WO2013002345A1 - Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents
Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- WO2013002345A1 WO2013002345A1 PCT/JP2012/066591 JP2012066591W WO2013002345A1 WO 2013002345 A1 WO2013002345 A1 WO 2013002345A1 JP 2012066591 W JP2012066591 W JP 2012066591W WO 2013002345 A1 WO2013002345 A1 WO 2013002345A1
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- 0 *c(cc1)ccc1-c1ccc(*c2cc(N)cc(N)c2)cc1 Chemical compound *c(cc1)ccc1-c1ccc(*c2cc(N)cc(N)c2)cc1 0.000 description 6
- JOYDHIOPPHIVSO-UHFFFAOYSA-N CC(C)OCCc(cc1)ccc1N Chemical compound CC(C)OCCc(cc1)ccc1N JOYDHIOPPHIVSO-UHFFFAOYSA-N 0.000 description 1
- RZLQZBSQFVOICL-UHFFFAOYSA-N Nc1cc([AlH]C(CC2)CCC2C(CC2)CCC2S)cc(N)c1 Chemical compound Nc1cc([AlH]C(CC2)CCC2C(CC2)CCC2S)cc(N)c1 RZLQZBSQFVOICL-UHFFFAOYSA-N 0.000 description 1
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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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- 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
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Definitions
- the present invention relates to a method for manufacturing a liquid crystal alignment film, a liquid crystal alignment film obtained by the manufacturing method, and a liquid crystal display element using the liquid crystal alignment film.
- the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
- the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
- an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
- the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. Further, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
- alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
- the main liquid crystal alignment film used industrially is a polyimide liquid crystal alignment treatment agent made of a solution of polyimide precursor (polyamic acid (polyamic acid), polyamic acid ester), polyimide, etc., applied to the substrate. Then, it is manufactured by forming a film.
- a surface stretching process by rubbing is performed after film formation.
- a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like has been proposed, and in recent years, studies for industrialization have been performed.
- the rubbing treatment is performed by rubbing the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on the substrate with a cloth such as cotton, nylon or polyester (rubbing), and liquid crystal in the rubbing direction (rubbing direction).
- This is a method of orientation. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
- a photo-alignment method As a method for aligning a liquid crystal alignment film in place of rubbing, a photo-alignment method has been actively studied. For example, a photo-alignment method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like has been proposed, and in recent years, studies for industrialization have been performed. There are several photo-alignment methods, but in general, anisotropy is formed on the surface of the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated (parallelized) light. The liquid crystal is aligned according to the above. As a main specific photo-alignment method, a decomposition type photo-alignment method is known.
- the decomposition type photo-alignment method means, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is caused by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure.
- This is a method of aligning liquid crystal with polyimide (for example, see Patent Document 1).
- a dimerization type photo-alignment method is also known.
- the dimerization type photo-alignment method is, for example, using polyvinyl cinnamate, irradiating polarized ultraviolet rays, causing a dimerization reaction at double bond portions of two side chains parallel to the polarized light, and orthogonal to the polarization direction.
- This is a method of aligning liquid crystals in the direction (see, for example, Non-Patent Document 1).
- the alignment treatment method of the liquid crystal alignment film by the photo-alignment method does not require rubbing, and there is no concern about generation of dust or static electricity.
- the alignment treatment method of the liquid crystal alignment film by the photo-alignment method can perform the alignment treatment even on the substrate of the liquid crystal display element having a concavo-convex surface, and is suitable as an industrial production process.
- the display characteristics of the liquid crystal display element can be improved by changing the structure of polyamic acid, polyamic acid ester, polyimide, etc., blending polyamic acid, polyamic acid ester, polyimide, etc. having different characteristics, and adding additives. Methods are used to improve liquid crystal alignment and electrical characteristics, and control the pretilt angle. For example, it has been proposed to use a polymer having a group having a specific structure as a side chain (see Patent Document 2).
- the photo-alignment method eliminates the rubbing process itself as compared with the rubbing process conventionally used industrially as an alignment processing method for liquid crystal display elements, and has a great advantage.
- it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes. Necessary.
- a large amount of ultraviolet irradiation of about several to several tens of joules (J) may be required.
- the amount of photoreactive groups introduced is increased. There is a need. Therefore, an unreacted group may remain even after ultraviolet irradiation.
- the unreacted group reacts due to backlight or external light, and the alignment state of the liquid crystal is changed. There is a problem that defects such as change occur.
- An object of this invention is to provide the manufacturing method of the liquid crystal aligning film which implement
- a thin film containing a polyimide or a polyimide precursor having a photoreactive group is formed on a substrate, and the front thin film surface is irradiated with polarized ultraviolet rays while being heated, and the substrate contains a polyimide precursor.
- a method for producing a liquid crystal alignment film comprising producing a liquid crystal alignment film comprising molecules.
- R 1 represents a divalent organic group
- R 2 represents a tetravalent organic group
- R 3 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms
- R 4 represents hydrogen.
- n 1 represents a positive integer.
- R 5 represents a divalent organic group constituting a photoreactive group.
- R 6 represents a tetravalent organic group,
- R 7 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
- R 8 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms, and
- n 2 represents a positive integer.
- R 9 represents a divalent organic group
- R 10 represents a divalent organic group constituting a photoreactive group
- n 3 represents a positive integer.
- the polyimide precursor having the photoreactive group is a polyimide precursor obtained by polycondensation reaction of a diamine component containing a diamine represented by the following formula [4] and tetracarboxylic dianhydride.
- the manufacturing method of the liquid crystal aligning film as described in said (1) is a polyimide precursor obtained by polycondensation reaction of a diamine component containing a diamine represented by the following formula [4] and tetracarboxylic dianhydride.
- X 1 represents a single bond or an alkylene group having 1 to 5 carbon atoms (provided that —CH 2 — which is not adjacent to each other may be replaced by an ether bond, an ester bond or an amide bond).
- X 2 represents —OCO—CH ⁇ CH— or —CH ⁇ CH—COO—
- X 3 represents a single bond, an alkylene group having 1 to 10 carbon atoms or a divalent benzene ring
- X 4 represents a single bond.
- X 5 is a single bond or an alkylene group having 1 to 6 carbon atoms (provided that —CH 2 — not adjacent to each other is an ether bond, ester bond) Or an amide bond may be substituted.)
- the formula [4] has one or more cinnamoyl groups.
- thermoforming film according to any one of (1) to (6), wherein the heating temperature is a temperature selected from a temperature range in which the polyimide precursor having the photoreactive group does not change to polyimide. Manufacturing method.
- achieves high photoreaction efficiency and enables highly efficient alignment processing is provided.
- the liquid crystal display device using the obtained liquid crystal alignment film has a high production efficiency and a small number of photoreactive residues in the liquid crystal alignment film, resulting in a defect that the liquid crystal alignment state changes even after long-term use. Hard to do.
- rubbing on the liquid crystal alignment film can be eliminated.
- a high-efficiency photoreaction can be realized in a polymer film containing a polyimide precursor, and a highly efficient liquid crystal alignment film can be produced.
- a liquid crystal display element having a liquid crystal alignment film using the above-mentioned poimide obtained from a novel diamine has a reduced change in the liquid crystal alignment performance due to AC driving, and the liquid crystal alignment performance hardly changes, and an afterimage Is unlikely to occur.
- the method for producing a liquid crystal alignment film of the present invention uses a method in which a polymer film containing a polyimide precursor is used and alignment treatment is performed by polarized light irradiation.
- a polyamic acid ester derivative film having a photoreactive group is formed on a substrate, and then heated, and the film surface is irradiated with polarized ultraviolet rays while maintaining the heated state, whereby a polyamic acid is formed on the substrate.
- a liquid crystal alignment film made of an ester derivative is formed.
- the polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention includes a repeating unit represented by the following formula [2] and a repeating unit represented by the following formula [1] together with the repeating unit represented by the following formula [1]. It contains at least one selected from repeating units represented.
- the repeating unit represented by the following formula [2] and formula [3] has a photoreactive group.
- R 1 is a divalent organic group.
- R 2 represents a tetravalent organic group.
- R 3 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
- R 4 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
- n 1 represents a positive integer.
- the repeating unit represented by the formula [1] includes a diamine component represented by the following formula [1-A] and a tetracarboxylic acid dihydride which is an anhydride of the tetracarboxylic acid represented by the following formula [1-B]. It can be obtained using an anhydride component.
- R 1 and R 2 are the same as R 1 and R 2 in the formula [1].
- diamine component represented by the above formula [1-A] examples include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, and 2,5-dimethyl-p-phenylenediamine.
- diamine component represented by the above formula [1-A] examples include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, or from these And the like having a macrocyclic substituent.
- diamine compounds represented by the following formulas [DA1] to [DA30] can be exemplified.
- a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or NH—.
- 3 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
- p represents an integer of 1 to 10.
- a 4 represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
- a 5 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
- a 6 represents 1 carbon atom.
- a 7 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2.
- a 8 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 9 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 —, —CH 2 —, —O—, or —NH—
- a 10 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.
- a 11 represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- a 12 represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- tetracarboxylic acid represented by the above formula [1-B] include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 2,3 , 4,5-tetrahydrofurantetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 3,4-dicarboxy-1,2,3,4 And alicyclic tetracarboxylic acids such as tetrahydro-1-naphthalene succinic acid.
- tetracarboxylic acids include 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-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluor
- the polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention is represented by the repeating unit represented by the following formula [2] and the repeating unit represented by the following formula [2] together with the repeating unit represented by the above formula [1]. Containing at least one selected from repeating units.
- the repeating unit represented by the following formula [2] and formula [3] has a photoreactive group. Therefore, the polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention has a photoreactive group.
- the photoreactive group is preferably a group that causes a crosslinking reaction upon irradiation with light.
- the polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention also contains at least one selected from repeating units represented by the following formula [2] and formula [3].
- R 5 represents a divalent organic group constituting a photoreactive group.
- R 6 represents a tetravalent organic group.
- R 7 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
- R 8 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
- n 2 represents a positive integer.
- R 9 represents a divalent organic group.
- R 10 represents a divalent organic group constituting a photoreactive group.
- n 3 represents a positive integer.
- the repeating unit represented by the above formula [2] includes a diamine component represented by the following formula [2-A] and a tetracarboxylic acid dihydrate which is an anhydride of the tetracarboxylic acid represented by the following formula [2-B]. It can be obtained using an anhydride component.
- R 5 and R 6 are the same as R 5 and R 6 in the formula [2].
- a photocrosslinkable diamine can be used as the diamine component represented by the above formula [2-A]. Specific examples thereof include the following compounds.
- Examples of the tetracarboxylic acid represented by the above formula [2-B] include the same tetracarboxylic acids as those described above for the tetracarboxylic acid represented by the formula [1-B].
- the repeating unit represented by the above formula [3] can be obtained using a diamine component represented by the following formula [3-A] and a dicarboxylic acid component represented by the following formula [3-B].
- R 9 and R 10 are the same as R 9 and R 10 in the formula [3].
- Examples of the diamine component represented by the above formula [3-A] include the same diamine components as those described above for the diamine component represented by the above formula [1-A].
- dicarboxylic acid component represented by the above formula [3-B] include the compounds shown below.
- the ratio of the content of the repeating unit represented by is as follows. When only the repeating unit represented by the above formula [2] is included, in terms of molar ratio, (the repeating unit represented by the formula [1]) / (the repeating unit represented by the formula [2]) is The range of 1/99 to 99/1 is preferable, and the range of 5/95 to 95/5 is more preferable.
- repeating unit represented by the above formula [3] in terms of molar ratio, (the repeating unit represented by the formula [1]) / (the repeating unit represented by the formula [3] ) Is preferably in the range of 1/99 to 99/1, more preferably in the range of 5/95 to 95/5.
- the repeating unit represented by the formula [1] in terms of molar ratio ) / ⁇ (Repeating unit represented by Formula [2]) + (Repeating unit represented by Formula [3]) ⁇ is preferably in the range of 1/99 to 99/1, and 5/95 to 95/5. The range which becomes is more preferable.
- the polyimide precursor having the photoreactive group is a polyimide precursor obtained by polycondensation reaction of a diamine component containing a novel diamine represented by the following formula (4) and tetracarboxylic dianhydride.
- a diamine component containing a novel diamine represented by the following formula (4) and tetracarboxylic dianhydride can be the body.
- X 1 , X 2 , X 3 , X 4 , and X 5 are as defined above. In formula (4), it has one or more cinnamoyl groups.
- the cinnamoyl group is represented by the following formula, and the diamine represented by formula (4) has at least one, preferably 2 to 4 cinnamoyl groups.
- the position of the amino group (—NH 2 ) of the benzene ring is not particularly limited. However, from the viewpoint of liquid crystal alignment performance and ease of synthesis, for example, —X 1 —X 2 — It is preferably present in the para position or the meta position with respect to X 3 -X 4 -X 5- .
- Preferred diamines represented by the formula (4) include the following diamines.
- X independently represents a single bond, a bonding group of ether (—O—), ester (—COO— or —OCO—) or amide (—CONH— or —NHCO—)
- Y represents independently Each represents a single bond or an alkylene group having 1 to 5 carbon atoms
- Z independently represents an alkylene group having 1 to 10 carbon atoms or a phenylene group, and in each formula, the bonding position of an amino group on the benzene ring, (The position of the linking group with respect to the central benzene ring is not particularly limited.)
- diamine represented by the formula (4) include the following diamines.
- the liquid crystal alignment film formed using the liquid crystal aligning agent containing polyimide precursors, such as polyamic acid and polyamic acid ester which use the diamine of this invention represented by the said Formula (4) as a raw material, polyimide, polyamide, etc. is , Changes in the liquid crystal alignment performance due to AC (alternating current) drive, for example, changes in the alignment orientation of the liquid crystal are reduced. Therefore, the liquid crystal display element having this liquid crystal alignment film has the effect that the liquid crystal alignment performance of the liquid crystal alignment film by AC driving is stable, so that an afterimage is hardly generated by AC driving and the afterimage characteristics by AC driving are very good. Play.
