was obtained. Obtained.
- PAA-2 polyamic acid
- PAA-2 polyamic acid
- a liquid crystal aligning agent-2 of the present invention was obtained by making a 74% by mass and BC 20% by mass solution.
- the number average molecular weight of this polyamic acid was 13,700, and the weight average molecular weight was 35,600.
- PAA-3 polyamic acid
- a liquid crystal aligning agent-3 of the present invention was obtained by preparing a solution of 74% by mass and BC of 20% by mass.
- the number average molecular weight of this polyamic acid was 11,000, and the weight average molecular weight was 31,300.
- Example 4 Synthesis of polyamic acid using CBDA / Diamine-4 As a diamine component in a 50 mL four-necked flask, 1.50 g (6.25 mmol) of Diamine-4 obtained in Synthesis Example 4 and 15 NMP were obtained. Add 1.0 g, cool to about 10 ° C., add 1.14 g (5.80 mmol) of CBDA, return to room temperature and react for 6 hours under a nitrogen atmosphere, and add a solution of polyamic acid (PAA-4) with a concentration of 15% by mass. Obtained.
- PAA-4 polyamic acid
- PAA-4 polyamic acid
- a liquid crystal aligning agent-4 of the present invention was obtained by making a solution with 74 mass% and BC 20 mass%.
- the number average molecular weight of this polyamic acid was 14,200, and the weight average molecular weight was 36,700.
- Example 5 Synthesis of soluble polyimide using CBDA / Diamine-1 and C16DAB As a diamine component in a 50 mL four-necked flask, 2.00 g (8.88 mmol) of Diamine-1 obtained in Synthesis Example 1 was obtained. 0.774 g (2.22 mmol) and 27.2 g of NMP were added, cooled to about 10 ° C., 1.81 g (10.3 mmol) of CBDA was added, returned to room temperature, reacted for 6 hours under a nitrogen atmosphere, and polyamic acid was added. A solution of 15% by mass of (PAA-6) was obtained.
- Example 6 Synthesis of soluble polyimide using CBDA / Diamine-2 and C16DAB As a diamine component in a 50 mL four-necked flask, 2.00 g (8.36 mmol) of Diamine-2 obtained in Synthesis Example 2 was obtained. 0.728 g (2.09 mmol) and 6.3 g of NMP were added, cooled to about 10 ° C., 1.90 g (9.71 mmol) of CBDA was added, returned to room temperature, reacted for 6 hours under a nitrogen atmosphere, and polyamic acid was added. A solution of 15% by mass of (PAA-7) was obtained.
- Example 7 Synthesis of soluble polyimide using CBDA / Diamine-3, C16DAB As a diamine component in a 50 mL four-necked flask, 2.00 g (7.47 mmol) of Diamine-3 obtained in Synthesis Example 3 was obtained. 0.651 g (1.87 mmol) and 24.7 g of NMP were added, cooled to about 10 ° C., 1.51 g (8.68 mmol) of CBDA was added, and the mixture was returned to room temperature and allowed to react for 6 hours under a nitrogen atmosphere. A solution of 15% by mass of (PAA-8) was obtained.
- Example 8 Synthesis of soluble polyimide using CBDA / Diamine-4, C16DAB As a diamine component in a 50 mL four-neck flask, 2.00 g (8.36 mmol) of Diamine-4 obtained in Synthesis Example 4 was obtained. 0.728 g (2.09 mmol) and 6.3 g of NMP were added, cooled to about 10 ° C., 1.90 g (9.71 mmol) of CBDA was added, returned to room temperature, reacted for 6 hours under a nitrogen atmosphere, and polyamic acid was added. A solution of 15% by mass of (PAA-8) was obtained.
- Example 9 ⁇ Synthesis of polyamic acid using CBDA / Diamine-1, DDM>
- Diamin-1 obtained in Synthesis Example 1 was 2.50 g (11.1 mmol)
- DDM was 0.943 g (4.77 mmol)
- NMP was 17.9 g
- ⁇ -BL 18.9 g cooled to about 10 ° C.
- added 2.89 g (14.8 mmol) of CBDA returned to room temperature, reacted for 6 hours in a nitrogen atmosphere, and a polyamic acid (PAA-10) solution having a concentration of 15% by mass Got.
