WO2014208609A1 - 液晶配向剤、液晶配向膜、液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜、液晶表示素子 Download PDFInfo
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- WO2014208609A1 WO2014208609A1 PCT/JP2014/066865 JP2014066865W WO2014208609A1 WO 2014208609 A1 WO2014208609 A1 WO 2014208609A1 JP 2014066865 W JP2014066865 W JP 2014066865W WO 2014208609 A1 WO2014208609 A1 WO 2014208609A1
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- liquid crystal
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- aligning agent
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- 0 *C(*1)=C1C1CCCC1 Chemical compound *C(*1)=C1C1CCCC1 0.000 description 20
- AINZARQGQHLZOE-UHFFFAOYSA-N C=C=CCC1=NC1 Chemical compound C=C=CCC1=NC1 AINZARQGQHLZOE-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N Cc1cc(N)ccc1N Chemical compound Cc1cc(N)ccc1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N Oc(cc1)ccc1-c(cc1)ccc1O Chemical compound Oc(cc1)ccc1-c(cc1)ccc1O VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N [O-][N+](c(cc1[N+]([O-])=O)ccc1F)=O Chemical compound [O-][N+](c(cc1[N+]([O-])=O)ccc1F)=O LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element.
- a liquid crystal display element that responds by an electric field to liquid crystal molecules that are aligned perpendicular to the substrate (also referred to as a vertical alignment method)
- ultraviolet light is applied while applying a voltage to the liquid crystal molecules during the manufacturing process.
- a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
- a technique for increasing the response speed of liquid crystal for example, see Patent Document 1 and Non-Patent Document 1 is known (PSA liquid crystal display).
- PSA liquid crystal display usually, the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound.
- the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that when the addition amount is increased, it precipitates at a low temperature.
- the addition amount of the polymerizable compound is reduced, a good alignment state cannot be obtained.
- the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered.
- the UV irradiation treatment necessary in the PSA mode is large, the components in the liquid crystal are decomposed and the reliability is lowered.
- Non-Patent Document 2 the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-Patent Document 2).
- a liquid crystal aligning agent to which a photopolymerizable compound is added is used.
- the photopolymerizable compound is not so soluble in the liquid crystal aligning agent, the photopolymerization added to the liquid crystal aligning agent is used.
- the addition amount of the functional compound is increased, the storage stability of the liquid crystal aligning agent is adversely affected.
- unreacted photopolymerizable compounds become impurities and cause burn-in, etc.
- Increasing the amount of UV irradiation to reduce unreacted photopolymerizable compounds damages liquid crystals and other components, and causes damage to liquid crystal display elements. It becomes a cause of reducing reliability.
- An object of the present invention is to solve the above-mentioned problems of the prior art, and a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display element without adding a photopolymerizable compound to the liquid crystal, and the liquid crystal An object is to provide an alignment film, a liquid crystal display element, and a diamine compound.
- a novel diamine compound having a group causing a photodimerization reaction and a group causing a photopolymerization reaction in the side chain (hereinafter also referred to as a specific diamine compound). .)
- a liquid crystal aligning agent containing at least one selected from a polyimide precursor obtained by reaction of a diamine component containing tetracarboxylic dianhydride component and an imidized polyimide By using a liquid crystal aligning agent containing at least one selected from a polyimide precursor obtained by reaction of a diamine component containing tetracarboxylic dianhydride component and an imidized polyimide.
- R 3 represents a group selected from —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—.
- R 4 represents: An alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are a fluorine atom or .
- R 4 is in the if any of the following groups not adjacent to each other, -CH 2 - may be replaced by these groups; -O- , —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—,
- R 5 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—
- R 6 represents a single bond
- R 6 represents a cinnamoyl group
- R 7 represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle,
- One or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be replaced with a fluorine atom or an organic group, and R 7 may be any of the following groups adjacent to each other: In this case, —CH 2 -
- liquid crystal aligning agent according to 1 or 2 wherein the diamine compound having a side chain for vertically aligning the liquid crystal is 10 mol% to 70 mol% in the diamine component.
- a liquid crystal display element comprising the liquid crystal alignment film according to 6.5.
- a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display element, in particular, a vertical alignment type liquid crystal display element, without containing a photopolymerizable compound in the liquid crystal.
- This liquid crystal aligning agent is not limited to the PSA type liquid crystal display element, but can be used for a liquid crystal display element that performs alignment treatment by irradiating polarized ultraviolet rays, for example. It is possible to obtain a liquid crystal alignment film effective in improving the above.
- the liquid crystal aligning agent of this invention is obtained by reaction with the diamine component containing the diamine compound represented by the said Formula [1], and the diamine compound which has a side chain which aligns a liquid crystal vertically, and a tetracarboxylic dianhydride component.
- the liquid crystal alignment agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.
- the diamine component which is a raw material of at least one polymer selected from a polyimide precursor contained in the liquid crystal aligning agent of the present invention and a polyimide obtained by imidizing the same is a diamine compound represented by the above formula [1] including.
- R 3 -R 4 -R 5 is a spacer moiety that connects the diaminobenzene skeleton in the side chain and R 6 that is a cinnamoyl group, and R 3 is a bonding group to the diaminobenzene skeleton in this spacer moiety.
- the linking group R 3 is —CH 2 — (ie methylene), —O— (ie ether), —CONH— (ie amide), —NHCO— (ie reverse amide), —COO— (ie ester), — It is selected from OCO— (ie reverse ester), —NH— (ie amino), —CO— (ie carbonyl).
- These linking groups R 3 can be formed by a general organic synthetic method. From the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO—, —NH— preferable.
- R 4 in the formula [1] is a central part of the spacer moiety, and is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle.
- any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group.
- the hydrogen atom to be replaced may be one place or a plurality of places.
- one or more —CH 2 — of the alkylene group, divalent carbocycle or heterocyclic ring is replaced with any of the following bonding groups when they are not adjacent to each other.
- R 4 may include a configuration of an alkylene group, a divalent carbocycle or a heterocycle-the linking group-alkylene group, a divalent carbocycle or a heterocycle.
- R 3 is —CH 2 —
- R 5 is —CH 2 —
- R 5 it means that the terminal on the R 5 side in R 4 may be the linking group.
- R 4 represents the structure of the linking group-alkylene group, divalent carbocycle or heterocyclic-the linking group, R 4 means that the structure may be any of the bonding groups.
- —CH 2 — replaced by the linking group may be at one location, and may be at multiple locations if the linking groups are not adjacent to each other.
- Specific examples of the divalent carbocycle or heterocycle include the following structures, but are not limited thereto.
- R 5 in the formula [1] represents a bonding group to R 6 in the spacer site.
- the linking group R 5 is selected from —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, and a single bond.
- These linking groups R 5 can be formed by ordinary organic synthetic techniques, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO—, —NH— Is preferred.
- R 7 in the formula [1] is a site where R 6 which is a cinnamoyl group and R 8 which is a photopolymerizable group selected from any one of an acryl group and a methacryl group are bonded, and R 7 is a single bond, Alternatively, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle, or a heterocycle. However, any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group. Further, the hydrogen atom to be replaced may be one place or a plurality of places.
- one or more —CH 2 — of the alkylene group, divalent carbocycle or heterocyclic ring is replaced with any of the following bonding groups when they are not adjacent to each other.
- R 7 is an alkylene group, a divalent carbocycle or a heterocycle-the linking group-alkylene group, a divalent carbocycle or a heterocycle, or the linking group-alkylene group, It means that it may contain a structure of carbocycle or heterocycle.
- —CH 2 — replaced by the linking group may be at one location, and may be at multiple locations if the linking groups are not adjacent to each other.
- Specific examples of the divalent carbocycle or heterocycle include the following structures, but are not limited thereto.
- R 8 in the formula [1] represents a photopolymerizable group selected from either an acrylic group or a methacryl group.
- the photopolymerizable group is a functional group that causes a polymerization reaction by light stimulation.
- a liquid crystal aligning agent containing at least one polymer selected from a polyimide precursor obtained by using such a diamine compound represented by the above formula [1] as a raw material and a polyimide obtained by imidizing it is used.