- the liquid crystal alignment film formed using the diamine represented by the above formula (4) has excellent liquid crystal alignment performance and can be substantially free of alignment defects.
- the liquid crystal alignment film obtained by using the diamine represented by the above formula (4) and the liquid crystal display element having the liquid crystal alignment film reduce the change in the liquid crystal alignment performance due to AC driving, and the AC driving.
- the reason why the afterimage is difficult to occur is not necessarily clear, but is estimated as follows.
- a specific photoreactive group derived from a diamine represented by the formula (4) capable of imparting orientation to a liquid crystal on a main chain of a polyimide precursor, polyimide, polyimide or the like that is, —HN—C 6 H).
- the method for synthesizing the diamine represented by the formula (4) is not particularly limited, and can be produced, for example, according to the synthesis examples described later. Any diamine represented by the above formula (a) can be synthesized by the following method.
- the diamine represented by the formula (a) can be obtained by synthesizing a corresponding dinitro compound represented by the following formula (a ′), and further reducing the nitro group in a solvent to convert it to an amino group.
- the method for reducing the dinitro compound is not particularly limited, and palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide and the like are usually used as a catalyst. From the viewpoint of selectively reducing only the nitro group with high yield while leaving the olefin unreduced, it is effective to use a chemical reduction method using iron or tin chloride.
- the reduction is performed by a reaction using a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, or alcohol as a solvent, and using hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, or the like as a reducing agent.
- a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, or alcohol
- hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, or the like as a reducing agent.
- the synthesis method of the dinitro compound represented by the formula (a ′) is not particularly limited, and can be synthesized by any method. As a specific example, for example, it can be synthesized by the method shown in the following reaction formula.
- the nitrobenzene compound A and the compound B having a carboxylic acid can be reacted with each other in a direct condensation method using, for example, DMAP / DCC or DMAP / EDC in an organic solvent, and the carboxylic acid is thionyl chloride, chloride.
- the carboxylic acid is thionyl chloride, chloride.
- DMAP is 4-N, N-dimethylaminopyridine
- DCC is dicyclohexylcarbodiimide
- EDC is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
- X and Y have the same meanings as X and Y in the formula (a), respectively.
- Specific examples include 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, 4-nitrobenzyl alcohol, Examples include 3-nitrobenzyl alcohol, 2-nitrobenzyl alcohol, 4-nitrophenethyl alcohol, 3-nitrophenethyl alcohol, 2-nitrophenethyl alcohol and the like.
- a linking group Y may be inserted between the benzene ring and the hydroxyl group as necessary. Further, other substituents may be bonded on the benzene ring, and the substitution position of the nitro group on the benzene ring is appropriately selected from those at which the target diamine is obtained.
- the compound shown here is an example and is not specifically limited.
- organic solvent examples include solvents that do not affect the reaction, specifically, aromatic solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and heptane; halogens such as dichloromethane and 1,2-dichloroethane.
- these usage-amounts are arbitrary.
- diamines can also be synthesized by using the same technique as the diamine represented by the above formula (a).
- the polyimide precursors such as polyamic acid and polyamic acid ester of the present invention are obtained by reacting a diamine component containing a diamine represented by the above formula (4) with a tetracarboxylic acid component.
- polyamic acid ester is obtained also by the method of converting the carboxyl group of polyamic acid into ester.
- the polyimide of this invention is obtained by imidating polyimide precursors, such as these polyamic acids and polyamic acid ester.
- the polyamide of this invention makes the diamine component and the dicarboxylic acid halide containing the diamine represented by the said Formula (4) react in base presence, or the diamine containing the diamine represented by the said Formula (1).
- any of polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, and polyamide are useful as a polymer for obtaining a liquid crystal alignment film.
- 1 type or 2 or more types may be sufficient as the diamine represented by Formula (4) contained in a diamine component, and a diamine component is 1 type of other diamines other than the diamine represented by Formula (4). Or two or more types may be included.
- the content of the diamine represented by the formula (4) is 10 mol% or more, preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on the total amount of the diamine component. In the present specification, unless otherwise specified, the ratio is based on the number of moles.
- Examples of other diamines other than the diamine represented by the above formula (4) that may be contained in the diamine component include the diamines listed as specific examples of the diamine component represented by the above formula [1-A]. Can be used.
- the above-mentioned other diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.
- the tetracarboxylic acid component is at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives.
- the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester.
- a polyamic acid can be obtained by reacting a diamine component with a tetracarboxylic acid dihalide, tetracarboxylic dianhydride, or the like.
- a polyamic acid ester can be obtained by reacting a tetracarboxylic acid diester dichloride with a diamine component or reacting a tetracarboxylic acid diester with a diamine component in the presence of an appropriate condensing agent or base.
- the tetracarboxylic acid component to be used may be one type or two or more types.
- tetracarboxylic acid component examples include a tetracarboxylic dianhydride represented by the following formula (5).
- Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and containing a non-aromatic cyclic hydrocarbon group having 4 to 8 carbon atoms.
- Z 1 examples include tetravalent organic groups represented by the following formulas (5a) to (5j).
- Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
- Z 6 and Z 7 Represents a hydrogen atom or a methyl group, which may be the same or different.
- a particularly preferable structure of Z 1 is the formula (5a), the formula (5c), the formula (5d), the formula (5e), the formula (5f), or the formula (5g) from the viewpoint of polymerization reactivity and ease of synthesis.
- a formula (5a), a formula (5e), a formula (5f), or a formula (5g) is preferred.
- the ratio of the tetracarboxylic dianhydride shown by Formula (5) with respect to the tetracarboxylic acid component whole quantity is not specifically limited,
- the tetracarboxylic dianhydride whose tetracarboxylic acid component is shown by the said Formula (5) is mentioned. It may be only.
- the tetracarboxylic acid component may contain a tetracarboxylic acid or a tetracarboxylic acid derivative other than the tetracarboxylic dianhydride represented by the formula (5) as long as the effects of the present invention are not impaired.
- 1 mol% or more of the total amount of the tetracarboxylic acid component is the tetracarboxylic dianhydride represented by the above formula (5), more preferably 5 mol% or more, and still more preferably 10 mol%. That's it.
- Examples of other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the above formula (5) include the tetracarboxylic acids exemplified as other examples of the tetracarboxylic acid represented by the above formula [1-B]. Carboxylic dianhydrides can be used as well.
- Tetracarboxylic acid diesters are not particularly limited. Specific examples are given below. Specific examples of the aliphatic tetracarboxylic acid diester 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,
- 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
- the dicarboxylic acid to be reacted with the diamine component to obtain the polyamide of the present invention is not particularly limited.
- Specific examples of the dicarboxylic acid or its derivative aliphatic dicarboxylic acid to be reacted with a diamine component to obtain a polyamide include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2 -Methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid and the like.
- 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 acid,
- 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 have an acid dihalide or anhydride structure.
- dicarboxylic acids are preferably dicarboxylic acids that can give a polyamide having a linear structure, from the viewpoint of maintaining 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 "-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid, these acid dihal
- tetracarboxylic dianhydride represented by the above formula (5) other tetracarboxylic acids and their tetracarboxylic acid derivatives, dicarboxylic acids, etc. are liquid crystal alignment properties, voltage holding ratios, accumulated charges, etc. when used as liquid crystal alignment films. Depending on the desired characteristics, one kind or a mixture of two or more kinds may be used.
- the reaction between the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent.
- the organic solvent used at that time is not particularly limited as long as the generated polyimide precursor such as polyamic acid dissolves. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, 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, ethy
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
- a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. Any of these methods may be used.
- the polymerization temperature can be selected from -20 to 150 ° C., but is preferably in the range of ⁇ 5 to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polyimide precursor (and thus polyimide), and if the concentration is too high, the viscosity of the reaction solution becomes too high. Uniform stirring becomes difficult.
- the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor formed increases as the molar ratio approaches 1.0.
- 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. It can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxyl group of the polyamic acid using a polymer reaction.
- a polyamic acid ester can be synthesized by reacting for a period of time.
- 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 condensing agent includes triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluro Nium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzo Oxazolyl) phosphonic acid diphenyl, 4- (4,6-dimeth
- 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, but N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferred from the viewpoint of the solubility of the monomer and polymer. You may use these 1 type or in mixture of 2 or more types.
- 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 external air from being mixed, for example, by reacting in a nitrogen atmosphere.
- the polyimide precursor thus polymerized is, for example, a polymer having a repeating unit represented by the following formula [h].
- R 11 is a tetravalent organic group derived from the starting tetracarboxylic acid component
- R 12 is a divalent organic group derived from the starting diamine component
- a 11 and A 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different
- j represents a positive integer.
- R 11 and R 12 may each be one type and a polymer having the same repeating unit, or R 11 and R 12 may be a plurality of types and a polymer having a repeating unit having a different structure. Good.
- R 11 is a group derived from a tetracarboxylic acid component represented by the following formula [k] or the like that is a raw material.
- R 12 is a group derived from a diamine component represented by the following formula [s], which is a raw material.
- R 12 is a group derived from a diamine represented by the above formula (4), —C 6 H 4 —X 1 —X 2 —X 3 —X 4 —X 5 —C 6 H 4 —.
- the main chain is —HN—C 6 H 4 —X 1 —X 2 —X 3 —X 4 —X by using the diamine represented by the above formula (4) as a raw material.
- This is a polyimide precursor having 5- C 6 H 4 —NH— introduced therein.
- a polyimide is obtained by dehydrating and ring-closing a polyimide precursor represented by the formula [h].
- Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
- the temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and is preferably performed while removing water generated by the imidization reaction from the system.
- the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor 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. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Of these, use of acetic anhydride is preferred 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.
- reaction solutions such as polyimide precursors, such as a polyamic acid and polyamic acid ester, and a polyimide.
- polyimide precursors such as a polyamic acid and polyamic acid ester, and a polyimide.
- the solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
- the polyimide precursor or polyimide deposited by precipitation in a solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- the polyimide precursor and polyimide recovered by precipitation are redissolved in an organic solvent, and reprecipitation and recovery are repeated 2 to 10 times, whereby impurities in the polyimide precursor and polyimide can be reduced.
- the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
- the dehydration cyclization rate (imidation rate) of the amic acid group of the polyimide is not necessarily 100%, and can be arbitrarily selected in the range of 0 to 100% depending on the application and purpose, but 50 to 100% preferable.
- Polyamide can be synthesized in the same manner as polyamic acid ester.
- the molecular weight of the polyimide precursor, polyimide, polyamide, etc. of the present invention is determined by GPC (in terms of the strength of the resulting polymer film (liquid crystal alignment film), workability during formation of the polymer film, and uniformity of the polymer film.
- the weight average molecular weight measured by Gel Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
- a thin film containing the above polyimide precursor is formed on a substrate, then heated, and further irradiated with polarized ultraviolet rays while maintaining the heated state. . Then, the liquid crystal alignment film containing the polyimide precursor is formed on the substrate by inducing a photocrosslinking reaction with high reaction efficiency by the polarized ultraviolet irradiation and introducing anisotropy into the thin film containing the polyimide precursor.
- polyimide is not contained in the thin film containing the polyimide precursor. Even if the polyimide is inevitably contained in the thin film containing the polyimide precursor, the content thereof is preferably 30 mol% or less, more preferably 20 mol% or less with respect to the polyimide precursor. 10 mol% or less is more preferable.
- Polyimide is a relatively rigid polymer material, and when it is contained in a large amount in a thin film, the flexibility of the film containing the polyimide precursor is impaired. Moreover, the effect of using heat treatment at the time of polarized light irradiation is impaired, and there is a possibility that the progress of the photoreaction in the film containing the polyimide precursor may be hindered. As a result, there is a concern that the introduction of anisotropy into the film containing the polyimide precursor by photoreaction may be hindered.
- the heating temperature of the thin film containing the polyimide precursor formed on the substrate is a temperature in a range that realizes high photoreaction efficiency of the thin film, and a temperature that does not cause a chemical reaction of the polyimide precursor. It is preferable to do. That is, as the upper limit of the heating temperature, it is preferable to select a temperature within a range in which a thermal reaction occurs and does not change to polyimide, depending on the type of polyimide precursor used. About a minimum, it is preferable to select the temperature which can express the photoreactive improvement effect mentioned later by the kind of polyimide precursor to be used.
- the heating temperature of the thin film containing the polyimide precursor formed on the substrate is 50 to 300 ° C., preferably 80 to 250 ° C., more preferably 150 to 200 ° C. .
- the heating of the thin film containing the polyimide precursor on the substrate and the maintenance of the heating state can be performed using, for example, a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like. Among these, it is preferable to select and use a hot plate that can be easily irradiated with ultraviolet rays.
- the substrate When irradiating polarized ultraviolet rays to the film surface of the thin film containing the polyimide precursor, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
- the wavelength of ultraviolet rays to be used ultraviolet rays in the range of 100 to 400 nm can be used.
- the optimum wavelength is selected through a filter or the like depending on the type of polyimide precursor to be used.
- ultraviolet rays in the range of 300 to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
- the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
- the photoreaction in a thin film containing the polyimide precursor to be used can be advanced with very high efficiency.
- the photoreaction in the thin film containing the polyimide precursor constituting the liquid crystal alignment film can be advanced with an ultraviolet irradiation amount of about 1/10 compared with the conventional photoalignment method, and the efficiency of the photoreaction is increased. It can be increased about 10 times.