- PAA-10 polyamic acid
- Example 10 ⁇ Synthesis of polyamic acid using CBDA / Diamine-2, DDM>
- Diamin-2 obtained in Synthesis Example 2 was 2.50 g (10.4 mmol)
- DDM was 0.887 g (4.47 mmol)
- NMP was 17.3 g
- ⁇ -BL 17.3 g cooled to about 10 ° C.
- added 2.72 g (13.9 mmol) of CBDA returned to room temperature, reacted for 6 hours in a nitrogen atmosphere, and a polyamic acid (PAA-11) solution having a concentration of 15% by mass Got.
- PAA-11 polyamic acid
- Example 11 ⁇ Synthesis of polyamic acid using CBDA / Diamine-3, DDM>
- a diamine component in a 50 mL four-neck flask 2.50 g (9.35 mmol) of Diamine-3 obtained in Synthesis Example 3, 0.794 g (4.01 mmol) of DDM, 16.2 g of NMP, ⁇ -BL 16.2 g was added, cooled to about 10 ° C., 2.43 g (12.4 mmol) of CBDA was added, returned to room temperature, reacted for 6 hours under a nitrogen atmosphere, and a polyamic acid (PAA-12) solution having a concentration of 15% by mass Got.
- PAA-12 polyamic acid
- Example 12 ⁇ Synthesis of polyamic acid using CBDA / Diamine-4, DDM>
- Diamin-4 obtained in Synthesis Example 4 was 2.50 g (10.4 mmol)
- DDM was 0.887 g (4.47 mmol)
- NMP was 17.3 g
- ⁇ -BL 17.3 g cooled to about 10 ° C.
- added 2.72 g (13.9 mmol) of CBDA returned to room temperature, reacted for 6 hours in a nitrogen atmosphere, and a polyamic acid (PAA-13) solution having a concentration of 15% by mass Got.
- PAA-13 polyamic acid
- ⁇ -BL 80.5 g was added to 7.00 g of this polyamic acid ester (PAE-1), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, 29.2 g of ⁇ -BL was added to this solution and stirred at 50 ° C. for 20 hours to obtain a polyamic acid ester (PAE-1) 6 mass% and ⁇ -BL 94 mass% solution. (BL-PAE) was obtained.
- Example 14 40 g of the polyamic acid solution for blending (BL-PAA2) prepared in the same manner as in Example 10 was weighed into a 200 mL Erlenmeyer flask, and 10 ml of the polyamic acid ester solution for blending (BL-PAE) prepared in the same manner as in Example 13 was used. 0.0 g was added and stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal aligning agent BL-7.
- Example 15 40 g of a polyamic acid solution for blending (BL-PAA3) prepared in the same manner as in Example 11 was weighed into a 200 mL Erlenmeyer flask, and 10 ml of a polyamic acid ester solution for blending (BL-PAE) prepared in the same manner as in Example 13 was used. 0.0 g was added and stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal aligning agent BL-8.
- BL-PAA3 polyamic acid solution for blending
- Example 16 40 g of a polyamic acid solution for blending (BL-PAA4) prepared in the same manner as in Example 12 was weighed into a 200 mL Erlenmeyer flask, and 10 ml of a polyamic acid ester solution for blending (BL-PAE) prepared in the same manner as in Example 13 was used. 0.0 g was added, and the mixture was stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal aligning agent BL-9.
- BL-PAA4 polyamic acid solution for blending
- Comparative Example 4 40 g of a polyamic acid solution for blending (BL-PAA5) prepared in the same manner as in Comparative Example 3 was weighed into a 200 mL Erlenmeyer flask, and 10 ml of a polyamic acid ester solution for blending (BL-PAE) prepared in the same manner as in Example 13 was used. 0.0 g was added and stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal aligning agent BL-10 (Comparative Example).
- liquid crystal cells were produced as follows.
- a liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C. for 70 seconds, and then baked on a hot plate at 220 ° C. for 10 minutes to form a coating film having a thickness of 100 nm. It was.
- this coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm.
- a substrate with a film was obtained.
- liquid crystal alignment film After preparing two substrates with a liquid crystal alignment film subjected to the liquid crystal alignment treatment in this manner, a spacer of 6 ⁇ m is sprayed on the surface of the one liquid crystal alignment film, and then a sealant is printed thereon, and another sheet is obtained.
- the substrates were laminated so that the liquid crystal alignment film faces each other and the rubbing direction was orthogonal (twisted nematic liquid crystal cell), and the sealing agent was cured to produce an empty cell.