- the cross-linking reaction by the photopolymerizable group derived from the diamine compound represented by the above formula [1] and the dimerization reaction by the group causing photodimerization proceed, and the resulting cross-linking site or dimerization site causes the liquid crystal molecules to Since the tilt direction is stored, the response speed of the obtained liquid crystal display element can be increased.
- the ratio is not particularly limited, but from the viewpoint of improving the response speed, it is preferable to use an amount of 10 mol% to 90 mol% in the diamine component used for the synthesis of the polyimide precursor, more preferably 10 mol of the diamine component. % To 60 mol%, particularly preferably 10 mol% to 40 mol%.
- the method for synthesizing the diamine compound represented by the above formula [1] is not particularly limited. For example, it can be obtained by reducing the nitro group of the dinitro compound represented by the following formula [1a] and converting it to an amino group. it can.
- the reduction is performed using a catalyst that does not hydrogenate the double bond.
- a catalyst that does not hydrogenate the double bond.
- the dinitro compound represented by the above formula [1a] is obtained by a method in which —R 4 —R 5 —R 6 —R 7 —R 8 which is a side chain moiety is bonded to dinitrobenzene via R 3. be able to.
- R 3 is an amide bond (—CONH—)
- dinitrobenzene acid chloride is reacted with an amino compound containing —R 4 —R 5 —R 6 —R 7 —R 8 in the presence of an alkali.
- a method is mentioned.
- R 3 is a reverse amide bond (—HNCO—)
- the amino group-containing dinitrobenzene is reacted with an acid chloride containing —R 4 —R 5 —R 6 —R 7 —R 8 in the presence of an alkali.
- R 3 is an ester bond (—COO—)
- R 3 is a method of reacting dinitrobenzene acid chloride with an alcohol compound containing —R 4 —R 5 —R 6 —R 7 —R 8 in the presence of an alkali.
- R 3 is an inverted ester bond (—OCO—)
- a hydroxy group-containing dinitrobenzene and an acid chloride compound containing —R 4 —R 5 —R 6 —R 7 —R 8 are present in the presence of an alkali. The method of making it react under is mentioned.
- R 3 is an ether bond (—O—)
- a method of reacting a halogen group-containing dinitrobenzene with an alcohol compound containing —R 4 —R 5 —R 6 —R 7 —R 8 in the presence of an alkali Is mentioned.
- R 3 is an amino bond (—NH—)
- a halogen group-containing dinitrobenzene is reacted with an amino compound containing —R 4 —R 5 —R 6 —R 7 —R 8 in the presence of an alkali.
- a method is mentioned.
- R 3 is a carbonyl bond (—CO—)
- an aldehyde group-containing dinitrobenzene and a boronic acid compound containing —R 4 —R 5 —R 6 —R 7 —R 8 are present in the presence of a palladium or copper catalyst.
- the method of performing a coupling reaction under is mentioned.
- R 3 is a carbon bond (—CH 2 —), it has an unsaturated bond at the end of R 4 side of halogen group-containing dinitrobenzene and —R 4 —R 5 —R 6 —R 7 —R 8.
- the method of utilizing a Heck reaction or Sonogashira cross coupling reaction with a compound is mentioned.
- Examples of the dinitrobenzene acid chloride include 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, and 3,5-dinitrobenzyl chloride.
- 2,4-dinitrobenzyl chloride and amino group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline and the like.
- Examples of the hydroxy group-containing nitrobenzene include 2,4-dinitrophenol, 3,5-dinitrophenol, and 2,6-dinitrophenol.
- Examples of the halogen group-containing dinitrobenzene include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, 2,4-dinitroiodobenzene, 3,5-dinitroiodobenzene, 2, Examples thereof include 6-dinitroiodobenzene.
- Examples of the aldehyde group-containing dinitrobenzene include 2,4-dinitroaldehyde, 3,5-dinitroaldehyde, 2,6-dinitroaldehyde and the like.
- Examples of the method for synthesizing the side chain moiety —R 4 —R 5 —R 6 —R 7 —R 8 include the following methods. For example, in the case where the structure of —R 4 —R 5 —R 6 —R 7 —R 8 has an amide bond (—CONH—), an acid chloride compound containing —R 4 and —R 6 —R 7 — R 8 amino compound, acid chloride compound containing —R 4 —R 5 —R 6 and amino compound containing —R 7 —R 8 , or acid chloride compound containing —R 4 —R 5 —R 6 —R 7 And an amino compound containing —R 8 is reacted in the presence of an alkali.
- an amino compound containing —R 4 and —R 6 —R 7 —R 8 An acid chloride compound containing-, an amino compound containing -R 4 -R 5 -R 6 and an acid chloride compound containing -R 7 -R 8 , or an amino compound containing -R 4 -R 5 -R 6 -R 7 And an acid chloride compound containing —R 8 in the presence of an alkali.
- a halogen compound containing —R 4 and —R 6 —R 7 —R 8 are An amino compound containing, a halogen compound containing -R 4 -R 5 -R 6 and an amino compound containing -R 7 -R 8 , a halogen compound containing -R 4 -R 5 -R 6 -R 7 and -R 8 An amino compound containing -R 4 , an amino compound containing -R 6 -R 7 -R 8 , an amino compound containing -R 4 -R 5 -R 6 and a halogen compound containing -R 7 -R 8 Alternatively, a method in which an amino compound containing —R 4 —R 5 —R 6 —R 7 and a halogen compound containing —R 8 are reacted in the presence of an alkali can be mentioned.
- an aldehyde compound containing —R 4 and —R 6 —R 7 —R 8 Boronic acid compounds containing, aldehyde compounds containing -R 4 -R 5 -R 6 and boronic acid compounds containing -R 7 -R 8 , aldehyde compounds containing -R 4 -R 5 -R 6 -R 7 and -R boronic acid compounds containing 8, aldehyde compounds including boronic acid compounds and -R 6 -R 7 -R 8 including -R 4, boron acid compound containing -R 4 -R 5 -R 6 and -R 7 -R Examples thereof include a method in which an aldehyde compound containing 8 or a boronic acid compound containing -R 4 -R 5 -R 6 -R 7 and an aldehyde compound containing
- the diamine component which is the raw material of the polyimide precursor which the liquid crystal aligning agent of this invention contains, and the polyimide obtained by imidating this is at least 1 sort (s) of a polymer is represented by the said Formula [1].
- a diamine compound having a side chain for vertically aligning the liquid crystal is included.
- the diamine compound having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a steroid group, and a part of hydrogen atoms of these groups.
- diamines having groups in which all fluorine atoms are replaced as side chains for example, diamines represented by the following formulas [A-1] to [A-24] can be exemplified, but the invention is not limited thereto. is not.
- a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
- a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
- 3 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
- a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —
- a 5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
- a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—
- a 7 represents fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.
- a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
- a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
- diamine compound having a side chain for vertically aligning the liquid crystal include diamines represented by the following formulas [A-25] to [A-30].
- a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
- a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
- diamine compound having a side chain for vertically aligning the liquid crystal include diamines represented by the following formulas [A-31] to [A-32].
- the above-mentioned diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
- the diamine component which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing it.
- the proportion of the diamine is not particularly limited, but it is preferable to use an amount of 10 mol% to 70 mol% in the diamine component used for the synthesis of the polyimide precursor, and more preferably 10 mol% to 50 mol% in the diamine component. Particularly preferred is 20 mol% to 40 mol%.
- the amount of the diamine having a side chain for vertically aligning the liquid crystal is 20 mol% to 40 mol% in the diamine component used for the synthesis of the polyimide precursor, the response speed is improved and the alignment of the liquid crystal is fixed. It is particularly excellent in terms of its ability to convert.
- the diamine component which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing it, is as long as the effects of the present invention are not impaired.
- the diamine compound represented by the formula [1] and a diamine having a side chain for vertically aligning the liquid crystal other diamines may be included. Examples of other diamines include p-phenylene diamine, 2,3,5,6-tetramethyl-p-phenylene diamine, 2,5-dimethyl-p-phenylene diamine, m-phenylene diamine, and 2,4-dimethyl.