- the present invention in the alignment treatment performed by irradiating light, it is possible to make the amount of ultraviolet irradiation much smaller than that of the conventional photo-alignment method. That is, in the present invention, a liquid crystal alignment film having the ability to control the alignment of liquid crystals is produced with a much smaller amount of UV irradiation than the number J to several tens J required in the conventional photo-alignment method. Is possible. Specifically, the liquid crystal alignment film can be produced with an ultraviolet irradiation amount in the range of 10 to 1000 mJ, preferably 20 to 800 mJ.
- a liquid crystal alignment film can be produced by irradiating ultraviolet rays having an intensity of 10 to 20 mW for several seconds to several tens of seconds, and the production throughput (processing ability) of the liquid crystal alignment film can be improved.
- a thin film containing a polyimide precursor is heated and irradiated with polarized ultraviolet rays while maintaining the heating state, so that high efficiency can be achieved with a small amount of ultraviolet irradiation.
- a liquid crystal alignment film can be manufactured. That is, the present invention can produce a liquid crystal alignment film with high production efficiency.
- a liquid crystal display element can be manufactured using the obtained liquid crystal aligning film using the manufacturing method of the liquid crystal aligning film of this invention. Next, a liquid crystal display element using the liquid crystal alignment film of the present invention will be described.
- the liquid-crystal aligning agent of this invention contains polyimide precursors, such as the said polyamic acid and polyamic acid ester, a polyimide, polyamide, etc.
- the liquid crystal alignment treatment agent is a solution for forming a liquid crystal alignment film, and is a solution in which a polymer component for forming a liquid crystal alignment 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, polyimide and polyamide.
- the polyimide precursor of the present invention is dissolved in a solvent, constitutes a liquid crystal alignment treatment agent, and can be used for forming a thin film containing the polyimide precursor. Can be used.
- the content of the polyimide precursor in the liquid crystal aligning agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 25% by mass. .
- all of the polymer components contained may be polyimide precursors such as the polyamic acid and polyamic acid ester of the present invention, polyimides, polyamides, etc.
- Other polymers may be mixed in polymer components such as polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, and polyamide.
- the content of the other polymer in the total amount of the polymer component is 0.5 to 50% by mass, preferably 1 to 30% by mass.
- the other polymer can be obtained, for example, using only a diamine other than the diamine represented by the above formula (4) of the present invention as a diamine component to be reacted with a tetracarboxylic dianhydride component, a dicarboxylic acid or the like.
- a diamine other than the diamine represented by the above formula (4) of the present invention as a diamine component to be reacted with a tetracarboxylic dianhydride component, a dicarboxylic acid or the like.
- examples thereof include a polyimide precursor, polyimide, and polyamide.
- polymers other than a polyimide precursor, polyimide, and polyamide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, and the like are also included.
- the polyamic acid of the present invention at least one selected from polyimide precursors such as polyamic acid esters, polyimides and polyamides, and other polymers mixed as necessary are totaled.
- the content is 0.1 to 30% by mass, preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass in the total amount of the polymer components.
- the organic 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 polymer components such as the polyimide precursor, polyimide, and polyamide of the present invention.
- 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,
- the liquid-crystal aligning agent of this invention is an organic solvent (it is also called a poor solvent) which improves the uniformity of the film thickness of a polymer film at the time of apply
- poor solvents that improve film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl 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-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoa Tate, Diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monomethyl ether, Dipropylene glycol mono
- These poor solvents may be used alone or in combination.
- the above poor solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the whole organic solvent contained in the liquid crystal alignment treatment 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 (manufactured by Asahi Glass Co., Ltd.).
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. is there.
- Examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.
- the amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts 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 dielectric or conductive material is used for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film.
- a substance, and further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
- the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by applying and baking on a substrate and then performing alignment treatment by rubbing treatment or light irradiation (radiation irradiation) as necessary.
- a liquid crystal alignment film of the present invention is formed of a polyimide precursor, polyimide, polyamide, or the like using the diamine represented by the above formula (4) as a raw material, so that the liquid crystal alignment performance by AC driving is hardly changed.
- the substrate is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving a liquid crystal is formed.
- an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
- a high-performance element such as a TFT type liquid crystal display 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 method are common. As other coating methods, there are a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, etc., and these may be used according to the purpose.
- the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven, an IR (infrared) oven, etc. It can be set as an alignment film (polymer thin film). If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
- the liquid crystal When the liquid crystal is horizontally or tilted, the liquid crystal can be aligned by treating the fired liquid crystal alignment film with rubbing, irradiation with polarized ultraviolet rays, or the like.
- irradiating light such as polarized ultraviolet rays
- the photoreactive group derived from diamine represented by the formula (4) undergoes a dimerization reaction, and the liquid crystal can be aligned with the anisotropy generated thereby.
- the irradiation with polarized ultraviolet light may be performed while heating the liquid crystal alignment film.
- the thin film containing the polyimide precursor formed on the substrate is heated at 80 to 250 ° C. using, for example, a hot plate.
- a temperature in a range in which a thermal reaction occurs and does not change to polyimide is selected depending on the type of polyimide precursor to be used.
- the temperature which expresses the improvement effect of photoreactivity is selected by the kind of polyimide precursor to be used.
- the light irradiation conditions are selected as described above, and the film surface of the thin film containing the polyimide precursor is polarized through a polarizing plate from a certain direction. Irradiate with ultraviolet light.
- a liquid crystal alignment film having a liquid crystal alignment control ability can be produced on the substrate.
- the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method. For example, two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal alignment treatment 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 the liquid crystal alignment film.
- liquid crystal display element of the present invention horizontal alignment (IPS: In-Plane Switching) method, twisted nematic (TN) method, OCB alignment (OCB: Optically Compensated Bend), vertical alignment (VA: Vertical (Alignment) method etc. are mentioned. Note that the liquid crystal alignment film only needs to be provided on at least one of the two substrates.
- 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.
- the liquid crystal alignment film is formed by applying the liquid crystal alignment treatment agent of the present invention on this substrate and then firing, and irradiating with radiation such as rubbing treatment or polarized ultraviolet rays as necessary. Is 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 positive liquid crystal having a positive dielectric anisotropy, a negative liquid crystal having a negative dielectric anisotropy, or the like can be used.
- a liquid crystal material used in a conventional horizontal alignment method for example, MLC-2041 manufactured by Merck Ltd. can be used.
- a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded together, the liquid crystal is injected under reduced pressure and sealed, 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. It can be illustrated.
- the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m. Further, in the case of a horizontal alignment type liquid crystal display element, after the liquid crystal is sealed in this way, a polarizing plate is disposed outside the substrate.
- the liquid crystal display device produced using the liquid crystal alignment treatment agent of the present invention has a liquid crystal alignment film in which the change in the liquid crystal alignment performance due to AC driving is suppressed, and thus has excellent afterimage characteristics, Image sticking is less likely to occur, and display defects and contrast are less likely to occur.
- Monomer (1) (20 g, 0.09 mol) was added to dry ethanol (60 ml), and the mixture was stirred and refluxed until all the solid was dissolved, and then stirred and refluxed for another 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure until a solid was slightly precipitated. The reaction solution of about 50% (volume) of dry ethanol was cooled at room temperature, and the precipitate was separated by filtration and then washed with ethanol to obtain the desired monomer (2). Further, the solvent of the filtrate was distilled off under reduced pressure to obtain a mixture of target isomers. The monomer (2) was obtained by recrystallizing the mixture of isomers with ethyl acetate. The yield was 10 g, and the yield was 35.2%.
- 1 H-NMR of the obtained monomer (2) is an NMR measurement apparatus in a solvent of deuterated dimethyl sulfoxide (abbreviated as DMSO) using TMS (Si (CH 3 ) 4 ) as a reference substance. (JEOL, 500 MHz).
- DMSO deuterated dimethyl sulfoxide
- JEOL 500 MHz
- the 1 H-NMR measurement results of the monomer (2) are shown below, but the same applies to other compounds.
- N, N′-dimethylformamide was added to a mixture of 4.77 g (0.015 mol) of monomer (2) and 35 ml of ethyl acetate.
- 3 ml of thionyl chloride was added and stirred to reflux. After confirming that all solids were dissolved, the mixture was further stirred and refluxed for 1 hour. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure.
- the product was purified by recrystallization from hexane to obtain purified monomer (3). The yield was 4.3 g, and the yield was 80.5%.
- the solvent for 1 H-NMR was deuterated chloroform (CDCl 3 ).
- N, N′-dimethylformamide was added to a mixture of 4.8 g (0.022 mol) of monomer (4) and 50 ml of ethyl acetate.
- 6 ml of thionyl chloride was added and stirred and refluxed. After confirming that all solids were dissolved, the mixture was further stirred and refluxed for 1 hour. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure.
- the product was purified by recrystallization from an ethyl acetate / hexane system to obtain a purified monomer (5).
- the yield was 3.5 g, and the yield was 62.4%.
- the reaction solution was poured into 800 ml of water, and the produced polymer was separated, followed by filtration and separation, and washing with ethanol and acetone. Next, the polymer was dried and then dissolved in NMP and purified by reprecipitation with ethanol and chloroform. Thereafter, the precipitate was separated by filtration and sufficiently dried to obtain a polyamic acid ester derivative (6FPAE2-8) powder (A) having an Mn of 31,400 and an Mw of 66,000.
- 6FPAE2-8) powder (A) having an Mn of 31,400 and an Mw of 66,000.
- the reaction solution was poured into 800 ml of water, and the produced polymer was separated, followed by filtration and separation, and washing with ethanol and acetone. Next, the polymer was dried and then dissolved in NMP and purified by reprecipitation with ethanol and chloroform. Thereafter, the precipitate was separated by filtration and sufficiently dried to obtain a polyamic acid ester derivative (6FPAE5-5) powder (B) having an Mn of 28,600 and an Mw of 52,800.
- 6FPAE5-5-5 powder (B) having an Mn of 28,600 and an Mw of 52,800.
- Example 1 NMP and BCS were added to the polyamic acid ester derivative (6FPAE2-8) powder (A) obtained in Synthesis Example 3 and diluted to 4% by mass to obtain a liquid crystal aligning agent (I). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
- Example 3 Using the liquid crystal aligning agent (I) containing the polyamic acid ester derivative (6FPAE2-8) obtained in Example 1, spin coating was performed on a transparent glass substrate (thickness 1.1 mm, width 30 mm, length 40 mm). Then, after drying for 5 minutes on a hot plate at 80 ° C., a coating film with a film thickness of 40 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
- Example 4 The liquid crystal alignment treatment agent (II) containing the polyamic acid ester derivative (6FPAE5-5) obtained in Example 2 was spin-coated on a transparent glass substrate and dried on a hot plate at 80 ° C. for 5 minutes. After that, a coating film having a thickness of 40 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
- the liquid crystal alignment treatment agent (II) containing the polyamic acid ester derivative (6FPAE5-5) obtained in Example 2 was spin-coated on a transparent glass substrate and dried on a hot plate at 80 ° C. for 5 minutes. After that, a coating film having a thickness of 40 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
- Example 5 The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used, heated to 240 ° C. on a hot plate, and kept constant with respect to the liquid crystal alignment film surface on the substrate while maintaining the heating state.
- Were irradiated with ultraviolet rays high pressure mercury lamp manufactured by Ushio Electric Co., Ltd., polarized light irradiation device manufactured by Mejiro Precision Co., Ltd.
- the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 500 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
- ⁇ Comparative example 2> Using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3, and maintaining this at room temperature, the ultraviolet light polarized through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate was irradiated.
- the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 4500 mJ.
- a substrate with a liquid crystal alignment film on which a liquid crystal alignment film was formed was obtained.
- Example 6 Using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 4, this was heated to 160 ° C. on a hot plate, and the liquid crystal alignment film surface on the substrate was kept constant while maintaining the heated state.
- the polarized ultraviolet rays were irradiated from the direction through the polarizing plate.
- the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 250 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
- Example 7 A substrate with a liquid crystal alignment film subjected to alignment treatment according to the same method as in Example 6 was obtained except that the heating temperature on the hot plate was 200 ° C.
- Example 8> A substrate with a liquid crystal alignment film that had been subjected to alignment treatment according to the same method as in Example 6 was obtained except that the heating temperature on the hot plate was 240 ° C.
- Table 1 summarizes the conditions for producing the substrates with the liquid crystal alignment films obtained in Examples 3 to 8, Comparative Example 1 and Comparative Example 2.
- Liquid crystal aligning agent A5 (described in [Example B] described later) was spin-coated on a quartz substrate (thickness 1.1 mm, width 40 mm, length 40 mm). Subsequently, after drying for 60 seconds with a 90 degreeC hotplate, it baked for 30 minutes with a 200 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the substrate was heated to 240 ° C.
- Example 3 In the same manner as in Example 9, a liquid crystal alignment film was formed, and the liquid crystal alignment film surface of the substrate was irradiated with 1000 mJ / cm 2 of ultraviolet light at 313 nm through a polarizing plate at room temperature (23 ° C.) to form a substrate with a liquid crystal alignment film. Obtained.
- FIG. 1 is an ultraviolet absorption spectrum of the liquid crystal alignment film before alignment treatment obtained in Example 3 and the liquid crystal alignment film obtained in Example 5.
- FIG. 1 shows an ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 5, and as an object for comparison, shows an ultraviolet absorption spectrum of the liquid crystal alignment film of Example 3 that has not been heated or irradiated with polarized ultraviolet light.
- the ultraviolet absorption spectrum of the liquid crystal alignment film of Example 5 (described as “Example 5” in FIG. 1) and the ultraviolet absorption spectrum of the liquid crystal alignment film of Example 3 (in FIG. In comparison with Example 3 ”, it can be seen that the absorbance in the vicinity of a wavelength of 350 nm is greatly reduced in the liquid crystal alignment film of Example 5. This decrease in absorbance is considered to be due to heating at 240 ° C.