- liquid crystal MLC-2003 manufactured by Merck & Co., Inc.
- was injected into the empty cell by a reduced pressure injection method was sealed to obtain a twisted nematic liquid crystal cell.
- the RDC measured in this manner is shown in the column of “RDC after DCon 1h (accumulation) and DCoff 10 min after relaxation” (relaxation) in Table 3.
- the RDC data shown in Table 3 is the result of RDC after holding the liquid crystal cell at 100 ° C. for 30 hours (high temperature aging).
- Example 4 Evaluation of orientation The produced liquid crystal cell was observed visually and the orientation state of the liquid crystal was observed. The results are shown in Table 3 with the case where the liquid crystal is aligned without defects being good and the case where the alignment defects are generated is defective.
- Examples 1 to 4 and Comparative Example 1 were evaluated as homopolymers (polyamic acid) of diamine and CBDA, but Examples 1 to 4 using the diamine compound of the present invention were diamines of the present invention.
- RDC accumulation RDC value after 1 hour of DCOn
- relaxation RDC value after 10 minutes of DCoff
- Examples 1 to 4 had lower ion density than that of Comparative Example 1 in the initial state and after high-temperature aging, which was a practical problem. There was no value. In Examples 1 to 4, the liquid crystal was aligned without defects, but in Comparative Example 1, the liquid crystal was defective and the alignment was poor compared to Examples 1 to 4.
- Examples 5 to 8 and Comparative Example 2 were evaluated as soluble polyimides, but in Examples 5 to 8 using the diamine of the present invention, soluble polyimides can be produced and phase separation and precipitation during printing do not occur. There was no pinhole or film unevenness and printability was good. In Examples 5 to 8, the accumulation and relaxation of RDC were also significantly smaller. The ion density was small both in the initial state and after high-temperature aging, and was a value with no practical problem. On the other hand, in Comparative Example 2 using Diamin-5 which is a diamine of Patent Document 3, a soluble polyimide could not be prepared. In Examples 5 to 8, the liquid crystal was aligned without defects.
- Examples 9 to 12 and Comparative Example 3 are evaluations of blended materials of a soluble polyimide and a polyamic acid using the diamine of the present invention. Since the diamine of the present invention is excellent in compatibility with the soluble polyimide, In the liquid crystal aligning agents of Examples 9 to 12, phase separation and precipitation during printing did not occur, pinholes and film unevenness were observed, and printability was good. On the other hand, in Comparative Example 3, soluble polyimide and polyamic acid were localized and phase-separated, and separated during the printing test, resulting in poor printability at the edge portion. In Examples 9 to 12, the accumulation and relaxation of RDC were significantly smaller than those in Comparative Example 3. In Examples 9 to 12, compared to Comparative Example 3, the ion density was small both in the initial state and after high temperature aging, and there were no practical problems. In any of Examples 9 to 12, the liquid crystal was aligned without defects.
- Examples 13 to 16 and Comparative Example 4 are evaluations of blend materials of a polyamic acid ester and a polyamic acid using the diamine of the present invention.
- the diamine of the present invention is compatible with the polyamic acid ester. Therefore, the liquid crystal aligning agents of Examples 13 to 16 did not cause phase separation or precipitation during printing, had no pinholes and film unevenness, and had good printability.
- the liquid crystal aligning agent of Comparative Example 4 had a poor phase separation property and a tendency to separate during printing as in Comparative Example 3, resulting in poor edge portion printing properties.
- the accumulation and relaxation of RDC were significantly smaller than those in Comparative Example 4.
- the ion density was small both in the initial state and after high-temperature aging, and there were no practical problems.
- the liquid crystal was aligned without defects.
- the liquid crystal aligning agent and the liquid crystal alignment film using the diamine of the present invention can obtain a liquid crystal alignment film having good printability and less accumulated charge and quick relaxation of accumulated charge. It was done.
- the liquid crystal aligning agent using the diamine according to the present invention can provide a liquid crystal aligning film having good printability and less accumulated charge and quick relaxation of accumulated charge. Therefore, the liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device, such as a TN (Twisted Nematic) liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, It is suitably used for various types of display elements such as VA liquid crystal display elements, IPS liquid crystal display elements, and OCB (Optically self-compensated Birefringence) liquid crystal display elements.