- the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
- the tetracarboxylic dianhydride component made to react with said diamine component is not specifically limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarbox
- the polyimide precursor that can be contained in the liquid crystal aligning agent of the present invention refers to a polyamic acid or a polyamic acid ester.
- a known synthesis method can be used.
- a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent.
- the reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
- the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid is soluble. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt
- organic solvent used in the reaction examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, e
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
- a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
- the method of adding alternately etc. is mentioned, You may use any of these methods.
- the diamine component or tetracarboxylic dianhydride 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.
- the body may be mixed and reacted to form a high molecular weight body.
- the temperature at the time of reacting the diamine component and the tetracarboxylic dianhydride component can be selected arbitrarily, and is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
- the reaction can be carried out at any concentration.
- the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on the reaction solution.
- the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.
- the method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and, as with the general polyamic acid synthesis method, as the tetracarboxylic dianhydride component, a tetracarboxylic acid having a corresponding structure is used.
- a corresponding polyamic acid can be obtained by reacting by a known method using a tetracarboxylic acid derivative such as tetracarboxylic acid dihalide.
- the polyamic acid ester can be synthesized by the following methods (1) to (3).
- a polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine component. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
- the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
- the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
- the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of polymer solubility. These may be used alone or in combination of two or more. Good.
- the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
- Polyamic acid ester is compoundable from a tetracarboxylic-acid diester dichloride and a diamine component.
- the tetracarboxylic acid diester dichloride and the diamine component are present 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 to 4 It can synthesize
- pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
- the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
- the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
- the polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
- 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.
- Polyamic acid ester is compoundable by polycondensing a tetracarboxylic-acid diester and a diamine component. Specifically, a tetracarboxylic acid diester and a diamine component are added in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can synthesize
- condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
- Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
- the amount of the condensing agent added is preferably 2 to 3 moles compared to the tetracarboxylic acid diester.
- tertiary amines such as pyridine and triethylamine can be used.
- the addition amount of the base is preferably 2 to 4 times mol with respect to the diamine component 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 to 1.0 times the mole of the diamine component.
- the synthesis method (1) or (2) is particularly preferable.
- the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
- a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
- Examples of the method for imidizing the above polyamic acid to form a polyimide include thermal imidation in which a polyamic acid solution is heated as it is, and catalytic imidation in which a catalyst is added to the polyamic acid solution.
- the imidation ratio from polyamic acid to polyimide is not necessarily 100%.
- 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 times mol, preferably 2 to 20 times mol of the amic acid group
- the amount of the acid anhydride is 1 to 50 times mol, preferably 3 to 30 times that of the amic acid group. Is a mole.
- 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.
- the reaction solution may be poured into a poor solvent and precipitated.
- 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 polymer precipitated in the poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
- the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- 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 liquid crystal aligning agent of the present invention includes a diamine component containing the diamine compound represented by the above formula [1] and a diamine compound having a side chain for vertically aligning the liquid crystal, and a tetracarboxylic dianhydride component. And at least one polymer selected from polyimides obtained by imidizing the polyimide precursors. It is obtained by a reaction between a diamine compound containing a diamine compound represented by the above formula [1] and a diamine compound having a side chain for vertically aligning a liquid crystal, and a tetracarboxylic dianhydride component.
- the total amount of at least one polymer selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor is preferably 1 to 10 (mass)%.
- the liquid crystal aligning agent of this invention is by reaction of the diamine component containing the diamine compound represented by the said Formula [1], and the diamine compound which has a side chain which aligns a liquid crystal perpendicularly, and a tetracarboxylic dianhydride component.
- You may contain other polymers other than the polyimide precursor obtained and at least 1 type of polymer selected from the polyimide obtained by imidating this polyimide precursor. In that case, it obtains by reaction with the diamine component and the tetracarboxylic dianhydride component containing the diamine compound which has a side chain which orientates the diamine compound represented by the said Formula [1] in the polymer all components in the perpendicular direction.
- the proportion of at least one polymer selected from the polyimide precursor obtained and the polyimide obtained by imidizing this polyimide precursor is preferably 10 (mass)% or more.
- the molecular weight of the polymer of the liquid crystal aligning agent is determined based on GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, workability at the time of forming the coating film, and uniformity of the coating film.
- the weight average molecular weight measured by the above method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
- the solvent which a liquid crystal aligning agent contains contains,
- a component such as at least one polymer selected from polyimides obtained by imidizing a precursor.
- combination of said polyamic acid can be mentioned.
- N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are from the viewpoint of solubility.
- two or more kinds of mixed solvents may be used.
- Solvents that improve the uniformity and smoothness of the coating include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Thor, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert
- the liquid crystal aligning agent of the present invention contains a polymerizable compound having a photopolymerizable or photocrosslinkable group at one or more terminals. That is, the polymerizable compound contained in the liquid crystal aligning agent of the present invention is a compound having one or more terminals having a group that undergoes photopolymerization or photocrosslinking.
- the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light.
- the polymerizable compound having a photocrosslinking group is a compound having a functional group capable of reacting with the polymer of the present invention and crosslinking with these upon irradiation with light.
- the polymerizable compound having a photocrosslinkable group also reacts with other polymerizable compounds having a photocrosslinkable group.
- Such a polymerizable compound is obtained by a reaction between a diamine compound represented by the above formula [1] and a diamine component containing a diamine compound having a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride component.
- a liquid crystal display element such as an SC-PVA type liquid crystal display is prepared by including it in a liquid crystal aligning agent together with at least one polymer selected from polyimides obtained by imidizing the polyimide precursor Compared to the case where a polymer having a side chain for vertically aligning the liquid crystal and a photoreactive side chain or the use of this polymerizable compound alone is used, the response speed is dramatically improved. The response speed can be sufficiently improved even with a small addition amount of the polymerizable compound.
- Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the following formula (II).
- the polymerizable compound examples include a polymerizable compound having a photopolymerizable group at each of two ends as represented by the following formula (III), and photopolymerization as represented by the following formula (IV).
- examples thereof include a polymerizable compound having a terminal having a group and a terminal having a photocrosslinkable group, and a polymerizable compound having a photocrosslinkable group at each of two terminals represented by the following formula (V).
- R 12, Z 1 and Z 2 are the same as R 12, Z 1 and Z 2 in the formula (II)
- Q 1 is a divalent organic group is there.
- Q 1 has a ring structure such as a phenylene group (—C 6 H 4 —), a biphenylene group (—C 6 H 4 —C 6 H 4 —), a cyclohexylene group (—C 6 H 10 —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.
- V is a single bond or represented by —R 1 O—
- R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R 1 O— and R 1 is A linear or branched alkylene group having 2 to 6 carbon atoms
- W represents a single bond or —OR 2 —
- R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR 2 — and R 2 represents a linear or A branched alkylene group having 2 to 6 carbon atoms.
- V and W may be the same or different, but if they are the same, synthesis is easy.
- the polymerizable compound represented by the above formula is a compound having a specific structure having ⁇ -methylene- ⁇ -butyrolactone groups which are polymerizable groups at both ends, so that the polymer has a rigid structure to fix the alignment of liquid crystals.
- a polyimide precursor and at least one polymer selected from polyimide obtained by imidizing this polyimide precursor are used.
- the response speed can be greatly improved by using the liquid crystal display device of the vertical alignment system such as the SC-PVA liquid crystal display to be used.
- the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent.
- a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added.
- the compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures.
- the polymerizable compound as described in the above formula having ⁇ -methylene- ⁇ -butyrolactone groups at both ends is sufficiently resistant to a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability. Can do.
- the photopolymerization or photocrosslinking group is a polymerizable compound having an acrylate group or a methacrylate group instead of an ⁇ -methylene- ⁇ -butyrolactone group
- the acrylate group or methacrylate group is a spacer such as an oxyalkylene group.
- the response speed is greatly improved, as in the case of the polymerizable compound having an ⁇ -methylene- ⁇ -butyrolactone group at both ends. be able to.
- the polymerizable compound has a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via a spacer such as an oxyalkylene group, the stability to heat is improved, or a high temperature, for example, 200 ° C. or higher. Can sufficiently withstand the firing temperature.
- polymerizable compound represented by the formula (III) include polymerizable compounds of the following formula.