- the absorption in the vicinity of the wavelength of 300 to 350 nm of the liquid crystal alignment film of Example 3 is understood as absorption derived from the photoreactive group contained in the polyamic acid ester derivative constituting the liquid crystal alignment film, and is heated at 240 ° C. on a hot plate. It can be seen that the photo-crosslinking reaction proceeded efficiently in the polyamic acid ester derivative film by the irradiation treatment with 500 mJ polarized ultraviolet light.
- the ultraviolet absorption spectrum of each liquid crystal alignment film was measured using the substrate with a liquid crystal alignment film on which the liquid crystal alignment film of Comparative Example 1 was formed and the substrate with the liquid crystal alignment film on which the liquid crystal alignment film of Comparative Example 2 was formed. did.
- the ultraviolet absorption spectrum of the liquid crystal alignment film before alignment treatment was measured and used as a comparison object.
- FIG. 2 is an ultraviolet absorption spectrum of the liquid crystal alignment film before alignment treatment obtained in Example 3 and the liquid crystal alignment film obtained in Comparative Examples 1 and 2.
- FIG. 2 the ultraviolet absorption spectrum of the liquid crystal aligning film of the comparative example 1 and the liquid crystal aligning film of the comparative example 2 is shown,
- the ultraviolet absorption spectrum of the liquid crystal aligning film of Example 3 which is not heated and polarized ultraviolet irradiation is made.
- the ultraviolet absorption spectrum of the liquid crystal alignment film of Example 3 (described as “Example 3” in FIG. 2) and the ultraviolet absorption spectrum of the liquid crystal alignment film of Comparative Example 1 (in FIG. Comparing Comparative Example 1 ”), it can be seen that the absorbance in the vicinity of the wavelength of 300 to 350 nm is decreased in the liquid crystal alignment film of Comparative Example 1.
- the liquid crystal alignment film of Comparative Example 2 when the ultraviolet absorption spectrum of the liquid crystal alignment film of Comparative Example 2 (referred to as “Comparative Example 2” in FIG. 2) is compared, the liquid crystal alignment film of Comparative Example 2 further has an absorbance around 300 to 350 nm. It turns out that it has fallen. From this, it can be seen that the absorbance of the liquid crystal alignment film near the wavelength of 300 to 350 nm decreases as the irradiation amount of polarized ultraviolet rays increases.
- Absorption in the vicinity of a wavelength of 300 to 350 nm is understood as absorption derived from a photoreactive group contained in the polyamic acid ester derivative constituting the liquid crystal alignment film, and photocrosslinking reaction occurs in the polyamic acid ester derivative film by irradiation with polarized ultraviolet rays. Can be seen.
- FIG. 1 and FIG. 2 are compared, the absorbance of the liquid crystal alignment film of Comparative Example 2 shown in FIG. 2 in the vicinity of the wavelength of 300 to 350 nm and the wavelength of the liquid crystal alignment film obtained in Example 5 of FIG. It can be seen that the absorbance around ⁇ 350 nm is equivalent.
- the irradiation amount of polarized ultraviolet rays in Example 5 is 500 mJ
- the irradiation amount of polarized ultraviolet rays in the liquid crystal alignment film of Comparative Example 2 is 4500 mJ. From this, it can be seen that the photoreaction progressed with very high efficiency in the liquid crystal alignment film of Example 5 in which heat treatment at 240 ° C. was used in combination with irradiation of polarized ultraviolet rays.
- FIG. 3 is an ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 9 of the present invention.
- Comparative Example 3 in which polarized ultraviolet rays were irradiated at room temperature and Comparative Example in which heating and polarized ultraviolet rays were not applied. 4 also shows the ultraviolet absorption spectrum of the liquid crystal alignment film of No. 4.
- the ultraviolet absorption spectrum of the liquid crystal alignment film of Example 9 (described as “Example 9” in FIG.
- the ultraviolet absorption spectrum of the liquid crystal alignment film was measured, and the absorbance at the absorption maximum near a wavelength of 350 nm was evaluated. It was 0.70.
- the degree of decrease in absorbance at the absorption maximum is slightly large.
- the degree of decrease in absorbance at the absorption maximum is It was equivalent.
- the heating temperature at the time of irradiation with polarized ultraviolet rays in the alignment treatment of the liquid crystal alignment film is particularly preferably 160 to 200 ° C., which can suppress the change of the polyamic acid ester derivative constituting the liquid crystal alignment film to polyimide. all right.
- Example 10 A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agent (I) obtained in Example 1, and a liquid crystal cell using the liquid crystal alignment film was manufactured.
- the liquid crystal cell was a parallel aligned liquid crystal cell corresponding to the characteristics of the liquid crystal alignment film.
- a liquid crystal display element can be constituted by sandwiching the obtained liquid crystal cell between a pair of polarizing plates.
- a liquid crystal alignment agent (I) is spin-coated on a glass substrate with an ITO electrode (length 30 mm ⁇ width 40 mm, thickness 1,1 mm) and dried on an 80 ° C. hot plate for 5 minutes. After that, a liquid crystal alignment film was formed as a 40 nm-thick coating film to obtain a substrate with a liquid crystal alignment film before the alignment treatment. It was found that all the liquid crystal alignment films formed on the substrate were excellent in film thickness uniformity, and the liquid crystal alignment treatment agent (I) exhibited excellent coating properties.
- the obtained substrate with a liquid crystal alignment film before the alignment treatment is heated to 240 ° C. on a hot plate and polarized from a certain direction with respect to the liquid crystal alignment film surface on the substrate while maintaining the heated state.
- the polarized ultraviolet light was irradiated through the plate.
- the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 250 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
- nematic liquid crystal ZLI-4792 manufactured by Merck & Co., Inc.
- ZLI-4792 manufactured by Merck & Co., Inc.
- Example 11 A liquid crystal cell was produced according to the same method as in Example 10 except that the irradiation amount of polarized ultraviolet rays was 500 mJ.
- Example 5 A liquid crystal cell was produced according to the same method as in Example 10 except that the irradiation amount of polarized ultraviolet rays was 50 mJ.
- Example 6 A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agent (I) obtained in Example 1, and a liquid crystal cell using the liquid crystal alignment film was manufactured.
- the liquid crystal cell was a parallel alignment liquid crystal cell as in Example 10.
- a liquid crystal alignment treatment agent (I) is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then a liquid crystal alignment film as a 40 nm-thick coating film. And a substrate with a liquid crystal alignment film before the alignment treatment was obtained.
- the obtained substrate with a liquid crystal alignment film before the alignment treatment was used, and while maintaining this at room temperature, the surface of the liquid crystal alignment film on the substrate was irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
- the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 50 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
- FIG. 4 is a diagram showing the liquid crystal cells of Examples 10 and 11 and Comparative Examples 5 to 8 in comparison with polarization micrographs.
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- p-PDA p-phenylenediamine
- NMP N-methyl-2-pyrrolidone
- BCS Butyl cellosolve
- APHFP Diamine [1] to [7]: Diamine [1] to [7] represented by the following formula
- ⁇ Measurement of molecular weight of polymer> The measurement conditions of the molecular weight of the polymer (polyamic acid or the like) are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
- terephthalaldehyde [A] (40.00 g, 298 mmol), pyridine (46 g), and piperidine (7.0 g) were added, and the reaction solution was heated to 100 ° C. with stirring.
- a pyridine solution 500 g
- malonic acid [B] 140.0 g, 1.34 mol
- HPLC high performance liquid chromatography
- Isophthalaldehyde [H] (50.00 g, 373 mol), pyridine (78 g), and piperidine (9.5 g) were added to a 2 L four-necked flask, and the reaction solution was heated to 100 ° C. with stirring. Then, a pyridine solution (600 g) of malonic acid [B] (169.5 g, 1.68 mol) was dropped into the reaction solution. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 40 ° C., and the reaction solution was poured into distilled water (1 L). Next, concentrated hydrochloric acid was added until the reaction solution became acidic, and then the solid was filtered.
- Liquid crystal aligning agent A1 NMP (5.0 g) was added to diamine [1] (1.20 g, 3.0 mmol), and the mixture was stirred and completely dissolved at room temperature, and then CBDA (0.53 g, 2.8 mmol) and NMP (5. 0 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A1. The number average molecular weight of this polyamic acid was 6000, and the weight average molecular weight was 10500.
- Liquid crystal aligning agent A2 NMP (5.4 g) was added to diamine [2] (1.37 g, 3.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.55 g, 2.8 mmol) and NMP (5. 4 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A2. The number average molecular weight of this polyamic acid was 3800, and the weight average molecular weight was 5000.
- Liquid crystal aligning agent A3 NMP (5.0 g) was added to diamine [3] (1.20 g, 3.0 mmol), and the mixture was stirred and completely dissolved at room temperature, and then CBDA (0.55 g, 2.8 mmol) and NMP (5. 0 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A3. The number average molecular weight of this polyamic acid was 8100, and the weight average molecular weight was 16000.
- Liquid crystal aligning agent A4 NMP (5.4 g) was added to diamine [4] (1.37 g, 3.0 mmol) and stirred at room temperature for complete dissolution, then CBDA (0.55 g, 2.8 mmol) and NMP (5. 4 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A4. The number average molecular weight of this polyamic acid was 5200, and the weight average molecular weight was 7600.
- NMP (32.3 g) was added to diamine [5] (7.06 g, 25.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (4.51 g, 23.0 mmol) and NMP (33. 2 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
- NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A5.
- the number average molecular weight of this polyamic acid was 10500, and the weight average molecular weight was 57000.
- NMP (Liquid crystal aligning agent A6) NMP (4.9 g) was added to diamine [6] (1.18 g, 3.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.53 g, 2.7 mmol) and NMP (4. 9 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A6. The number average molecular weight of this polyamic acid was 8800, and the weight average molecular weight was 35000.
- NMP (Liquid crystal aligning agent A7) NMP (5.6 g) was added to diamine [7] (1.14 g, 4.5 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.83 g, 4.2 mmol) and NMP (5.2. 6 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A7. The number average molecular weight of this polyamic acid was 13800, and the weight average molecular weight was 35500.
- NMP (27.0 g) was added to diamine [5] (3.53 g, 12.5 mmol) and p-PDA (1.35 g, 12.5 mmol), and the mixture was stirred at room temperature until completely dissolved, and then CBDA ( 4.66 g, 23.8 mmol) and NMP (27.0 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
- NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and the liquid crystal aligning agent A8 was obtained by stirring at room temperature for 5 hours.
- the number average molecular weight of this polyamic acid was 11500, and the weight average molecular weight was 25000.
- Liquid crystal aligning agent B1 NMP (22.0 g) was added to DA-1 (5.10 g, 14.0 mmol), and the mixture was stirred and completely dissolved at room temperature. Then, CBDA (2.66 g, 13.6 mmol) and NMP (22.0 g) were added. ) And reacted at room temperature for 5 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent B1. The number average molecular weight of this polyamic acid was 6500, and the weight average molecular weight was 26000.
- Example 1 Using the liquid crystal aligning agent A1, a liquid crystal cell was produced according to the procedure shown below.
- the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
- the pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m.
- the pixel electrode forming each pixel is configured by arranging a plurality of dog-shaped electrode elements whose central part is bent, so that the shape of each pixel is not rectangular, and is similar to the electrode element in the central part. It has a shape that bends and resembles a bold-faced koji.
- Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different.
- the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode are formed so as to form an angle of ⁇ 10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
- Liquid crystal aligning agent A1 was spin-coated on the prepared substrate with electrodes. Subsequently, after drying for 60 seconds with a 90 degreeC hotplate, it baked for 30 minutes with a 200 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the substrate was placed on a hot plate at 240 ° C., and the surface of the liquid crystal alignment film was irradiated with 313 nm ultraviolet rays at 20 mJ / cm 2 via a polarizing plate to obtain a substrate with a liquid crystal alignment film.
- a liquid crystal alignment film was formed using a liquid crystal alignment treatment agent A1 on a glass substrate having a columnar spacer with a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and subjected to alignment treatment. .
- a sealant (XN-1500T, manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was cured to produce an empty cell.
- Liquid crystal MLC-2041 manufactured by Merck & Co., Inc.
- IPS liquid crystal cell
- IPS Mode liquid crystal cell IPS Mode liquid crystal cell
- the IPS mode liquid crystal cell obtained above is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the light source is turned on with no voltage applied, and the transmitted light has the highest luminance.
- the arrangement angle of the liquid crystal cell was adjusted so as to be small.
- the rotation angle (alignment azimuth angle) when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial alignment azimuth.
- an AC voltage of 8 V PP was applied for 24 hours at a frequency of 30 Hz in a room temperature environment.
- Example 2 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A2 was used instead of the liquid crystal alignment treatment agent A1.
- Example 3 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A3 was used instead of the liquid crystal alignment treatment agent A1.
- Example 4 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A4 was used instead of the liquid crystal alignment treatment agent A1.
- Example 5 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A5 was used instead of the liquid crystal alignment treatment agent A1.
- Example 6 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A6 was used instead of the liquid crystal alignment treatment agent A1.
- Example 7 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A7 was used instead of the liquid crystal alignment treatment agent A1.
- Example 8 A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A8 was used instead of the liquid crystal alignment treatment agent A1.
- the diamine represented by the above formula (4) is used as a raw material in the main chain skeleton of the polyimide polymer in spite of the low temperature and short time measurement conditions of 24 hours at room temperature. It can be seen that in Examples 1 to 6 in which the photoreactive group is introduced, the difference in orientation azimuth before and after AC driving is small and the afterimage characteristics are remarkably improved as compared with Comparative Example 1. Also. In Examples 1 to 6, the liquid crystal orientation was also good. Furthermore, also in Example 7 which copolymerized other diamine, it turned out that a favorable liquid crystal aligning performance and AC image sticking characteristic are shown.
- liquid crystal aligning agent of the present invention by using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film excellent in liquid crystal alignment and afterimage characteristics can be obtained.