- TN Transmission Nematic liquid crystal display element
- STN liquid crystal display element STN liquid crystal display element
- TFT liquid crystal display element a TFT liquid crystal display element
- VA liquid crystal display elements IPS liquid crystal display elements
- OCB Optically self-compensated Birefringence
Abstract
Description
本発明のジアミンは、下記式[1]で表されるものである。
[ジアミンの合成]
下記で用いた略号は以下の通りである。
DMF:N,N-ジメチルホルムアミド
THF:テトラヒドロフラン
RT:室温(25℃)
1H NMR (400 MHz,[D6]-DMSO)δ: 6.87-6.23(Aromatic-H、7H)、4.77-4.68(s-br、2H)、4.39-4.38(s-br、2H)、3,62-3,58(t、2H)、2.89-2.87(t、2H)
1H NMR (400 MHz,[D6]-DMSO)δ: 6.86-6.84(d、2H)、6.56-6.22(Aromatic-H、7H)、4.77-4.68(s-br、2H)、4.39-4.38(s-br、2H)、4.83-4.81(m、1H)、3,42-3,38(dd、1H)、2.89-2.87(dd、1H)1.48-1.47(s、3H)
1H NMR (400 MHz,[D6]-DMSO)δ: 6.86-6.22(Aromatic-H、7H)、4.74-4.66(s-br、2H)、4.41-4.39(s-br、2H)、4.23-4.21(m、1H)、1.48-1.14(s、9H)
1H NMR (400 MHz,[D6]-DMSO)δ: 6.85-6.35(Aromatic-H、7H)、5.00-4.98(s-br、2H)、4.59-4.58(s-br、2H)、3,94-3,93(m、2H)、2.89-2.87(m、2H)、2.66-2.64(m、2H)
1H NMR (400 MHz,[D6]-DMSO)δ: 7.25-6.28(Aromatic-H、9H)、5.20(s-br、2H)、4.56(s-br、2H)
下記に使用した化合物の略号は、以下のとおりである。また、各実施例及び比較例で合成した重合体の原料及び液晶配向剤の組成を表1及び表2に示す。
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
TDA:3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物
CBDE:1,2,3,4-シクロブタンテトラカルボン酸ジメチルエステル
p-PDA:1,4-フェニレンジアミン
DDM:4,4-ジアミノジフェニルメタン
C16DAB:4-ヘキサデシルオキシ-1,3-ジアミノベンゼン
DMT-MM:4-(4,6-ジメトキシー1,3,5-トリアジンー2-イル)4-メトキシモルホリウムクロリド n-水和物
<有機溶媒>
NMP:N-メチル-2-ピロリドン
γ-BL:γ-ブチロラクトン
BC:ブチルセロソルブ
DPM:ジプロピレングリコールモノメチルエーテル
重合反応により得られたポリマーの分子量は、該ポリマーをGPC(常温ゲル浸透クロマトグラフィー)装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として数平均分子量と重量平均分子量を算出した。
GPC装置:Shodex社製 (GPC-101)
カラム:Shodex社製 (KD803、KD805の直列)
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:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量 約900,000、150,000、100,000、30,000)、および、ポリマーラボラトリー社製 ポリエチレングリコール(分子量 約12,000、4,000、1,000)。
ポリイミドのイミド化率は次のようにして測定した。ポリイミド粉末20mgをNMRサンプル管(草野科学社製 NMRサンプリングチューブスタンダード)に入れ、重水素化ジメチルスルホキシド(DMSO-d6、0.05%TMS混合品)0.53mLを添加し、超音波をかけて完全に溶解させた。この溶液を日本電子データム(株)製NMR測定器(JNW-ECA500)にて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5~10.0ppm付近に現れるアミド酸のNH基に由来するプロトンピーク積算値とを用い以下の式によって求めた。なお、上記式において、xはアミド酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミック酸(イミド化率が0%)の場合におけるアミド酸のNH基プロトン1個に対する基準プロトンの個数割合である。
イミド化率(%)=(1-α・x/y)×100