- V represents a single bond or —R 1 O—
- R 1 represents a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R 1 O— and represented by R 1 Is a linear or branched alkylene group having 2 to 6 carbon atoms
- W is a single bond or —OR 2 —
- R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms.
- -OR 2 - synthesis and represented by R 2 .V and W is a linear or branched alkylene group having 2 to 6 carbon atoms may be the same or different structure but the same R 12 is H or an alkyl group having 1 to 4 carbon atoms.
- These polymerizable compounds are preferably 1% by weight to 30% by weight and more preferably 1% by weight to 20% by weight with respect to the solid content in the liquid crystal aligning agent from the viewpoint of solubility and the ability to develop a pretilt angle. 1 to 10% by weight is more preferable.
- the method for producing such a polymerizable compound is not particularly limited, and for example, it can be produced according to the synthesis examples described later.
- the polymerizable compound represented by the following formula (1) can be synthesized by combining techniques in organic synthetic chemistry.
- taraga and the like represented by the following reaction formula are prepared by the method proposed by P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990) using SnCl 2 and 2- (bromomethyl) acrylic acid. It can be synthesized by reacting (2- (bromomethyl) propenoic acid) with aldehyde or ketone.
- Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.
- R ′ represents a monovalent organic group.
- 2- (bromomethyl) acrylic acid is proposed by K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). Can be synthesized by the following method.
- the liquid crystal aligning agent may contain components other than those described above. Examples thereof include 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.
- 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 (manufactured by Asahi Glass Co., Ltd.).
- the ratio of use thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.
- compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
- a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added.
- 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 total amount of the polymer contained in the liquid crystal aligning agent.
- liquid crystal aligning agent is added with a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired. May be.
- ⁇ Liquid crystal alignment film> By applying and baking this liquid crystal aligning agent on a substrate, a liquid crystal alignment film for vertically aligning liquid crystals can be formed.
- 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.
- a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a 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 the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
- the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include a screen printing method, an offset printing method, a flexographic printing method, an inkjet method, a dip method, a roll coater, a slit coater, and a spinner.
- the firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at any temperature of, for example, 100 ° C. to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably Is from 150 ° C to 250 ° C.
- This baking can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
- the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm.
- the liquid crystal display element of the present invention is formed by two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
- a liquid crystal display element comprising a liquid crystal cell having the liquid crystal alignment film.
- the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
- various devices such as a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, and the like are available. Can be mentioned.
- the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used, and ultraviolet light is applied to the liquid crystal alignment film and the liquid crystal layer while applying voltage to the photopolymerizability of the polyimide precursor and the polyimide side chain.
- the group and the group causing photodimerization that is, the photopolymerizable group derived from the diamine compound represented by the above formula [1] and the group causing photodimerization
- the alignment of the liquid crystal is efficiently fixed, A liquid crystal display device with significantly excellent response speed is obtained.
- a photopolymerizable compound is added to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal display device having a response speed of the same or higher.
- 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 As a specific example, the thing similar to the board
- a substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed on one side substrate, and a slit pattern or projection pattern is not formed on the opposite substrate. The process can be simplified and high transmittance can be obtained.
- 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 a liquid crystal and a substrate is used.
- a substrate In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
- the 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 a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Alternatively, MLC-2041 or the like can be used.
- a liquid crystal material used in a conventional vertical alignment method for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Alternatively, MLC-2041 or the like can be used.
- a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are spread on the liquid crystal alignment film on one substrate, and the surface on which the liquid crystal alignment film is formed is on the inside. There is a method in which the other substrate is attached and liquid crystal is injected under reduced pressure to seal.
- a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
- the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. And applying ultraviolet rays while maintaining this electric field.
- the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
- the ultraviolet irradiation amount is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and It is preferable because the production efficiency is increased by reducing the ultraviolet irradiation time.
- the reaction of the photopolymerizable group of the polyimide precursor or the side chain of the polyimide and the group causing photodimerization proceeds, that is, The cross-linking reaction by the photopolymerizable group derived from the diamine compound represented by the formula [1] and the dimerization reaction by the group causing photodimerization proceed, and the direction in which the liquid crystal molecules are inclined is memorized by the resulting cross-linking site or dimerization site As a result, the response speed of the obtained liquid crystal display element can be increased.
- the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing process or a photo-alignment process. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
- NMP N-methyl-2-pyrrolidone
- BCS Butyl cellosolve
- the molecular weight measurement conditions for polyimide are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
- the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 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 proton of the NH group 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 ⁇ Measurement of 1 HNMR>
- Apparatus Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz
- Solvent deuterated dimethyl sulfoxide (DMSO-d 6 ), deuterated chloroform (CDCl 3 )
- reaction solution was poured into 1M aqueous hydrochloric acid (2 L) and stirred for a while.
- Ethyl acetate (1 L) was added thereto, the aqueous layer was removed by liquid separation operation, the organic layer was washed 3 times with saturated brine (500 mL), the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. Leaving 158 g of DA-1-1 (reddish brown viscous body). The obtained compound was directly used in the next step.
- the obtained filtrate was evaporated using a rotary evaporator, 50 mL of formic acid was added, and the mixture was stirred while heating to 50 ° C. After completion of the reaction, the reaction system was poured into 500 mL of water, and the precipitate was filtered. The filtrate was washed with isopropyl alcohol and dried to obtain 7.4 g of DA-1-3 (yellow solid) (yield 81%).
- the cyclohexane ring indicated by ⁇ in the above reaction formula indicates that the three-dimensional structure is a 1,4-trans-cyclohexane ring.
- a reaction vessel was charged with compound DA-3-2 (20.29 g, 54.8 mmol) and DCM (100 g). After purging with nitrogen, trifluoroacetic acid (31.2 g, 274 mol) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (200 mL) and extracted with ethyl acetate (1 L). Thereafter, the organic layer was washed three times with saturated brine (200 g), the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off with an evaporator to obtain a crude product of compound DA-3-3. The obtained crude product was dispersed and washed with methanol (30 g), filtered and dried to obtain Compound DA-3-3 (yield 10.9 g, yield 64%). The results of measuring the obtained compound by 1 H-NMR are shown below.
- compound DA-3-4 (17.00 g, 33.4 mmol), iron (11.2 g, 201 mmol), ethyl acetate (150 g), ammonium chloride (5.35 g, 100 mmol), distilled water (50 g) were added. In addition, heating and stirring were performed at 70 ° C. After confirming the completion of the reaction by HPLC, the solid was removed by celite filtration and washing with ethyl acetate (200 mL). The filtrate was washed 3 times with saturated brine (200 g), the organic layer was dried over magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a crude product of compound DA-10.
- the reaction solution was allowed to cool to room temperature ( ⁇ 30 degrees) and then filtered with a filter aid (KC floc). Ethyl acetate and water were added to the filtrate for liquid separation, and the organic layer was washed with water three times. Activated carbon was added to the organic layer and stirred, followed by filtration with KC floc. The filtrate was washed with water three times and dried over magnesium sulfate, and then the solvent was distilled off. Ethyl acetate (36 g) and hexane (288 g) were added to the residue, and the mixture was stirred at room temperature for crystallization. The filtered material was collected by filtration and dried at 40 ° C. to obtain 107 g of DA-10 (yellow crystals) (yield 83%). The results of measuring the obtained compound by 1 H-NMR are shown below.
- DA-13-1 (73.9 g, 360 mmol), 2-methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester (85.9 g, 328 mmol), potassium carbonate (107 g, 984 mmol) Potassium iodide (3.2 g, 36 mmol) was dissolved in N, N-dimethylformamide (514 g). The mixture was heated to 100 ° C. and reacted for 3.5 hours.
- the reaction solution was added dropwise to water (2600 g) and stirred.
- the precipitate was filtered to obtain 192 g of a yellow filtrate.
- Acetonitrile (170 g) was added to the obtained filtrate and stirred for 30 minutes, followed by filtration to obtain 162 g of a pale yellow filtrate.
- the obtained filtrate was dissolved in ethyl acetate (200 g) at 60 ° C., hexane (180 g) was added, and the mixture was cooled to 0 ° C.