- a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in liquid crystal alignment and afterimage characteristics, so that a liquid crystal display device that is unlikely to cause display defects, contrast reduction, image sticking, etc. It can be.
- ⁇ Comparative Example 9> The liquid crystal alignment performance evaluation was performed by performing the same operation as in Example 1 except that the liquid crystal alignment treatment agent A1 was used and the surface of the liquid crystal alignment film was irradiated with 20 mJ / cm 2 of 313 nm ultraviolet light at room temperature via a polarizing plate. went.
- ⁇ Comparative Example 10> Liquid crystal alignment performance evaluation was performed by performing the same operation as Comparative Example 9 except that the liquid crystal alignment treatment agent A2 was used instead of the liquid crystal alignment treatment agent A1.
- ⁇ Comparative Example 11> Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A3 was used instead of the liquid crystal alignment treatment agent A1.
- the liquid crystal orientation is improved by irradiating polarized ultraviolet rays while performing the heat treatment at 240 ° C. This is considered to be derived from the fact that the photodimerization reaction of the cinnamoyl group is promoted by performing ultraviolet irradiation while performing the heat treatment.
- a liquid crystal alignment film that achieves high photoreaction efficiency and enables high-efficiency alignment treatment is obtained.
- the liquid crystal alignment film can be used efficiently and even for a long period of use. It is possible to provide a liquid crystal display element in which a defect such as a change in the alignment state of the liquid crystal hardly occurs.
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
現在、工業的に利用されている主な液晶配向膜は、ポリイミド前駆体(ポリアミック酸(ポリアミド酸)、ポリアミック酸エステル)、ポリイミド等の溶液からなるポリイミド系の液晶配向処理剤を、基板に塗布し成膜することで作製される。
また、基板面に対して液晶を水平配向、平行配向又は傾斜配向等させる場合は、成膜した後、ラビングによる表面延伸処理が行われている。そして、ラビング処理に代わるものとして、偏光紫外線照射等による異方性光化学反応を利用する方法が提案されており、近年では工業化に向けた検討が行われている。 That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. Further, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
Currently, the main liquid crystal alignment film used industrially is a polyimide liquid crystal alignment treatment agent made of a solution of polyimide precursor (polyamic acid (polyamic acid), polyamic acid ester), polyimide, etc., applied to the substrate. Then, it is manufactured by forming a film.
In addition, when the liquid crystal is horizontally aligned, parallel aligned, or inclinedly aligned with respect to the substrate surface, a surface stretching process by rubbing is performed after film formation. As an alternative to the rubbing treatment, a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like has been proposed, and in recent years, studies for industrialization have been performed.
光配向法には幾つかの方法があるが、一般的には直線偏光又はコリメート(平行化)した光によって液晶配向膜を構成する有機膜の表面に異方性を形成し、その異方性に従って液晶を配向させるものである。
主な具体的な光配向法としては、分解型の光配向法が知られている。分解型の光配向法とは、例えば、ポリイミド膜に偏光紫外線を照射し、分子構造の紫外線吸収の偏光方向依存性を利用して異方的な分解を生じさせ、分解せずに残されたポリイミドにより液晶を配向させる方法である(例えば、特許文献1参照。)。 As a method for aligning a liquid crystal alignment film in place of rubbing, a photo-alignment method has been actively studied. For example, a photo-alignment method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like has been proposed, and in recent years, studies for industrialization have been performed.
There are several photo-alignment methods, but in general, anisotropy is formed on the surface of the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated (parallelized) light. The liquid crystal is aligned according to the above.
As a main specific photo-alignment method, a decomposition type photo-alignment method is known. The decomposition type photo-alignment method means, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is caused by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. This is a method of aligning liquid crystal with polyimide (for example, see Patent Document 1).
上記のように、光配向法による液晶配向膜の配向処理方法では、ラビングが不要であり、発塵や静電気の発生の懸念が無い。また、光配向法による液晶配向膜の配向処理方法は、表面に凹凸のある液晶表示素子の基板においても配向処理を施すことができ、工業的な生産プロセスとしても好適である。
また、液晶表示素子の表示特性の向上は、ポリアミック酸、ポリアミック酸エステル、ポリイミド等の構造を変更する方法、特性の異なるポリアミック酸、ポリアミック酸エステル、ポリイミド等をブレンドする方法、さらに添加剤を加える方法などを使い、液晶配向性や電気特性等の改善、プレチルト角のコントロール等が行われている。例えば、特定の構造の基を側鎖として有する重合体を用いることが提案されている(特許文献2参照)。
しかしながら、液晶表示素子の高性能化、大面積化、表示デバイスの省電力化などが進み、液晶配向膜に求められる特性も厳しいものになってきている。特許文献2等の従来の液晶配向処理剤を用いた場合、焼き付き特性が不十分で、AC(交流)駆動によって液晶配向性能が変化して残像が生じてしまうことが問題であった。 A dimerization type photo-alignment method is also known. The dimerization type photo-alignment method is, for example, using polyvinyl cinnamate, irradiating polarized ultraviolet rays, causing a dimerization reaction at double bond portions of two side chains parallel to the polarized light, and orthogonal to the polarization direction. This is a method of aligning liquid crystals in the direction (see, for example, Non-Patent Document 1).
As described above, the alignment treatment method of the liquid crystal alignment film by the photo-alignment method does not require rubbing, and there is no concern about generation of dust or static electricity. Moreover, the alignment treatment method of the liquid crystal alignment film by the photo-alignment method can perform the alignment treatment even on the substrate of the liquid crystal display element having a concavo-convex surface, and is suitable as an industrial production process.
In addition, the display characteristics of the liquid crystal display element can be improved by changing the structure of polyamic acid, polyamic acid ester, polyimide, etc., blending polyamic acid, polyamic acid ester, polyimide, etc. having different characteristics, and adding additives. Methods are used to improve liquid crystal alignment and electrical characteristics, and control the pretilt angle. For example, it has been proposed to use a polymer having a group having a specific structure as a side chain (see Patent Document 2).
However, as liquid crystal display elements have higher performance, larger area, and lower power consumption of display devices, characteristics required for liquid crystal alignment films have become severe. When a conventional liquid crystal alignment treatment agent such as Patent Document 2 is used, there is a problem that image sticking characteristics are insufficient, and liquid crystal alignment performance is changed by AC (alternating current) driving, resulting in an afterimage.
しかし、例えば、上記した特許文献1に記載の分解型の光配向法では、ポリイミド膜に出力500Wの高圧水銀灯からの紫外光を60分間照射する必要があるなど、長時間かつ大量の紫外線照射が必要となる。 The photo-alignment method eliminates the rubbing process itself as compared with the rubbing process conventionally used industrially as an alignment processing method for liquid crystal display elements, and has a great advantage.
However, for example, in the decomposition type photo-alignment method described in
すなわち、より光反応効率の高い液晶配向膜用の有機膜材料の開発及び光反応効率を高めることができる液晶配向膜の製造方法の開発が求められている。 Further, in the dimerization type photo-alignment method, a large amount of ultraviolet irradiation of about several to several tens of joules (J) may be required. Furthermore, in order to obtain uniform liquid crystal alignment even when the irradiation amount of ultraviolet rays to the liquid crystal alignment film can be as small as several tens to several hundred millijoules (mJ), the amount of photoreactive groups introduced is increased. There is a need. Therefore, an unreacted group may remain even after ultraviolet irradiation. In a liquid crystal display device using such a liquid crystal alignment film, the unreacted group reacts due to backlight or external light, and the alignment state of the liquid crystal is changed. There is a problem that defects such as change occur. As described above, it is understood that a large amount of ultraviolet irradiation is required or an unreacted photoreactive group remains due to the low photoreaction efficiency of the organic film used for the liquid crystal alignment film.
That is, development of an organic film material for a liquid crystal alignment film having higher photoreaction efficiency and development of a method for producing a liquid crystal alignment film capable of increasing photoreaction efficiency are required.
さらに、本発明は、新規なジアミンを用いて得られるポリイミド前駆体を使用する液晶配向膜の製造方法、得られた液晶配向膜を使用したAC駆動による液晶配向性能の変化が低減され残像特性が良好な液晶表示素子を提供することをお目的とする。 An object of this invention is to provide the manufacturing method of the liquid crystal aligning film which implement | achieves high photoreaction efficiency and enables highly efficient alignment processing, and the liquid crystal display element provided with the obtained liquid crystal aligning film.
Furthermore, the present invention provides a method for producing a liquid crystal alignment film using a polyimide precursor obtained by using a novel diamine, a change in liquid crystal alignment performance by AC driving using the obtained liquid crystal alignment film, and an afterimage characteristic. An object is to provide a good liquid crystal display element.
(1)基板上に光反応基を有するポリイミド若しくはポリイミド前駆体を含有する薄膜を形成し、前薄膜面を加熱しながら、偏光した紫外線を照射し、前記基板上にポリイミド前駆体を含有する高分子からなる液晶配向膜を製造することを特徴とする液晶配向膜の製造方法。
(2)前記光反応基を有するポリイミド前駆体は、下記の式[1]で表される繰り返し単位及び下記の式[2]で表される繰り返し単位を含有する前記(1)に記載の液晶配向膜の製造方法。 As a result of intensive studies, the present inventor has completed the present invention as summarized in the following (1) to (12).
(1) A thin film containing a polyimide or a polyimide precursor having a photoreactive group is formed on a substrate, and the front thin film surface is irradiated with polarized ultraviolet rays while being heated, and the substrate contains a polyimide precursor. A method for producing a liquid crystal alignment film, comprising producing a liquid crystal alignment film comprising molecules.
(2) The liquid crystal according to (1), wherein the polyimide precursor having the photoreactive group contains a repeating unit represented by the following formula [1] and a repeating unit represented by the following formula [2]. A method for producing an alignment film.
(式[3]において、R9は2価の有機基を表し、R10は光反応性基を構成する2価の有機基を表す。n3は正の整数を表す。)
(In Formula [3], R 9 represents a divalent organic group, R 10 represents a divalent organic group constituting a photoreactive group, and n 3 represents a positive integer.)
(6)前記光反応基を有するポリイミド前駆体の含有量が、0.1~30質量%であり、溶剤を含有する液晶配向処理剤を用いて前記薄膜を形成する前記(1)~(5)のいずれかに記載の液晶配向膜の製造方法。 (5) The method for producing a liquid crystal alignment film according to any one of (1) to (4), wherein the thin film has a thickness of 5 to 300 nm.
(6) The content of the polyimide precursor having the photoreactive group is 0.1 to 30% by mass, and the thin film is formed using a liquid crystal aligning agent containing a solvent. ) For producing a liquid crystal alignment film.
(9)前記加熱の温度は、80℃~250℃の範囲内である前記(1)~(8)のいずれかに記載の液晶配向膜の製造方法。
(10)紫外線の照射量が、100~1000mJである前記(1)~(9)のいずれかに記載の液晶配向膜の製造方法。 (8) The method for producing a liquid crystal alignment film according to any one of (1) to (7), wherein the heating temperature is in the range of 50 ° C. to 300 ° C.
(9) The method for producing a liquid crystal alignment film according to any one of (1) to (8), wherein the heating temperature is in the range of 80 ° C. to 250 ° C.
(10) The method for producing a liquid crystal alignment film according to any one of (1) to (9), wherein the irradiation amount of ultraviolet rays is 100 to 1000 mJ.
本発明では、さらに、液晶配向膜に対するラビングが不要にできる。また、ポリイミド前駆体を含有する高分子膜における高い反応効率の光反応を実現して高効率な液晶配向膜の製造を可能とする。
さらに、本発明において、新規なジアミンから得られるポイミド前記体を使用して液晶配向膜を有する液晶表示素子は、AC駆動による液晶配向性能の変化が低減し、液晶配向性能が変化し難く、残像が発生し難い。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the liquid crystal aligning film which implement | achieves high photoreaction efficiency and enables highly efficient alignment processing is provided. The liquid crystal display device using the obtained liquid crystal alignment film has a high production efficiency and a small number of photoreactive residues in the liquid crystal alignment film, resulting in a defect that the liquid crystal alignment state changes even after long-term use. Hard to do.
In the present invention, further, rubbing on the liquid crystal alignment film can be eliminated. In addition, a high-efficiency photoreaction can be realized in a polymer film containing a polyimide precursor, and a highly efficient liquid crystal alignment film can be produced.
Furthermore, in the present invention, a liquid crystal display element having a liquid crystal alignment film using the above-mentioned poimide obtained from a novel diamine has a reduced change in the liquid crystal alignment performance due to AC driving, and the liquid crystal alignment performance hardly changes, and an afterimage Is unlikely to occur.
本発明の液晶配向膜の製造方法において用いられるポリイミド前駆体は、下記の式[1]で表される繰り返し単位とともに、下記の式[2]で表される繰り返し単位及び下記式[3]で表される繰り返し単位から選ばれる少なくともいずれか一方を含有する。下記の式[2]及び式[3]で表される繰り返し単位は、光反応基を有する。 The method for producing a liquid crystal alignment film of the present invention uses a method in which a polymer film containing a polyimide precursor is used and alignment treatment is performed by polarized light irradiation. For example, a polyamic acid ester derivative film having a photoreactive group is formed on a substrate, and then heated, and the film surface is irradiated with polarized ultraviolet rays while maintaining the heated state, whereby a polyamic acid is formed on the substrate. A liquid crystal alignment film made of an ester derivative is formed.
The polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention includes a repeating unit represented by the following formula [2] and a repeating unit represented by the following formula [1] together with the repeating unit represented by the following formula [1]. It contains at least one selected from repeating units represented. The repeating unit represented by the following formula [2] and formula [3] has a photoreactive group.