50mL四口フラスコにジアミン成分として、合成実施例1で得られたDiamine-1を1.50g(6.65mmol)、NMPを15.3gを加え、約10℃に冷却し、CBDAを1.22g(6.20mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-1)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例2で得られたDiamine-2を1.50g(6.25mmol)、NMPを15.0gを加え、約10℃に冷却し、CBDAを1.14g(5.80mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-2)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例3で得られたDiamine-3を1.50g(5.80mmol)、NMPを14.3gを加え、約10℃に冷却し、CBDAを1.02g(5.20mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-3)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例4で得られたDiamine-4を1.50g(6.25mmol)、NMPを15.0gを加え、約10℃に冷却し、CBDAを1.14g(5.80mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-4)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成比較例1で得られたDiamine-5を1.50g(6.75mmol)、NMPを15.4gを加え、約10℃に冷却し、CBDAを1.23g(6.25mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-5)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例1で得られたDiamine-1を2.00g(8.88mmol)、C16DABを0.774g(2.22mmol)、NMPを27.2gを加え、約10℃に冷却し、CBDAを1.81g(10.3mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-6)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例2で得られたDiamine-2を2.00g(8.36mmol)、C16DABを0.728g(2.09mmol)、NMPを6.3gを加え、約10℃に冷却し、CBDAを1.90g(9.71mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-7)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例3で得られたDiamine-3を2.00g(7.47mmol)、C16DABを0.651g(1.87mmol)、NMPを24.7gを加え、約10℃に冷却し、CBDAを1.51g(8.68mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-8)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成実施例4で得られたDiamine-4を2.00g(8.36mmol)、C16DABを0.728g(2.09mmol)、NMPを6.3gを加え、約10℃に冷却し、CBDAを1.90g(9.71mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-8)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、合成比較例1で得られたDiamine-5を2.00g(8.96mmol)、C16DABを0.781g(2.24mmol)、NMPを27.3gを加え、約10℃に冷却し、CBDAを2.04g(10.4mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-9)の濃度15質量%の溶液を得た。
<CBDA/Diamine-1、DDMを用いたポリアミック酸の合成>
50mL四口フラスコにジアミン成分として、合成実施例1で得られたDiamine-1を2.50g(11.1mmol)、DDMを0.943g(4.77mmol)、NMPを17.9g、γ-BLを17.9g加え、約10℃に冷却し、CBDAを2.89g(14.8mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-10)の濃度15質量%の溶液を得た。
50mL四口フラスコにジアミン成分として、p-PDAを2.00g(18.5mmol)、C16DABを0.718g(2.06mmol)、NMPを35.4gを加え、約10℃に冷却し、TDAを6.12g(20.4mmol)加え、窒素雰囲気下40℃で20時間反応させ、ポリアミック酸(PAA-15)の濃度20質量%の溶液を得た。
調製したブレンド用ポリアミック酸溶液(BL-PAA1)を200mL三角フラスコに40g測り取り、調製したブレンド用ポリイミド溶液(BL-SPI)10.0gを加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-1を得た。
<CBDA/Diamine-2、DDMを用いたポリアミック酸の合成>
50mL四口フラスコにジアミン成分として、合成実施例2で得られたDiamine-2を2.50g(10.4mmol)、DDMを0.887g(4.47mmol)、NMPを17.3g、γ-BLを17.3g加え、約10℃に冷却し、CBDAを2.72g(13.9mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-11)の濃度15質量%の溶液を得た。