- the precipitate was filtered, washed with hexane and dried to obtain 117 g of DA-13-2 (pale yellow solid) (yield 81%).
- the reaction solution was allowed to cool to room temperature ( ⁇ 30 ° C.) and then filtered through KC floc.
- the filtrate was concentrated, tetrahydrofuran was distilled off, ethyl acetate and activated carbon were added to the residue, and the mixture was stirred and filtered.
- the filtrate was separated, and the organic layer was washed 3 times with water and dried over sodium sulfate.
- the filtered filtrate was concentrated and purified by silica gel column to obtain 41 g of DA-13 (ocher solid) (yield 40%).
- the results of measuring the obtained compound by 1 H-NMR are shown below.
- Examples 1 to 4 and Comparative Example 1 >> (Example 1) BODA (1.25 g, 5.0 mmol), DA-1 (3.38 g, 7.0 mmol), DA-6 (1.14 g, 3.0 mmol) were dissolved in NMP (20.1 g) at 60 ° C. Then, CBDA (0.92 g, 4.7 mmol) and NMP (6.7 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
- NMP (22.0 g) was added to the obtained polyimide powder (A) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.
- NMP (22.0 g) was added to the obtained polyimide powder (B) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.
- Example 3 TCA (1.12 g, 5.0 mmol), DA-3 (2.24 g, 5.0 mmol), DA-8 (1.05 g, 2.0 mmol), 3AMPDA (0.73 g, 3.0 mmol) were added to NMP ( 12.2 g), and after reacting at 80 ° C. for 5 hours, CBDA (0.94 g, 4.8 mmol) and NMP (6.1 g) are added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.
- NMP (22.0 g) was added to the obtained polyimide powder (C) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.
- Example 4 CBDA (1.92 g, 10.0 mmol), DA-4 (3.73 g, 8.0 mmol), DA-9 (0.80 g, 2.0 mmol) were reacted at room temperature in NMP (36.58 g) for 10 hours. Then, NMP (32.3 g) and BCS (32.3 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (D1). The number average molecular weight of this polyamic acid was 9,000, and the weight average molecular weight was 32,000. In addition, 0.06 g of polymerizable compound RM1 (in terms of solid content) with respect to 10.0 g of the liquid crystal aligning agent (D1). The liquid crystal aligning agent (D2) was prepared by stirring at room temperature for 3 hours and dissolving.
- NMP (22.0 g) was added to the obtained polyimide powder (E) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.
- Example 5 Using the liquid crystal aligning agent (A2) obtained in Example 1, a liquid crystal cell was prepared according to the procedure shown below.
- the liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed, After drying for 90 seconds on this hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
- a sealant (solvent type thermosetting epoxy resin) was printed thereon.
- the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
- Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
- the response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, with a voltage of 40 Vp-p applied to the liquid crystal cell, UV was applied from the outside of the liquid crystal cell through a 365 nm band-pass filter at 10 J / cm 2 . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the cell after UV irradiation was measured. The results are shown in Table 1.
- a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector.
- the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
- a rectangular wave with a voltage of ⁇ 6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope.
- the luminance when no voltage is applied is obtained.
- a voltage of 0% and ⁇ 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
- Example 6 The same operation as in Example 5 was performed except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.
- Example 7 Except for using the liquid crystal aligning agent (C2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.
- Example 8 The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (D2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.
- Example 2 The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (A1) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.
- Example 3 The same operation as in Example 5 was performed except that the liquid crystal aligning agent (B1) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.
- Example 4 Except for using the liquid crystal aligning agent (C1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed, and the response speed before and after UV irradiation was compared. The pretilt angle was measured.
- Example 5 The same operation as in Example 5 was performed except that the liquid crystal aligning agent (D1) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.
- Example 6 The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (E2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.
- NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at room temperature for 5 hours.
- BODA (3.50 g, 14.0 mmol), DA-13 (5.21 g, 10.5 mmol), DA-6 (5.33 g, 14.0 mmol), 3AMPDA (2.54 g, 10.5 mmol) with NMP ( 61.9 g) and after reacting at 60 ° C. for 3 hours, CBDA (4.05 g, 20.7 mmol) and NMP (20.6 g) were added, and the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.
- NMP (44.0 g) was added to the obtained polyimide powder (H) (6.0 g) and dissolved by stirring at 50 ° C. for 3 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (H1) was obtained by stirring at room temperature for 5 hours.