上記の式[2]で表される繰り返し単位のみが含まれる場合、モル比換算で、(式[1]で表される繰り返し単位)/(式[2]で表される繰り返し単位)は、1/99~99/1の範囲が好ましく、5/95~95/5となる範囲がより好ましい。
同様に、上記の式[3]で表される繰り返し単位のみが含まれる場合、モル比換算で、(式[1]で表される繰り返し単位)/(式[3]で表される繰り返し単位)は、1/99~99/1の範囲が好ましく、5/95~95/5となる範囲がより好ましい。
また、上記の式[2]で表される繰り返し単位及び上記の式[3]で表される繰り返し単位の両方が含まれる場合、モル比換算で、(式[1]で表される繰り返し単位)/{(式[2]で表される繰り返し単位)+(式[3]で表される繰り返し単位)}は、1/99~99/1の範囲が好ましく、5/95~95/5となる範囲がより好ましい。 In the polyimide precursor used in the method for producing a liquid crystal alignment film of the present invention, the repeating unit represented by the above formula [2] and / or the above formula [3] with respect to the repeating unit represented by the above formula [1]. The ratio of the content of the repeating unit represented by is as follows.
When only the repeating unit represented by the above formula [2] is included, in terms of molar ratio, (the repeating unit represented by the formula [1]) / (the repeating unit represented by the formula [2]) is The range of 1/99 to 99/1 is preferable, and the range of 5/95 to 95/5 is more preferable.
Similarly, when only the repeating unit represented by the above formula [3] is included, in terms of molar ratio, (the repeating unit represented by the formula [1]) / (the repeating unit represented by the formula [3] ) Is preferably in the range of 1/99 to 99/1, more preferably in the range of 5/95 to 95/5.
Further, when both the repeating unit represented by the above formula [2] and the repeating unit represented by the above formula [3] are included, the repeating unit represented by the formula [1] in terms of molar ratio ) / {(Repeating unit represented by Formula [2]) + (Repeating unit represented by Formula [3])} is preferably in the range of 1/99 to 99/1, and 5/95 to 95/5. The range which becomes is more preferable.
また、本発明のポリアミドは、上記式(4)で表されるジアミンを含むジアミン成分とジカルボン酸のハライドとを塩基存在下で反応させる、又は上記式(1)で表されるジアミンを含むジアミン成分とジカルボン酸とを適当な縮合剤、塩基の存在下にて反応させることによって得られる。
ポリアミック酸、ポリアミック酸エステル等のポリイミド前駆体、ポリイミド及びポリアミドのいずれも液晶配向膜を得るための重合体として有用である。なお、ジアミン成分に含まれる式(4)で表されるジアミンは、1種類でも2種類以上でもよく、また、ジアミン成分は、式(4)で表されるジアミン以外のその他のジアミンを1種類又は2種類以上含んでいてもよい。 The polyimide precursors such as polyamic acid and polyamic acid ester of the present invention are obtained by reacting a diamine component containing a diamine represented by the above formula (4) with a tetracarboxylic acid component. In addition, polyamic acid ester is obtained also by the method of converting the carboxyl group of polyamic acid into ester. Moreover, the polyimide of this invention is obtained by imidating polyimide precursors, such as these polyamic acids and polyamic acid ester.
Moreover, the polyamide of this invention makes the diamine component and the dicarboxylic acid halide containing the diamine represented by the said Formula (4) react in base presence, or the diamine containing the diamine represented by the said Formula (1). It can be obtained by reacting the component with dicarboxylic acid in the presence of a suitable condensing agent and base.
Any of polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, and polyamide are useful as a polymer for obtaining a liquid crystal alignment film. In addition, 1 type or 2 or more types may be sufficient as the diamine represented by Formula (4) contained in a diamine component, and a diamine component is 1 type of other diamines other than the diamine represented by Formula (4). Or two or more types may be included.
なお、本明細書において、特に記載がなければ、割合は、モル数を基準とするものである。 The content of the diamine represented by the formula (4) is 10 mol% or more, preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on the total amount of the diamine component.
In the present specification, unless otherwise specified, the ratio is based on the number of moles.
例えば、テトラカルボン酸ジハライド、テトラカルボン酸二無水物などとジアミン成分とを反応させることで、ポリアミック酸を得ることができる。また、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の反応や、テトラカルボン酸ジエステルとジアミン成分とを適当な縮合剤や塩基の存在下で反応させることにより、ポリアミック酸エステルを得ることができる。なお、用いるテトラカルボン酸成分は、1種類でも2種類以上でもよい。 The tetracarboxylic acid component is at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives. Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester.
For example, a polyamic acid can be obtained by reacting a diamine component with a tetracarboxylic acid dihalide, tetracarboxylic dianhydride, or the like. In addition, a polyamic acid ester can be obtained by reacting a tetracarboxylic acid diester dichloride with a diamine component or reacting a tetracarboxylic acid diester with a diamine component in the presence of an appropriate condensing agent or base. In addition, the tetracarboxylic acid component to be used may be one type or two or more types.
(式(5a)中、Z2~Z5は水素原子、メチル基、塩素原子又はベンゼン環を表し、それぞれ、同じであっても異なってもよく、式(5g)中、Z6及びZ7は水素原子又はメチル基を表し、それぞれ、同じであっても異なってもよい。)
(In formula (5a), Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In formula (5g), Z 6 and Z 7 Represents a hydrogen atom or a methyl group, which may be the same or different.
脂肪族テトラカルボン酸ジエステルの具体的な例としては1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,2-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、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ジアルキルエステル、1,2,3,4-シクロペンタンテトラカルボン酸ジアルキルエステル、2,3,4,5-テトラヒドロフランテトラカルボン酸ジアルキルエステル、1,2,4,5-シクロヘキサンテトラカルボン酸ジアルキルエステル、3,4-ジカルボキシ-1-シクロヘキシルコハク酸ジアルキルエステル、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ジアルキルエステル、1,2,3,4-ブタンテトラカルボン酸ジアルキルエステル、ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸ジアルキルエステル、3,3',4,4'-ジシクロヘキシルテトラカルボン酸ジアルキルエステル、2,3,5-トリカルボキシシクロペンチル酢酸ジアルキルエステル、シス-3,7-ジブチルシクロオクタ-1,5-ジエン-1,2,5,6-テトラカルボン酸ジアルキルエステル、トリシクロ[4.2.1.02,5]ノナン-3,4,7,8-テトラカルボン酸-3,4:7,8-ジアルキルエステル、ヘキサシクロ[6.6.0.12,7.03,6.19,14.010,13]ヘキサデカン-4,5,11,12-テトラカルボン酸-4,5:11,12-ジアルキルエステル、4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドロナフタレンー1,2-ジカルボンジアルキルエステル等が挙げられる。 Tetracarboxylic acid diesters are not particularly limited. Specific examples are given below.
Specific examples of the aliphatic tetracarboxylic acid diester 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-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8- Tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5- Diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3, 4: 7,8 A dialkyl ester, hexacyclo [6.6.0.1 2,7 . 0 3,6 . 1 9,14 . 0 10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2, Examples include 3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester.
テトラフルオロボラート、O-(ベンゾトリアゾール-1-イル)-N,N,N',N'-テトラメチルウロニウムヘキサフルオロホスファート、(2,3-ジヒドロ-2-チオキソ-3-ベンゾオキサゾリル)ホスホン酸ジフェニル、4-(4,6-ジメトキシ-1,3,5-トリアジン-2-イル)4-メトキシモルホリウムクロリド
n-水和物等が使用できる。 Further, when polycondensation of tetracarboxylic acid diester and diamine component in the presence of a condensing agent, the condensing agent includes triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluro Nium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzo Oxazolyl) phosphonic acid diphenyl, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4- Toki Simo sulfo potassium chloride n- hydrates can be used.
(式[h]中、R11は、原料のテトラカルボン酸成分に由来する4価の有機基であり、R12は、原料のジアミン成分に由来する2価の有機基であり、A11及びA12は、水素原子又は炭素数1~4のアルキル基であり、それぞれ同じであっても異なってもよく、jは正の整数を示す。)
(In the formula [h], R 11 is a tetravalent organic group derived from the starting tetracarboxylic acid component, R 12 is a divalent organic group derived from the starting diamine component, and A 11 and A 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and j represents a positive integer.)
(式[k]及び式[s]中、R11及びR12は、式[h]で定義したものと同じである。)
(In formula [k] and formula [s], R 11 and R 12 are the same as defined in formula [h].)
塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもピリジンは反応を進行させるのに適度な塩基性を持つので好ましい。
酸無水物としては、無水酢酸、無水トリメリット酸、無水ピロメリット酸等を挙げることができる。中でも無水酢酸を用いると反応終了後の精製が容易となるので好ましい。触媒イミド化によるイミド化率は、触媒量と反応温度、反応時間を調節することにより制御することができる。 The catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor 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.
Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Of these, use of acetic anhydride is preferred 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.
ポリイミドは比較的剛直な高分子材料であり、薄膜中に多く含まれると、ポリイミド前駆体を含有する膜の柔軟性が損なわれる。また、偏光照射時に加熱処理を併用する効果が損なわれ、ポリイミド前駆体を含有する膜中での光反応の進行を妨げる可能性がある。その結果、光反応によるポリイミド前駆体を含有する膜への異方性の導入を妨げる懸念がある。 In the present invention, it is desirable that polyimide is not contained in the thin film containing the polyimide precursor. Even if the polyimide is inevitably contained in the thin film containing the polyimide precursor, the content thereof is preferably 30 mol% or less, more preferably 20 mol% or less with respect to the polyimide precursor. 10 mol% or less is more preferable.
Polyimide is a relatively rigid polymer material, and when it is contained in a large amount in a thin film, the flexibility of the film containing the polyimide precursor is impaired. Moreover, the effect of using heat treatment at the time of polarized light irradiation is impaired, and there is a possibility that the progress of the photoreaction in the film containing the polyimide precursor may be hindered. As a result, there is a concern that the introduction of anisotropy into the film containing the polyimide precursor by photoreaction may be hindered.
具体的には、基板上に形成されたポリイミド前駆体を含有する薄膜の加熱温度は50~300℃であり、好ましくは80~250℃の範囲であり、150~200℃とすることがさらに好ましい。
基板上のポリイミド前駆体を含有する薄膜の加熱とその加熱状態の維持は、例えば、ホットプレート、熱循環型オーブン又はIR(赤外線)型オーブンなどを用いて行うことができる。なかでも、紫外線照射を行うことが容易なホットプレートを選択して用いることが好ましい。 Therefore, the heating temperature of the thin film containing the polyimide precursor formed on the substrate is a temperature in a range that realizes high photoreaction efficiency of the thin film, and a temperature that does not cause a chemical reaction of the polyimide precursor. It is preferable to do. That is, as the upper limit of the heating temperature, it is preferable to select a temperature within a range in which a thermal reaction occurs and does not change to polyimide, depending on the type of polyimide precursor used. About a minimum, it is preferable to select the temperature which can express the photoreactive improvement effect mentioned later by the kind of polyimide precursor to be used.
Specifically, the heating temperature of the thin film containing the polyimide precursor formed on the substrate is 50 to 300 ° C., preferably 80 to 250 ° C., more preferably 150 to 200 ° C. .
The heating of the thin film containing the polyimide precursor on the substrate and the maintenance of the heating state can be performed using, for example, a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like. Among these, it is preferable to select and use a hot plate that can be easily irradiated with ultraviolet rays.
また、本発明の液晶配向膜の製造方法を利用し、得られた液晶配向膜を用いて液晶表示素子を製造することができる。
次に、本発明の液晶配向膜を用いた液晶表示素子について説明する。 As described above, in the method for producing a liquid crystal alignment film of the present invention, a thin film containing a polyimide precursor is heated and irradiated with polarized ultraviolet rays while maintaining the heating state, so that high efficiency can be achieved with a small amount of ultraviolet irradiation. A liquid crystal alignment film can be manufactured. That is, the present invention can produce a liquid crystal alignment film with high production efficiency.
Moreover, a liquid crystal display element can be manufactured using the obtained liquid crystal aligning film using the manufacturing method of the liquid crystal aligning film of this invention.
Next, a liquid crystal display element using the liquid crystal alignment film of the present invention will be described.
本発明においては、上記重合体成分として、本発明の上記ポリアミック酸、ポリアミック酸エステル等のポリイミド前駆体、ポリイミド及びポリアミドから選択される少なくとも一種を含有する。 The liquid-crystal aligning agent of this invention contains polyimide precursors, such as the said polyamic acid and polyamic acid ester, a polyimide, polyamide, etc. The liquid crystal alignment treatment agent is a solution for forming a liquid crystal alignment film, and is a solution in which a polymer component for forming a liquid crystal alignment film is dispersed or dissolved in an organic solvent. Here, the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.
In the present invention, the polymer component contains at least one selected from polyimide precursors such as the polyamic acid and polyamic acid ester of the present invention, polyimide and polyamide.
偏光紫外線の照射は、液晶配向膜を加熱しながら照射してもよい。 After the liquid crystal alignment treatment agent is applied on the substrate, the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven, an IR (infrared) oven, etc. It can be set as an alignment film (polymer thin film). If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the liquid crystal can be aligned by treating the fired liquid crystal alignment film with rubbing, irradiation with polarized ultraviolet rays, or the like. For example, by irradiating light such as polarized ultraviolet rays, the photoreactive group derived from diamine represented by the formula (4) undergoes a dimerization reaction, and the liquid crystal can be aligned with the anisotropy generated thereby. .
The irradiation with polarized ultraviolet light may be performed while heating the liquid crystal alignment film.