調製したブレンド用ポリアミック酸溶液(BL-PAA2)を200mL三角フラスコにそれぞれ40g測り取り、実施例9と同様の方法で調製したブレンド用ポリイミド溶液(BL-SPI)10.0gを加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-2を得た。
<CBDA/Diamine-3、DDMを用いたポリアミック酸の合成>
50mL四口フラスコにジアミン成分として、合成実施例3で得られたDiamine-3を2.50g(9.35mmol)、DDMを0.794g(4.01mmol)、NMPを16.2g、γ-BLを16.2g加え、約10℃に冷却し、CBDAを2.43g(12.4mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-12)の濃度15質量%の溶液を得た。
調製したブレンド用ポリアミック酸溶液(BL-PAA3)を200mL三角フラスコにそれぞれ40g測り取り、実施例9と同様の方法で調製したブレンド用ポリイミド溶液(BL-SPI)10.0gを加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-3を得た。
<CBDA/Diamine-4、DDMを用いたポリアミック酸の合成>
50mL四口フラスコにジアミン成分として、合成実施例4で得られたDiamine-4を2.50g(10.4mmol)、DDMを0.887g(4.47mmol)、NMPを17.3g、γ-BLを17.3g加え、約10℃に冷却し、CBDAを2.72g(13.9mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-13)の濃度15質量%の溶液を得た。
調製したブレンド用ポリアミック酸溶液(BL-PAA4)を200mL三角フラスコにそれぞれ40g測り取り、実施例9と同様の方法で調製したブレンド用ポリイミド溶液(BL-SPI)10.0gを加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-4を得た。
<CBDA/Diamine-5、DDMを用いたポリアミック酸の合成>
50mL四口フラスコにジアミン成分として、合成比較例1で得られたDiamine-5を2.50g(11.2mmol)、DDMを0.952g(4.80mmol)、NMPを18.1g、γ-BLを18.1g加え、約10℃に冷却し、CBDAを2.92g(14.9mmol)加え、室温に戻し窒素雰囲気下6時間反応させ、ポリアミック酸(PAA-14)の濃度15質量%の溶液を得た。
調製したブレンド用ポリアミック酸溶液(BL-PAA4)を200mL三角フラスコにそれぞれ40g測り取り、実施例9と同様の方法で調製したブレンド用ポリイミド溶液(BL-SPI)10.0gを加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-5を得た。
<ブレンド用PAE>
100mL四口フラスコにCBDEを6.35g(24.4mmol)、ジアミン成分として、p-PDAを250g(23.1mmol)、C16DABを0.896g(2.57mmol)、NMPを71.5g、トリエチルアミン0.60g(5.90mmol)を加え、約10℃に冷却し、DMT-MMを21.3g(77.1mmol)加え、室温に戻し窒素雰囲気下24時間反応させ、ポリアミック酸エステル(PAE-1)の濃度12質量%の溶液を得た。
実施例9と同様の方法で調製したブレンド用ポリアミック酸溶液(BL-PAA1)を200mL三角フラスコに40g測り取り、調製したブレンド用ポリアミック酸エステル溶液(BL-PAE)を10.0g加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-6を得た。
実施例10と同様にして調製したブレンド用ポリアミック酸溶液(BL-PAA2)を200mL三角フラスコに40g測り取り、実施例13と同様にして調製したブレンド用ポリアミック酸エステル溶液(BL-PAE)を10.0g加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-7を得た。
実施例11と同様にして調製したブレンド用ポリアミック酸溶液(BL-PAA3)を200mL三角フラスコに40g測り取り、実施例13と同様にして調製したブレンド用ポリアミック酸エステル溶液(BL-PAE)を10.0g加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-8を得た。
実施例12と同様にして調製したブレンド用ポリアミック酸溶液(BL-PAA4)を200mL三角フラスコに40g測り取り、実施例13と同様にして調製したブレンド用ポリアミック酸エステル溶液(BL-PAE)を10.0g加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-9を得た。
比較例3と同様にして調製したブレンド用ポリアミック酸溶液(BL-PAA5)を200mL三角フラスコに40g測り取り、実施例13と同様にして調製したブレンド用ポリアミック酸エステル溶液(BL-PAE)を10.0g加え、窒素雰囲気下で20時間撹拌させ、ブレンド系液晶配向剤BL-10(比較例)を得た。