- Example 12 Except for using the liquid crystal aligning agent (F2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.
- Example 13 Except for using the liquid crystal aligning agent (G2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.
- Example 14 The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (H2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.
- Comparative Example 6 even when a polymer having only a methacrylic group at the photosensitive side chain site and a polymerizable compound are used in combination, sufficient response speed improvement and tilt expression ability are obtained by irradiation with 365 nm ultraviolet rays. It was not obtained.
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Abstract
Description
本発明の液晶配向剤が含有するポリイミド前駆体及びこれをイミド化して得られるポリイミドから選択される少なくとも1種の重合体の原料であるジアミン成分は、上記式[1]で表されるジアミン化合物を含む。
また、本発明の液晶配向剤が含有するポリイミド前駆体及びこれをイミド化して得られるポリイミドから選択される少なくとも1種の重合体の原料であるジアミン成分は、上記式[1]で表されるジアミン化合物以外に、液晶を垂直に配向させる側鎖を有するジアミン化合物を含む。液晶を垂直に配向させる側鎖を有するジアミン化合物としては、長鎖のアルキル基、長鎖アルキル基の途中に環構造や枝分かれ構造を有する基、ステロイド基や、これらの基の水素原子の一部又は全部をフッ素原子に置き換えた基を側鎖として有するジアミン、例えば下記の式[A-1]~式[A-24]で示されるジアミンを例示することができるが、これに限定されるものではない。
また、本発明の液晶配向剤が含有するポリイミド前駆体及びこれをイミド化して得られるポリイミドから選択される少なくとも1種の重合体の原料であるジアミン成分は、本発明の効果を損なわない限りにおいて、上記式[1]で表されるジアミン化合物や上記液晶を垂直に配向させる側鎖を有するジアミン以外の、その他のジアミンを含んでいてもよい。その他のジアミンとしては、例えば、p-フェニレンジアミン、2,3,5,6-テトラメチル-p-フェニレンジアミン、2,5-ジメチル-p-フェニレンジアミン、m-フェニレンジアミン、2,4-ジメチル-m-フェニレンジアミン、2,5-ジアミノトルエン、2,6-ジアミノトルエン、2,5-ジアミノフェノール、2,4-ジアミノフェノール、3,5-ジアミノフェノール、3,5-ジアミノベンジルアルコール、2,4-ジアミノベンジルアルコール、4,6-ジアミノレゾルシノール、4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジヒドロキシ-4,4’-ジアミノビフェニル、3,3’-ジカルボキシ-4,4’-ジアミノビフェニル、3,3’-ジフルオロ-4,4’-ビフェニル、3,3’-トリフルオロメチル-4,4’-ジアミノビフェニル、3,4’-ジアミノビフェニル、3,3’-ジアミノビフェニル、2,2’-ジアミノビフェニル、2,3’-ジアミノビフェニル、4,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、2,2’-ジアミノジフェニルメタン、2,3’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、2,2’-ジアミノジフェニルエーテル、2,3’-ジアミノジフェニルエーテル、4,4’-スルホニルジアニリン、3,3’-スルホニルジアニリン、ビス(4-アミノフェニル)シラン、ビス(3-アミノフェニル)シラン、ジメチル-ビス(4-アミノフェニル)シラン、ジメチル-ビス(3-アミノフェニル)シラン、4,4’-チオジアニリン、3,3’-チオジアニリン、4,4’-ジアミノジフェニルアミン、3,3’-ジアミノジフェニルアミン、3,4’-ジアミノジフェニルアミン、2,2’-ジアミノジフェニルアミン、2,3’-ジアミノジフェニルアミン、N-メチル(4,4’-ジアミノジフェニル)アミン、N-メチル(3,3’-ジアミノジフェニル)アミン、N-メチル(3,4’-ジアミノジフェニル)アミン、N-メチル(2,2’-ジアミノジフェニル)アミン、N-メチル(2,3’-ジアミノジフェニル)アミン、4,4’-ジアミノベンゾフェノン、3,3’-ジアミノベンゾフェノン、3,4’-ジアミノベンゾフェノン、1,4-ジアミノナフタレン、2,2’-ジアミノベンゾフェノン、2,3’-ジアミノベンゾフェノン、1,5-ジアミノナフタレン、1,6-ジアミノナフタレン、1,7-ジアミノナフタレン、1,8-ジアミノナフタレン、2,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,7-ジアミノナフタレン、2,8-ジアミノナフタレン、1,2-ビス(4-アミノフェニル)エタン、1,2-ビス(3-アミノフェニル)エタン、1,3-ビス(4-アミノフェニル)プロパン、1,3-ビス(3-アミノフェニル)プロパン、1,4-ビス(4-アミノフェニル)ブタン、1,4-ビス(3-アミノフェニル)ブタン、ビス(3,5-ジエチル-4-アミノフェニル)メタン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(4-アミノベンジル)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、4,4’-[1,4-フェニレンビス(メチレン)]ジアニリン、4,4’-[1,3-フェニレンビス(メチレン)]ジアニリン、3,4’-[1,4-フェニレンビス(メチレン)]ジアニリン、3,4’-[1,3-フェニレンビス(メチレン)]ジアニリン、3,3’-[1,4-フェニレンビス(メチレン)]ジアニリン、3,3’-[1,3-フェニレンビス(メチレン)]ジアニリン、1,4-フェニレンビス[(4-アミノフェニル)メタノン]、1,4-フェニレンビス[(3-アミノフェニル)メタノン]、1,3-フェニレンビス[(4-アミノフェニル)メタノン]、1,3-フェニレンビス[(3-アミノフェニル)メタノン]、1,4-フェニレンビス(4-アミノベンゾエート)、1,4-フェニレンビス(3-アミノベンゾエート)、1,3-フェニレンビス(4-アミノベンゾエート)、1,3-フェニレンビス(3-アミノベンゾエート)、ビス(4-アミノフェニル)テレフタレート、ビス(3-アミノフェニル)テレフタレート、ビス(4-アミノフェニル)イソフタレート、ビス(3-アミノフェニル)イソフタレート、N,N’-(1,4-フェニレン)ビス(4-アミノベンズアミド)、N,N’-(1,3-フェニレン)ビス(4-アミノベンズアミド)、N,N’-(1,4-フェニレン)ビス(3-アミノベンズアミド)、N,N’-(1,3-フェニレン)ビス(3-アミノベンズアミド)、N,N’-ビス(4-アミノフェニル)テレフタルアミド、N,N’-ビス(3-アミノフェニル)テレフタルアミド、N,N’-ビス(4-アミノフェニル)イソフタルアミド、N,N’-ビス(3-アミノフェニル)イソフタルアミド、9,10-ビス(4-アミノフェニル)アントラセン、4,4’-ビス(4-アミノフェノキシ)ジフェニルスルホン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2’-ビス(4-アミノフェニル)ヘキサフルオロプロパン、2,2’-ビス(3-アミノフェニル)ヘキサフルオロプロパン、2,2’-ビス(3-アミノ-4-メチルフェニル)ヘキサフルオロプロパン、2,2’-ビス(4-アミノフェニル)プロパン、2,2’-ビス(3-アミノフェニル)プロパン、2,2’-ビス(3-アミノ-4-メチルフェニル)プロパン、3,5-ジアミノ安息香酸、2,5-ジアミノ安息香酸、1,3-ビス(4-アミノフェノキシ)プロパン、1,3-ビス(3-アミノフェノキシ)プロパン、1,4-ビス(4-アミノフェノキシ)ブタン、1,4-ビス(3-アミノフェノキシ)ブタン、1,5-ビス(4-アミノフェノキシ)ペンタン、1,5-ビス(3-アミノフェノキシ)ペンタン、1,6-ビス(4-アミノフェノキシ)へキサン、1,6-ビス(3-アミノフェノキシ)へキサン、1,7-ビス(4-アミノフェノキシ)ヘプタン、1,7-(3-アミノフェノキシ)ヘプタン、1,8-ビス(4-アミノフェノキシ)オクタン、1,8-ビス(3-アミノフェノキシ)オクタン、1,9-ビス(4-アミノフェノキシ)ノナン、1,9-ビス(3-アミノフェノキシ)ノナン、1,10-(4-アミノフェノキシ)デカン、1,10-(3-アミノフェノキシ)デカン、1,11-(4-アミノフェノキシ)ウンデカン、1,11-(3-アミノフェノキシ)ウンデカン、1,12-(4-アミノフェノキシ)ドデカン、1,12-(3-アミノフェノキシ)ドデカンなどの芳香族ジアミン、ビス(4-アミノシクロヘキシル)メタン、ビス(4-アミノ-3-メチルシクロヘキシル)メタンなどの脂環式ジアミン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノへキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,11-ジアミノウンデカン、1,12-ジアミノドデカンなどの脂肪族ジアミンが挙げられる。
ポリイミド前駆体を得るために、上記のジアミン成分と反応させるテトラカルボン酸二無水物成分は、特に限定されない。具体的には、ピロメリット酸、2,3,6,7-ナフタレンテトラカルボン酸、1,2,5,6-ナフタレンテトラカルボン酸、1,4,5,8-ナフタレンテトラカルボン酸、2,3,6,7-アントラセンテトラカルボン酸、1,2,5,6-アントラセンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、2,3,3’,4-ビフェニルテトラカルボン酸、ビス(3,4-ジカルボキシフェニル)エーテル、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、ビス(3,4-ジカルボキシフェニル)スルホン、ビス(3,4-ジカルボキシフェニル)メタン、2,2-ビス(3,4-ジカルボキシフェニル)プロパン、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス(3,4-ジカルボキシフェニル)プロパン、ビス(3,4-ジカルボキシフェニル)ジメチルシラン、ビス(3,4-ジカルボキシフェニル)ジフェニルシラン、2,3,4,5-ピリジンテトラカルボン酸、2,6-ビス(3,4-ジカルボキシフェニル)ピリジン、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸、3,4,9,10-ペリレンテトラカルボン酸、1,3-ジフェニル-1,2,3,4-シクロブタンテトラカルボン酸、オキシジフタルテトラカルボン酸、1,2,3,4-シクロブタンテトラカルボン酸、1,2,3,4-シクロペンタンテトラカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸、1,2,3,4-テトラメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,2-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,2,3,4-シクロヘプタンテトラカルボン酸、2,3,4,5-テトラヒドロフランテトラカルボン酸、3,4-ジカルボキシ-1-シクロへキシルコハク酸、2,3,5-トリカルボキシシクロペンチル酢酸、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、ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸、ビシクロ[4,3,0]ノナン-2,4,7,9-テトラカルボン酸、ビシクロ[4,4,0]デカン-2,4,7,9-テトラカルボン酸、ビシクロ[4,4,0]デカン-2,4,8,10-テトラカルボン酸、トリシクロ[6.3.0.0<2,6>]ウンデカン-3,5,9,11-テトラカルボン酸、1,2,3,4-ブタンテトラカルボン酸、4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドリナフタレン-1,2-ジカルボン酸、ビシクロ[2,2,2]オクト-7-エン-2,3,5,6-テトラカルボン酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロへキサン-1,2-ジカルボン酸、テトラシクロ[6,2,1,1,0,2,7]ドデカ-4,5,9,10-テトラカルボン酸、3,5,6-トリカルボキシノルボルナン-2:3,5:6ジカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸等が挙げられる。勿論、テトラカルボン酸二無水物も、液晶配向膜にした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、1種類または2種類以上併用してもよい。