上記範囲内の選択された温度で加熱を行いながら、上述したように光照射条件を選択して、ポリイミド前駆体を含有する薄膜の膜面に対し、一定の方向から偏光板を介して偏光された紫外線を照射する。こうして基板上に、液晶の配向制御能を備えた液晶配向膜を製造することができる。 The thin film containing the polyimide precursor formed on the substrate is heated at 80 to 250 ° C. using, for example, a hot plate. At this time, as the upper limit of the heating temperature, a temperature in a range in which a thermal reaction occurs and does not change to polyimide is selected depending on the type of polyimide precursor to be used. About a minimum, the temperature which expresses the improvement effect of photoreactivity is selected by the kind of polyimide precursor to be used.
While heating at a selected temperature within the above range, the light irradiation conditions are selected as described above, and the film surface of the thin film containing the polyimide precursor is polarized through a polarizing plate from a certain direction. Irradiate with ultraviolet light. Thus, a liquid crystal alignment film having a liquid crystal alignment control ability can be produced on the substrate.
[実施例A] EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited thereto.
[Example A]
モノマー(3)は、反応式(i)に従い合成した。 <Synthesis Example 1 (Synthesis of Monomer (3))>
Monomer (3) was synthesized according to reaction formula (i).
なお、得られたモノマー(2)の1H-NMRは、TMS(Si(CH3)4)を基準物質として、重水素化ジメチルスルホキシド(DMSOと略称する。)の溶媒中で、NMR測定装置(JEOL社製、500MHz)を用いて行った。モノマー(2)の1H-NMR測定結果を以下に示すが、他の化合物についても同様である。
1H-NMR(500MHz, DMSO, δppm)=1.27(t, J=7.09Hz, 6H, -CH2-CH3-), 4.28(q, J=7.04Hz, 4H, -CH2-CH3), 7.96(S, 2H, Ph). Monomer (1) (20 g, 0.09 mol) was added to dry ethanol (60 ml), and the mixture was stirred and refluxed until all the solid was dissolved, and then stirred and refluxed for another 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure until a solid was slightly precipitated. The reaction solution of about 50% (volume) of dry ethanol was cooled at room temperature, and the precipitate was separated by filtration and then washed with ethanol to obtain the desired monomer (2). Further, the solvent of the filtrate was distilled off under reduced pressure to obtain a mixture of target isomers. The monomer (2) was obtained by recrystallizing the mixture of isomers with ethyl acetate. The yield was 10 g, and the yield was 35.2%.
In addition, 1 H-NMR of the obtained monomer (2) is an NMR measurement apparatus in a solvent of deuterated dimethyl sulfoxide (abbreviated as DMSO) using TMS (Si (CH 3 ) 4 ) as a reference substance. (JEOL, 500 MHz). The 1 H-NMR measurement results of the monomer (2) are shown below, but the same applies to other compounds.
1 H-NMR (500MHz, DMSO, δppm) = 1.27 (t, J = 7.09Hz, 6H, -CH 2 -CH 3- ), 4.28 (q, J = 7.04Hz, 4H, -CH 2 -CH 3 ) , 7.96 (S, 2H, Ph).
1H-NMR(500MHz, CDCl3, δppm)=1.43(t, J= 7.12Hz,6H, -CH2-CH3-), 4.46(q, J=7.1Hz, 4H, -CH2-CH3), 8.16(S, 2H, Ph). A small amount of N, N′-dimethylformamide was added to a mixture of 4.77 g (0.015 mol) of monomer (2) and 35 ml of ethyl acetate. Next, 3 ml of thionyl chloride was added and stirred to reflux. After confirming that all solids were dissolved, the mixture was further stirred and refluxed for 1 hour. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure. The product was purified by recrystallization from hexane to obtain purified monomer (3). The yield was 4.3 g, and the yield was 80.5%. The solvent for 1 H-NMR was deuterated chloroform (CDCl 3 ).
1 H-NMR (500MHz, CDCl 3 , δppm) = 1.43 (t, J = 7.12Hz, 6H, -CH 2 -CH 3- ), 4.46 (q, J = 7.1Hz, 4H, -CH 2 -CH 3 ), 8.16 (S, 2H, Ph).
モノマー(5)は、反応式(ii)に従い合成した。 <Synthesis Example 2 (Synthesis of Monomer (5))>
Monomer (5) was synthesized according to reaction formula (ii).
1H-NMR(500MHz, CDCl3, δppm)=6.72 (d, J=15.7Hz, 2H, -CH=CH-), 7.65(S, 4H, Ph), 7.82(d, J=15.7Hz, 2H, -CH=CH-) A small amount of N, N′-dimethylformamide was added to a mixture of 4.8 g (0.022 mol) of monomer (4) and 50 ml of ethyl acetate. Next, 6 ml of thionyl chloride was added and stirred and refluxed. After confirming that all solids were dissolved, the mixture was further stirred and refluxed for 1 hour. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure. The product was purified by recrystallization from an ethyl acetate / hexane system to obtain a purified monomer (5). The yield was 3.5 g, and the yield was 62.4%. The solvent for 1 H-NMR was deuterated chloroform (CDCl 3 ).
1 H-NMR (500MHz, CDCl 3 , δppm) = 6.72 (d, J = 15.7Hz, 2H, -CH = CH-), 7.65 (S, 4H, Ph), 7.82 (d, J = 15.7Hz, 2H , -CH = CH-)
ポリアミック酸エステル誘導体の分子量の測定は、後記する[実施例B]に記載したポリマーの分子量測定方法と同様に行なった。 (Molecular weight measurement)
The molecular weight of the polyamic acid ester derivative was measured in the same manner as the polymer molecular weight measurement method described in [Example B] described later.
APHFP1.49g(4.5mmol)とLiCl 1.5gを60mlの乾燥NMPに加え、室温で固体が全て溶解するまで攪拌した。その後、クロロトリメチルシラン0.12gを加えた。この溶液にモノマー(3)0.31g(0.9mmol)、モノマー(5)0.91g(3.5mmol)、及び乾燥THF5mlの混合溶液を室温で滴下し、滴下漏斗を2mlの乾燥THFで洗い流した後、1時間攪拌した。その後、徐々に反応温度を上げ、40℃でさらに3時間攪拌した。反応終了後、反応溶液を800mlの水に注ぎ、生成したポリマーを分離した後、濾過分別し、エタノールとアセトンで洗浄した。次いで、ポリマーを乾燥させた後、NMPに溶解し、エタノール、及びクロロホルムにより再沈殿させて精製した。その後、沈殿物を濾過分別し、十分に乾燥させ、Mnが31,400であり、Mwが66,000のポリアミック酸エステル誘導体(6FPAE2-8)粉末(A)を得た。 <Synthesis Example 3 (Synthesis of 6FPAE2-8)>
APHFP 1.49 g (4.5 mmol) and LiCl 1.5 g were added to 60 ml of dry NMP and stirred at room temperature until all solids were dissolved. Thereafter, 0.12 g of chlorotrimethylsilane was added. To this solution, a mixed solution of 0.31 g (0.9 mmol) of monomer (3), 0.91 g (3.5 mmol) of monomer (5) and 5 ml of dry THF was dropped at room temperature, and the dropping funnel was washed away with 2 ml of dry THF. And stirred for 1 hour. Thereafter, the reaction temperature was gradually raised, and the mixture was further stirred at 40 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into 800 ml of water, and the produced polymer was separated, followed by filtration and separation, and washing with ethanol and acetone. Next, the polymer was dried and then dissolved in NMP and purified by reprecipitation with ethanol and chloroform. Thereafter, the precipitate was separated by filtration and sufficiently dried to obtain a polyamic acid ester derivative (6FPAE2-8) powder (A) having an Mn of 31,400 and an Mw of 66,000.
APHFP1.49g(4.5mmol)とLiCl 1.5gを60mlの乾燥NMPに加え、室温で固体が全て溶解するまで攪拌した。その後、クロロトリメチルシラン0.12gを加えた。この溶液にモノマー(3)0.77g(2.2mmol)、モノマー(5)0.57g(2.2mmol)、及び乾燥THF5mlの混合溶液を室温で滴下し、滴下漏斗を2mlの乾燥THFで洗い流した後、1時間攪拌した。その後、徐々に反応温度を上げ、40℃でさらに3時間攪拌した。反応終了後、反応溶液を800mlの水に注ぎ、生成したポリマーを分離した後、濾過分別し、エタノールとアセトンで洗浄した。次いで、ポリマーを乾燥させた後、NMPに溶解し、エタノール、及びクロロホルムにより再沈殿させて精製した。その後、沈殿物を濾過分別し、十分に乾燥させ、Mnが28,600であり、Mwが52,800のポリアミック酸エステル誘導体(6FPAE5-5)粉末(B)を得た。 <Synthesis Example 4 (Synthesis of 6FPAE5-5)>
APHFP 1.49 g (4.5 mmol) and LiCl 1.5 g were added to 60 ml of dry NMP and stirred at room temperature until all solids were dissolved. Thereafter, 0.12 g of chlorotrimethylsilane was added. To this solution, a mixed solution of 0.77 g (2.2 mmol) of monomer (3), 0.57 g (2.2 mmol) of monomer (5) and 5 ml of dry THF was added dropwise at room temperature, and the dropping funnel was rinsed with 2 ml of dry THF. And stirred for 1 hour. Thereafter, the reaction temperature was gradually raised, and the mixture was further stirred at 40 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into 800 ml of water, and the produced polymer was separated, followed by filtration and separation, and washing with ethanol and acetone. Next, the polymer was dried and then dissolved in NMP and purified by reprecipitation with ethanol and chloroform. Thereafter, the precipitate was separated by filtration and sufficiently dried to obtain a polyamic acid ester derivative (6FPAE5-5) powder (B) having an Mn of 28,600 and an Mw of 52,800.
合成例3で得られたポリアミック酸エステル誘導体(6FPAE2-8)粉末(A)にNMP及びBCSを加えて4質量%に希釈し、液晶配向処理剤(I)を得た。この液晶配向処理剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。 <Example 1>
NMP and BCS were added to the polyamic acid ester derivative (6FPAE2-8) powder (A) obtained in Synthesis Example 3 and diluted to 4% by mass to obtain a liquid crystal aligning agent (I). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
合成例4で得られたポリアミック酸エステル誘導体(6FPAE5-5)粉末(B)にNMP及びBCSを加えて4質量%に希釈し、液晶配向処理剤(II)を得た。この液晶配向処理剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。 <Example 2>
NMP and BCS were added to the polyamic acid ester derivative (6FPAE5-5) powder (B) obtained in Synthesis Example 4 and diluted to 4% by mass to obtain a liquid crystal aligning agent (II). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
実施例1で得られたポリアミック酸エステル誘導体(6FPAE2-8)を含有する液晶配向処理剤(I)を用い、透明なガラス基板(厚さ1.1mm、横30mm、縦40mm)上にスピンコートし、80℃のホットプレート上で5分間乾燥させた後、膜厚40nmの塗膜を形成し、配向処理前の液晶配向膜付き基板を得た。 <Example 3>
Using the liquid crystal aligning agent (I) containing the polyamic acid ester derivative (6FPAE2-8) obtained in Example 1, spin coating was performed on a transparent glass substrate (thickness 1.1 mm, width 30 mm, length 40 mm). Then, after drying for 5 minutes on a hot plate at 80 ° C., a coating film with a film thickness of 40 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
実施例2で得られたポリアミック酸エステル誘導体(6FPAE5-5)を含有する液晶配向処理剤(II)を用い、透明なガラス基板上にスピンコートし、80℃のホットプレート上で5分間乾燥させた後、膜厚40nmの塗膜を形成し、配向処理前の液晶配向膜付き基板を得た。 <Example 4>
The liquid crystal alignment treatment agent (II) containing the polyamic acid ester derivative (6FPAE5-5) obtained in Example 2 was spin-coated on a transparent glass substrate and dried on a hot plate at 80 ° C. for 5 minutes. After that, a coating film having a thickness of 40 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
実施例3で得られた配向処理前の液晶配向膜付き基板を用い、これをホットプレート上で240℃に加熱し、その加熱状態を維持したまま、基板上の液晶配向膜面に対して一定の方向から偏光板(目白プレシジョン社製)を介して偏光された紫外線(ウシオ電機社製高圧水銀ランプ、目白プレシジョン社製偏光照射装置)を照射した。偏光された紫外線の強度は、波長365nmで14mWとし、紫外線照射量は500mJとした。こうして、配向処理された液晶配向膜付き基板を得た。 <Example 5>
The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used, heated to 240 ° C. on a hot plate, and kept constant with respect to the liquid crystal alignment film surface on the substrate while maintaining the heating state. Were irradiated with ultraviolet rays (high pressure mercury lamp manufactured by Ushio Electric Co., Ltd., polarized light irradiation device manufactured by Mejiro Precision Co., Ltd.) through a polarizing plate (made by Mejiro Precision Co., Ltd.). The intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 500 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
実施例3で得られた配向処理前の液晶配向膜付き基板を用い、これを室温に維持したまま、基板上の液晶配向膜面に対して一定の方向から偏光板を介して偏光された紫外線を照射した。偏光された紫外線の強度は、波長365nmで14mWとし、紫外線照射量は500mJとした。こうして、液晶配向膜の形成された液晶配向膜付き基板を得た。 <Comparative Example 1>
Using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3, and maintaining this at room temperature, the ultraviolet light polarized through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate Was irradiated. The intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 500 mJ. Thus, a substrate with a liquid crystal alignment film on which a liquid crystal alignment film was formed was obtained.
実施例3で得られた配向処理前の液晶配向膜付き基板を用い、これを室温に維持したまま、基板上の液晶配向膜面に対して一定の方向から偏光板を介して偏光された紫外線を照射した。偏光された紫外線の強度は、波長365nmで14mWとし、紫外線照射量は4500mJとした。こうして、液晶配向膜の形成された液晶配向膜付き基板を得た。 <Comparative example 2>
Using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3, and maintaining this at room temperature, the ultraviolet light polarized through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate Was irradiated. The intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 4500 mJ. Thus, a substrate with a liquid crystal alignment film on which a liquid crystal alignment film was formed was obtained.