実施例1~16及び比較例1~4で調製した液晶配向剤を、洗浄したCr板上に配向膜印刷機(日本写真印刷社製「オングストローマー」)を用いてフレキソ印刷を行なうことにより塗布性試験を行なった。アニロックスロールに約1.0mLの液晶配向剤を滴下し、空運転を10回実施した後、10分間印刷機を止め、印刷版を乾燥させた。その後、Cr基板1枚に印刷を行い、印刷後の基板は70℃のホットプレート上に5分間放置して、塗膜の仮乾燥を行い、膜状態の観察を行った。観察は目視と光学顕微鏡(ニコン社製「ECLIPSE ME600」)にて50倍で観察した。ピンホールが観察されなかった場合を良好、ピンホールが観察された場合を不良とし、また、エッジ部の膜厚にムラが生じなかった場合を良好、エッジ部の膜厚にムラが生じた場合を不良として評価した。結果を表3に示す。
実施例1~16及び比較例1~4で調製した液晶配向剤について、以下のようにして液晶セルを作製した。液晶配向剤を透明電極付きガラス基板にスピンコートし、80℃のホットプレート上で70秒間乾燥させた後、220℃のホットプレート上で10分間焼成を行い、膜厚100nmの塗膜を形成させた。ラビングによる液晶配向処理について、この塗膜面をロール径120mmのラビング装置でレーヨン布を用いて、ロール回転数1000rpm、ロール進行速度50mm/sec、押し込み量0.3mmの条件でラビングし、液晶配向膜付き基板を得た。
上記の[液晶セルの作製]に記載の方法で作製した液晶セルについて、初期状態のイオン密度を測定し、また、100℃で30時間保持(高温エージング)した後のイオン密度測定を行った。イオン密度測定においては、液晶セルに電圧±10V、周波数0.01Hzの三角波を印可した時のイオン密度を測定した。測定温度は80℃で行った。測定装置は、いずれの測定も東陽テクニカ社製6245型液晶物性評価装置を用いた。結果を表3に示す。
作製した液晶セルに、23℃の温度下で直流電圧を0Vから0.1V間隔で1.0Vまで印加し、各電圧でのフリッカー振幅レベルを測定し、フリッカー振幅と印加直流電圧における検量線を作成した。5分間アースした後、輝度が半分となる交流電圧(V50)と、直流電圧5.0Vを印加し、1時間後のフリッカー振幅レベルを測定し、予め作成した検量線と照らし合わせる事によりRDCを見積もった(フリッカー参照法)。その後、直流電圧を0Vにし、同様の方法にて10分後のRDCを見積もることで、RDCの緩和を測定した。このようにして測定したRDCを、表3の「DCon 1h後(蓄積)及びDCoff 10min後のRDC(緩和)」の欄に示す。また、尚、表3に示したRDCのデータは液晶セルを100℃で30時間保持(高温エージング)した後のRDCの結果である。
作製した液晶セルを目視にて観察し、液晶の配向状態を観察した。液晶が欠陥なく配向していた場合を良好、配向欠陥が生じた場合を不良として、結果を表3に示す。
この結果、実施例1~4及び比較例1は、ジアミンとCBDAのホモポリマー(ポリアミック酸)とした評価であるが、本発明のジアミン化合物を用いた実施例1~4は、本発明のジアミン化合物を用いなかった比較例1と比較して、RDCの蓄積(DCon 1時間後のRDC値)と、緩和(DCoff 10分後のRDC値)が、顕著に小さかった。また、ポリアミック酸単独であるため印刷性に大きな差は確認できなかったが、実施例1~4は、比較例1と比較して、初期状態も高温エージング後もイオン密度が小さく、実用上問題のない値であった。そして、実施例1~4では、液晶が欠陥無く配向していたが、比較例1では液晶に欠陥が生じ実施例1~4と比較して配向性が悪かった。
Claims (13)
- 前記R12が炭素数1~6の炭化水素基であることを特徴とする請求項3記載のジアミン。
- R12がメチル基であることを特徴とする請求項4に記載のジアミン。
- n=1であることを特徴とする請求項1~5のいずれか一項に記載のジアミン。
- テトラカルボン酸及びその誘導体から選択される少なくとも一種と、請求項1~7のいずれか一項に記載のジアミンを含むジアミン成分とを反応させて得られることを特徴とするポリイミド前駆体。
- 請求項1~7のいずれか一項に記載のジアミンは、テトラカルボン酸及びその誘導体の総モル量を100モル%とするとき、5~95モル%であることを特徴とする請求項8に記載のポリイミド前駆体。
- 請求項8又は9に記載のポリイミド前駆体をイミド化して得られることを特徴とするポリイミド。
- 請求項8に記載のポリイミド前駆体、請求項9に記載のポリイミド前駆体、及び、請求項10に記載のポリイミドから選択される少なくとも一種を含有することを特徴とする液晶配向剤。
- 請求項11に記載の液晶配向剤を基板に塗布し焼成して得られることを特徴とする液晶配向膜。
- 請求項12に記載の液晶配向膜を具備することを特徴とする液晶表示素子。
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JPWO2013147083A1 (ja) * | 2012-03-30 | 2015-12-14 | 日産化学工業株式会社 | ポリイミド系の液晶配向処理剤、液晶配向膜、及び液晶表示素子 |
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CN105446012A (zh) * | 2014-09-19 | 2016-03-30 | 株式会社日本显示器 | 液晶显示装置及取向膜材料 |
KR102420194B1 (ko) * | 2014-10-20 | 2022-07-12 | 닛산 가가쿠 가부시키가이샤 | 액정 배향제, 액정 배향막, 및 그것을 사용한 액정 표시 소자 |
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CN111732516B (zh) * | 2020-07-31 | 2021-01-05 | 南昌大学 | 一种n-芳基取代杂环化合物的制备方法 |
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