本発明の液晶配向剤に含有され得るポリイミド前駆体とは、ポリアミック酸もしくはポリアミック酸エステルを指す。
ポリアミック酸エステルは、テトラカルボン酸二無水物とジアミン成分から得られるポリアミック酸をエステル化することによって合成することができる。具体的には、ポリアミック酸とエステル化剤を有機溶剤の存在下で-20℃~150℃、好ましくは0℃~50℃において、30分~24時間、好ましくは1~4時間反応させることによって合成することができる。
ポリアミック酸エステルは、テトラカルボン酸ジエステルジクロリドとジアミン成分から合成することができる。具体的には、テトラカルボン酸ジエステルジクロリドとジアミン成分とを塩基と有機溶剤の存在下で-20℃~150℃、好ましくは0℃~50℃において、30分~24時間、好ましくは1~4時間反応させることによって合成することができる。
ポリアミック酸エステルは、テトラカルボン酸ジエステルとジアミン成分を重縮合することにより合成することができる。具体的には、テトラカルボン酸ジエステルとジアミン成分を縮合剤、塩基、有機溶剤の存在下で0℃~150℃、好ましくは0℃~100℃において、30分~24時間、好ましくは3~15時間反応させることによって合成することができる。
上記したポリアミック酸をイミド化させてポリイミドとする方法としては、ポリアミック酸の溶液をそのまま加熱する熱イミド化や、ポリアミック酸の溶液に触媒を添加する触媒イミド化が挙げられる。なお、ポリアミック酸からポリイミドへのイミド化率は、必ずしも100%である必要はない。
本発明の液晶配向剤は、上述したように、上記式[1]で表されるジアミン化合物及び液晶を垂直に配向させる側鎖を有するジアミン化合物を含むジアミン成分と、テトラカルボン酸二無水物成分との反応で得られるポリイミド前駆体及び該ポリイミド前駆体をイミド化して得られるポリイミドから選択される少なくとも1種の重合体を含有するものである。液晶配向剤が含有する、上記式[1]で表されるジアミン化合物及び液晶を垂直に配向させる側鎖を有するジアミン化合物を含むジアミン成分と、テトラカルボン酸二無水物成分との反応で得られるポリイミド前駆体及び該ポリイミド前駆体をイミド化して得られるポリイミドから選択される少なくとも1種の重合体の総量は、1~10(質量)%であることが好ましい。
本発明の液晶配向剤は、1つ以上の末端に光重合または光架橋する基を有する重合性化合物を含有する。すなわち、本発明の液晶配向剤が含有する重合性化合物は、光重合または光架橋する基を有する末端を、1つ以上持っている化合物である。ここで、光重合する基を有する重合性化合物とは、光を照射することにより重合を生じさせる官能基を有する化合物である。また、光架橋する基を有する重合性化合物とは、光を照射することにより、本発明の重合体と反応してこれらと架橋することができる官能基を有する化合物である。なお、光架橋する基を有する重合性化合物は、光架橋する基を有する重合性化合物同士でも反応する。
このような重合性化合物の製造方法は特に限定されず、例えば後述する合成例に従って製造することができる。例えば、下記式(1)で表される重合性化合物は、有機合成化学における手法を組み合わせることによって合成することができる。例えば、下記反応式で表されるタラガ等がP.Talaga,M.Schaeffer,C.Benezra and J.L.Stampf,Synthesis,530(1990)で提案する方法により、SnCl2を用いて2-(ブロモメチル)アクリル酸(2-(bromomethyl)propenoic acid)と、アルデヒドまたはケトンとを反応させて、合成することができる。なお、Amberlyst 15は、ロームアンドハース社製の強酸性イオン交換樹脂である。
また、2-(ブロモメチル)アクリル酸は、下記反応式で表されるラマラーン等がK.Ramarajan,K.Kamalingam,D.J.O' Donnell and K.D.Berlin, Organic Synthesis,vol.61,56-59(1983)で提案する方法で合成することができる。
この液晶配向剤を基板上に塗布して焼成することにより、液晶を垂直に配向させる液晶配向膜を形成することができる。
本発明の液晶表示素子は、対向するように配置された2枚の基板と、基板間に設けられた液晶層と、基板と液晶層との間に設けられ本発明の液晶配向剤により形成された上記液晶配向膜とを有する液晶セルを具備する液晶表示素子である。具体的には、本発明の液晶配向剤を2枚の基板上に塗布して焼成することにより液晶配向膜を形成し、この液晶配向膜が対向するように2枚の基板を配置し、この2枚の基板の間に液晶で構成された液晶層を挟持し、液晶配向膜及び液晶層に電圧を印加しながら紫外線を照射することで作製される液晶セルを具備する液晶表示素子である。このような本発明の液晶表示素子としては、ツイストネマティック(TN:Twisted Nematic)方式、垂直配向(VA:Vertical Alignment)方式や、水平配向(IPS:In-Plane Switching)方式等、種々のものが挙げられる。
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
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
TCA:2,3,5-トリカルボキシシクロペンチル酢酸-1,4:2,3-二無水物
(ジアミン)
DBA:3,5-ジアミノ安息香酸
3AMPDA:3,5-ジアミノ-N-(ピリジン-3-イルメチル)ベンズアミド
下記式DA-1~DA-5で表される光反応性ジアミン
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
<添加剤>
3AMP:3-ピコリルアミン
<重合性化合物>
下記式RM1、RM2で表される重合性化合物
NMP: N-メチル-2-ピロリドン
BCS: ブチルセロソルブ
また、ポリイミドの分子量測定条件は、以下の通りである。
装置:センシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC-7200)、
カラム:Shodex社製カラム(KD-803、KD-805)
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9000,000、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)。
<1HNMRの測定>
装置:フーリエ変換型超伝導核磁気共鳴装置(FT-NMR)INOVA-400(Varian製)400MHz
溶媒:重水素化ジメチルスルホキシド(DMSO-d6)、重水素化クロロホルム(CDCl3)
標準物質:テトラメチルシラン(TMS)
(合成例1-1) DA-1の前駆体DA-1-1の合成
1H NMR (400 MHz,[D6]-DMSO): δ7.62-7.64 (d,2H), 7.56-7.68 (d,1H), 6.91-6.93 (d,2H), 6.44-6.48 (d,1H), 6.42 (s,1H), 6.00 (s,1H), 5.91 (s,1H), 5.69-5.72 (d,2H), 5.66 (s,1H), 4.36 (s,2H), 4.32 (s,2H), 3.96-4.00 (t,2H), 3.71-3.74 (t,2H), 1.84 (s,3H), 1.62-1.72 (m,4H), 1.40-1.44 (m,4H)
1H NMR(400MHz,[D6]-DMSO):δ7.54-7.67(d,2H),7.60(s,1H),6.94-6.97(d,2H),6.48-6.52(d,1H),6.42-6.43(s,2H),6.01-6.05(m,2H),5.70(s,1H),4.99(s,4H),4.36-4.40(m,4H),4.15-4.19(m,2H),4.00-4.03(m,2H),1.88(s,3H),1.66-1.75(m,4H),1.36-1.46(m,4H)
反応容器に化合物DA-3-1(74.43g、261mmol)、トリエチルアミン(29.81g、295mmol)、THF(1,000g)を仕込み、窒素置換後、内温が10℃を越えないように注意しながらメタクリロイルクロリド(27.01g、258mmol)のTHF(100g)溶液を滴下した。反応終了をHPLCで確認後、反応溶液を蒸留水(3L)へ注ぎ、酢酸エチル(1.5L)で抽出した。有機層を飽和食塩水(500g)で3回洗浄後、硫酸マグネシウムで乾燥し、ろ過、溶媒留去し、化合物DA-3-2の粗物を得た。得られた粗物をメタノール(100g)で分散洗浄し、ろ過、固体を乾燥させ、化合物[12]を得た(収量72.9g、収率80%)。得られた化合物を1H-NMRで測定した結果を以下に示す。
1H NMR (400 MHz,[D6]-DMSO):δ7.64-7.66 (d,2H), 7.58-7.62 (d,1H), 6.95-6.97 (d,2H), 6.60-6.62 (d,1H), 6.44-6.48 (d,1H), 6.02 (s,1H), 5.89 (s,1H), 5.78-5.81 (d,1H), 5.66 (s,1H), 4.65 (s,2H), 4.59 (s,2H), 4.08-4.17 (m,4H), 4.00-4.03 (t,2H), 2.65-2.69 (t,2H), 1.87 (s,3H), 1.62-1.74 (m,4H), 1.39-1.45 (m,4H)
(合成例5-1) DA-10の前駆体DA-10-1の合成
H), 6.71-6.67 (d,1H), 6.02 (s,1H), 5.84-5.83 (d,2H), 5.79-5.78 (d,2H), 5.67-5.66 (d,1H), 4.94 (s,1H), 4.80 (s,4H), 4.10-4.07 (t,2H), 4.01-3.98 (t,2H), 1.87 (s,3H), 1.74-1.70 (quint,2H), 1.63-1.60 (quint,2H), 1.41-1.33 (m,8H)
(合成例6-1) DA-11の前駆体DA-11-1の合成
(合成例7-1) DA-13の前駆体DA-13-1の合成
放冷後、N,N-ジメチルホルムアミド、トリエチルアミンを減圧留去した。酢酸エチル(500g)と水(200g)を加え分液し、有機層を水で3回洗浄した。有機層を溶媒留去し、DA-13-1(黄色オイル)を137g得た(収率98%)。
(実施例1)
BODA(1.25g、 5.0mmol)、DA-1(3.38g、7.0mmol)、DA-6(1.14g、3.0mmol)をNMP(20.1g)中で溶解し、60℃で5時間反応させたのち、CBDA(0.92g、4.7mmol)とNMP(6.7g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(30g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(2.2g)、およびピリジン(6.9g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(440ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(A1)を得た。このポリイミドのイミド化率は50%であり、数平均分子量は15,000、重量平均分子量は46,000であった。
BODA(1.25g、 5.0mmol)、DA-2(2.55g、5.0mmol)、DA-7(0.87g、2.0mmol)、DBA(0.46g、3.0mmol)をNMP(18.2g)中で溶解し、60℃で5時間反応させたのち、CBDA(0.92g、4.7mmol)とNMP(6.1g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(29g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(2.4g)、およびピリジン(7.6g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(430ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(B1)を得た。このポリイミドのイミド化率は51%であり、数平均分子量は14,000、重量平均分子量は39,000であった。
TCA(1.12g、 5.0mmol)、DA-3(2.24g、5.0mmol)、DA-8(1.05g、2.0mmol)、3AMPDA(0.73g、3.0mmol)をNMP(12.2g)中で溶解し、80℃で5時間反応させたのち、CBDA(0.94g、4.8mmol)とNMP(6.1g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(29g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(2.4g)、およびピリジン(7.6g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(430ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(C1)を得た。このポリイミドのイミド化率は51%であり、数平均分子量は11,000、重量平均分子量は31,000であった。
CBDA(1.92g、10.0mmol)、DA-4(3.73g、8.0mmol)、DA-9(0.80g、2.0mmol)を室温、NMP(36.58g)中で10時間反応させたのち、NMP(32.3g)、BCS(32.3g)を加え、室温で5時間攪拌することにより液晶配向剤(D1)を得た。このポリアミック酸の数平均分子量は9,000、重量平均分子量は32,000であった
また、上記の液晶配向剤(D1)10.0gに対して重合性化合物RM1を0.06g(固形分に対して10質量%)添加し、室温で3時間攪拌して溶解させ、液晶配向剤(D2)を調製した。
BODA(1.25g、 5.0mmol)、DA-5(1.06g、4.0mmol)、DA-9(1.20g、3.0mmol)、DBA(0.46g、3.0mmol)をNMP(14.7g)中で溶解し、60℃で5時間反応させたのち、CBDA(0.94g、4.8mmol)とNMP(4.9g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(23g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(2.4g)、およびピリジン(7.4g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(350ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(E)を得た。このポリイミドのイミド化率は50%であり、数平均分子量は17000、重量平均分子量は48000であった。
<液晶セルの作製>
(実施例5)
実施例1で得られた液晶配向剤(A2)を用いて下記に示すような手順で液晶セルの作製を行った。実施例1で得られた液晶配向剤(A2)を、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面にスピンコートし、80℃のホットプレートで90秒間乾燥した後、200℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜を形成した。
まず、バックライト、クロスニコルの状態にした一組の偏光版、光量検出器の順で構成される測定装置において、一組の偏光版の間に液晶セルを配置した。このときライン/スペースが形成されているITO電極のパターンがクロスニコルに対して45°の角度になるようにした。そして、上記の液晶セルに電圧±6V、周波数1kHzの矩形波を印加し、光量検出器によって観測される輝度が飽和するまでの変化をオシロスコープにて取り込み、電圧を印加していない時の輝度を0%、±4Vの電圧を印加し、飽和した輝度の値を100%として、輝度が10%から90%まで変化するのにかかる時間を応答速度とした。
名菱テクニカ製LCDアナライザーLCA-LUV42Aを使用した。
液晶配向剤(A2)のかわりに液晶配向剤(B2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(C2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(D2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(A1)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(B1)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(C1)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(D1)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(E2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
(実施例9)
BODA(3.50g、14.0mmol)、DA-10(5.85g、10.5mmol)、DA-6(5.33g、14.0mmol)、3AMPDA(2.54g、10.5mmol)をNMP(63.8g)中で溶解し、60℃で3時間反応させたのち、CBDA(4.05g、20.7mmol)とNMP(21.3g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(95g)にNMPを加え6。5質量%に希釈した後、イミド化触媒として無水酢酸(8.0g)、およびピリジン(24.7g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(1,300ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(F)を得た。このポリイミドのイミド化率は60%であり、数平均分子量は13,000、重量平均分子量は45,000であった。
BODA(3.50g、14.0mmol)、DA-11(4.75g、10.5mmol)、DA-6(5.33g、14.0mmol)、3AMPDA(2.54g、10.5mmol)をNMP(60.5g)中で溶解し、60℃で3時間反応させたのち、CBDA(4.05g、20.7mmol)とNMP(20.2g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(95g)にNMPを加え6。5質量%に希釈した後、イミド化触媒として無水酢酸(8.0g)、およびピリジン(24.7g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(1,300ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(G)を得た。このポリイミドのイミド化率は60%であり、数平均分子量は12,000、重量平均分子量は39,000であった。
BODA(3.50g、14.0mmol)、DA-13(5.21g、10.5mmol)、DA-6(5.33g、14.0mmol)、3AMPDA(2.54g、10.5mmol)をNMP(61.9g)中で溶解し、60℃で3時間反応させたのち、CBDA(4.05g、20.7mmol)とNMP(20.6g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液(95g)にNMPを加え6。5質量%に希釈した後、イミド化触媒として無水酢酸(8.0g)、およびピリジン(24.7g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(1,300ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミド粉末(H)を得た。このポリイミドのイミド化率は60%であり、数平均分子量は10,000、重量平均分子量は27,000であった。
<液晶セルの作製>
(実施例12)
液晶配向剤(A2)のかわりに液晶配向剤(F2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(G2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
液晶配向剤(A2)のかわりに液晶配向剤(H2)を用いた以外は実施例5と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行なった。
Claims (10)
- 下記式[1]で表されるジアミン化合物及び液晶を垂直に配向させる側鎖を有するジアミン化合物を含むジアミン成分と、テトラカルボン酸二無水物成分との反応で得られるポリイミド前駆体及びこれをイミド化して得られるポリイミドから選択される少なくとも1種の重合体、および重合性化合物を含有することを特徴とする液晶配向剤。
- 式[1]で表されるジアミン化合物が、ジアミン成分中の10モル%~90モル%であることを特徴とする請求項1に記載の液晶配向剤。
- 液晶を垂直に配向させる側鎖を有するジアミン化合物が、ジアミン成分中の10モル%~70モル%であることを特徴とする請求項1または請求項2に記載の液晶配向剤。
- 請求項1から請求項4のいずれか一項に記載の液晶配向剤から得られることを特徴とする液晶配向膜。
- 請求項5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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JP6478052B2 (ja) | 2019-03-06 |
CN105492965A (zh) | 2016-04-13 |
KR20160024949A (ko) | 2016-03-07 |
TWI642725B (zh) | 2018-12-01 |
KR102303303B1 (ko) | 2021-09-16 |
CN105492965B (zh) | 2019-04-09 |
TW201518407A (zh) | 2015-05-16 |
JPWO2014208609A1 (ja) | 2017-02-23 |
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