実施例4で得られた配向処理前の液晶配向膜付き基板を用い、これをホットプレート上で160℃に加熱し、その加熱状態を維持したまま、基板上の液晶配向膜面に対して一定の方向から偏光板を介して偏光された紫外線を照射した。偏光された紫外線の強度は、波長365nmで14mWとし、紫外線照射量は250mJとした。こうして、配向処理された液晶配向膜付き基板を得た。 <Example 6>
Using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 4, this was heated to 160 ° C. on a hot plate, and the liquid crystal alignment film surface on the substrate was kept constant while maintaining the heated state. The polarized ultraviolet rays were irradiated from the direction through the polarizing plate. The intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 250 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
ホットプレート上での加熱温度を200℃としたこと以外、実施例6と同様の方法に従い配向処理された液晶配向膜付き基板を得た。 <Example 7>
A substrate with a liquid crystal alignment film subjected to alignment treatment according to the same method as in Example 6 was obtained except that the heating temperature on the hot plate was 200 ° C.
ホットプレート上での加熱温度を240℃としたこと以外、実施例6と同様の方法に従い配向処理された液晶配向膜付き基板を得た。
実施例3~8、比較例1及び比較例2において得られた液晶配向膜付き基板の作製条件について表1にまとめて示す。 <Example 8>
A substrate with a liquid crystal alignment film that had been subjected to alignment treatment according to the same method as in Example 6 was obtained except that the heating temperature on the hot plate was 240 ° C.
Table 1 summarizes the conditions for producing the substrates with the liquid crystal alignment films obtained in Examples 3 to 8, Comparative Example 1 and Comparative Example 2.
液晶配向処理剤A5(後記する[実施例B]に記載)を、石英基板(厚さ1.1mm、横40mm、縦40mm)にスピンコートした。次いで、90℃のホットプレートで60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。次いで、ホットプレート上で240℃に加熱し、その加熱状態を維持したまま、基板上の液晶配向膜面に偏光板を介して313nmの紫外線を1000mJ/cm2照射し、液晶配向膜付き基板を得た。
<比較例3>
実施例9と同様にして、液晶配向膜を形成し、室温(23℃)で基板の液晶配向膜面に偏光板を介して313nmの紫外線を1000mJ/cm2照射し、液晶配向膜付き基板を得た。
<比較例4>
実施例9と同様にして、液晶配向膜を形成し、加熱及び紫外線照射のない液晶配向膜付き基板を得た。比較例4の紫外線吸収スペクトルは、実施例9及び比較例3の比較対象とした。
実施例9、比較例3、4において得られた液晶配向膜付き基板の作製条件について表2にまとめて示す。 <Example 9>
Liquid crystal aligning agent A5 (described in [Example B] described later) was spin-coated on a quartz substrate (thickness 1.1 mm, width 40 mm, length 40 mm). Subsequently, after drying for 60 seconds with a 90 degreeC hotplate, it baked for 30 minutes with a 200 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the substrate was heated to 240 ° C. on a hot plate, and while maintaining the heated state, the surface of the liquid crystal alignment film on the substrate was irradiated with 1000 mJ / cm 2 of 313 nm ultraviolet light via a polarizing plate, and the substrate with a liquid crystal alignment film was formed. Obtained.
<Comparative Example 3>
In the same manner as in Example 9, a liquid crystal alignment film was formed, and the liquid crystal alignment film surface of the substrate was irradiated with 1000 mJ / cm 2 of ultraviolet light at 313 nm through a polarizing plate at room temperature (23 ° C.) to form a substrate with a liquid crystal alignment film. Obtained.
<Comparative Example 4>
In the same manner as in Example 9, a liquid crystal alignment film was formed, and a substrate with a liquid crystal alignment film without heating and ultraviolet irradiation was obtained. The ultraviolet absorption spectrum of Comparative Example 4 was used as a comparison target of Example 9 and Comparative Example 3.
Table 2 summarizes the conditions for producing the substrates with liquid crystal alignment films obtained in Example 9 and Comparative Examples 3 and 4.
(紫外吸収スペクトルの測定方法)
液晶配向膜の紫外吸収スペクトルの測定は、UV-Vis吸光高度測定法により行なった。
実施例5で得られた配向処理された液晶配向膜付き基板を用い、液晶配向膜の紫外吸収スペクトルを測定した。併せて、実施例3で得られた配向処理前の液晶配向膜付き基板を用い、配向処理前の液晶配向膜の紫外吸収スペクトルを測定して比較対象とした。 [
(Measurement method of ultraviolet absorption spectrum)
The ultraviolet absorption spectrum of the liquid crystal alignment film was measured by the UV-Vis absorption height measurement method.
Using the alignment-treated substrate with a liquid crystal alignment film obtained in Example 5, the ultraviolet absorption spectrum of the liquid crystal alignment film was measured. In addition, using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3, the ultraviolet absorption spectrum of the liquid crystal alignment film before alignment treatment was measured and used as a comparison object.
図3は本発明の実施例9で得られた液晶配向膜の紫外吸収スペクトルであり、比較対象として、室温にて偏光紫外線を照射した比較例3及び加熱や偏光紫外線照射がなされていない比較例4の液晶配向膜の紫外吸収スペクトルを併せて示す。図3に示すように、実施例9の液晶配向膜の紫外吸収スペクトル(図3中では、「実施例9」と記載した。)と比較例3の液晶配向膜の紫外吸収スペクトル(図3中では、「比較例3」と記載した。)を比較すると、実施例9の液晶配向膜において波長310nm付近の吸光度が大きく低下していることが分かる。この吸光度の低下は、ホットプレート上での240℃の加熱と1000mJの偏光紫外線の照射処理によるものと解される。実施例9の液晶配向膜の波長300nm~350nm近辺の吸収は、液晶配向膜を構成するポリアミック酸誘導体の含有する光反応基に由来する吸収と解され、ホットプレート上での240℃の加熱と1000mJの偏光紫外線の照射処理により、ポリアミック酸誘導体の膜において光架橋反応が効率良く進行したことが分かる。偏光した紫外線の照射時に240℃での加熱処理を併用した実施例9の液晶配向膜では、非常に高い効率で光反応が進行したことがわかる。 1 and FIG. 2 are compared, the absorbance of the liquid crystal alignment film of Comparative Example 2 shown in FIG. 2 in the vicinity of the wavelength of 300 to 350 nm and the wavelength of the liquid crystal alignment film obtained in Example 5 of FIG. It can be seen that the absorbance around ˜350 nm is equivalent. The irradiation amount of polarized ultraviolet rays in Example 5 is 500 mJ, and the irradiation amount of polarized ultraviolet rays in the liquid crystal alignment film of Comparative Example 2 is 4500 mJ. From this, it can be seen that the photoreaction progressed with very high efficiency in the liquid crystal alignment film of Example 5 in which heat treatment at 240 ° C. was used in combination with irradiation of polarized ultraviolet rays. In the case of the liquid crystal alignment film of Example 5, the efficiency of the photoreaction is improved about 10 times compared to the case of the liquid crystal alignment film such as Comparative Examples 1 and 2 that does not use heat treatment at the time of polarized light irradiation. all right.
FIG. 3 is an ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 9 of the present invention. For comparison, Comparative Example 3 in which polarized ultraviolet rays were irradiated at room temperature and Comparative Example in which heating and polarized ultraviolet rays were not applied. 4 also shows the ultraviolet absorption spectrum of the liquid crystal alignment film of No. 4. As shown in FIG. 3, the ultraviolet absorption spectrum of the liquid crystal alignment film of Example 9 (described as “Example 9” in FIG. 3) and the ultraviolet absorption spectrum of the liquid crystal alignment film of Comparative Example 3 (in FIG. 3) Then, it was described as “Comparative Example 3”.), It was found that the absorbance in the vicinity of the wavelength of 310 nm was greatly reduced in the liquid crystal alignment film of Example 9. This decrease in absorbance is considered to be due to heating at 240 ° C. on a hot plate and irradiation treatment with 1000 mJ polarized ultraviolet rays. The absorption in the vicinity of the wavelength of 300 nm to 350 nm of the liquid crystal alignment film of Example 9 is understood as absorption derived from the photoreactive group contained in the polyamic acid derivative constituting the liquid crystal alignment film, and heating at 240 ° C. on the hot plate It can be seen that the photocrosslinking reaction proceeded efficiently in the polyamic acid derivative film by the irradiation with 1000 mJ polarized ultraviolet light. It can be seen that in the liquid crystal alignment film of Example 9 in which the heat treatment at 240 ° C. was used in combination with the irradiation of polarized ultraviolet rays, the photoreaction proceeded with very high efficiency.
実施例6で得られた配向処理された液晶配向膜付き基板を用い、液晶配向膜の紫外吸収スペクトルを測定した。併せて、実施例4で得られた配向処理前の液晶配向膜付き基板を用い、紫外吸収スペクトルを測定して比較対象とした。実施例4で得られた液晶配向膜の紫外吸収スペクトルにおける波長350nm付近の吸収極大の吸光度は1.0であるのに対し、実施例6の液晶配向膜の紫外吸収スペクトルにおける波長350nm付近の吸収極大の吸光度は0.76であり、実施例の6の液晶配向膜の波長350nm付近の吸光度が大きく低下していることが分かった。その結果から、偏光した紫外線の照射時に160℃での加熱処理を併用した実施例6の液晶配向膜では、高い効率で光反応が進行したことがわかった。 [Evaluation 2 of liquid crystal alignment film]
Using the alignment-treated substrate with a liquid crystal alignment film obtained in Example 6, the ultraviolet absorption spectrum of the liquid crystal alignment film was measured. In addition, using the substrate with a liquid crystal alignment film before alignment treatment obtained in Example 4, an ultraviolet absorption spectrum was measured and used as a comparison target. The absorbance at the absorption maximum near a wavelength of 350 nm in the ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 4 is 1.0, whereas the absorption near the wavelength of 350 nm in the ultraviolet absorption spectrum of the liquid crystal alignment film in Example 6 is obtained. The maximum absorbance was 0.76, and it was found that the absorbance around the wavelength of 350 nm of the liquid crystal alignment film of Example 6 was greatly reduced. From the results, it was found that the photoreaction progressed with high efficiency in the liquid crystal alignment film of Example 6 in which the heat treatment at 160 ° C. was used in combination with the irradiation of polarized ultraviolet rays.
以上の評価結果から、偏光した紫外線を液晶配向膜に照射する時に加熱処理を併用する場合、160℃の加熱温度で光反応効率の向上の効果が十分となり、200℃以上の加熱温度においても、光反応効率の向上効果は、160℃の場合とほぼ同等となることがわかった。すなわち、液晶配向膜の配向処理における偏光紫外線照射時の加熱温度としては、液晶配向膜を構成するポリアミック酸エステル誘導体のポリイミドへの変化を抑制できる、160~200℃とすることが特に好ましいことがわかった。 Similarly, using the alignment-treated substrate with a liquid crystal alignment film obtained in Examples 7 and 8, the ultraviolet absorption spectrum of the liquid crystal alignment film was measured, and the absorbance at the absorption maximum near a wavelength of 350 nm was evaluated. It was 0.70. When compared with the liquid crystal alignment film of Example 6, the degree of decrease in absorbance at the absorption maximum is slightly large. In the liquid crystal alignment film of Example 7 and the liquid crystal alignment film of Example 8, the degree of decrease in absorbance at the absorption maximum is It was equivalent.
From the above evaluation results, when heat treatment is used in combination with irradiation of polarized ultraviolet rays to the liquid crystal alignment film, the effect of improving the photoreaction efficiency is sufficient at a heating temperature of 160 ° C., and even at a heating temperature of 200 ° C. or higher, It was found that the effect of improving the photoreaction efficiency was almost the same as that at 160 ° C. That is, the heating temperature at the time of irradiation with polarized ultraviolet rays in the alignment treatment of the liquid crystal alignment film is particularly preferably 160 to 200 ° C., which can suppress the change of the polyamic acid ester derivative constituting the liquid crystal alignment film to polyimide. all right.
実施例1で得られた液晶配向処理剤(I)を用いて液晶配向膜を作製し、その液晶配向膜を用いた液晶セルを製造した。液晶セルは、液晶配向膜の特性に対応して、平行配向の液晶セルとした。得られた液晶セルを一対の偏光板で挟持することにより液晶表示素子を構成することができる。 <Example 10>
A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agent (I) obtained in Example 1, and a liquid crystal cell using the liquid crystal alignment film was manufactured. The liquid crystal cell was a parallel aligned liquid crystal cell corresponding to the characteristics of the liquid crystal alignment film. A liquid crystal display element can be constituted by sandwiching the obtained liquid crystal cell between a pair of polarizing plates.
この液晶配向膜付き基板を2枚用意し、一方の液晶配向膜面上に14μmのスペーサ(日本触媒社製、真し球)を散布した後、この上からシール剤(三井化学社製XN-1500T)を塗布した。次いで、他方の基板と液晶配向膜面が向き合うようにして貼り合わせた後、シール剤を150℃で150間加熱することにより硬化して空セルを作製した。この空セルに毛細管現象を利用し、液晶の等方相温度以上である105℃で、ネマティック液晶(メルク社製ZLI-4792)を注入して、液晶セルを得た。 Using the obtained substrate with a liquid crystal alignment film before the alignment treatment, this is heated to 240 ° C. on a hot plate and polarized from a certain direction with respect to the liquid crystal alignment film surface on the substrate while maintaining the heated state. The polarized ultraviolet light was irradiated through the plate. The intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 250 mJ. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
Two substrates with this liquid crystal alignment film were prepared, and 14 μm spacers (manufactured by Nippon Shokubai Co., Ltd., true sphere) were sprayed on one liquid crystal alignment film surface, and then a sealing agent (XN- 1500T) was applied. Subsequently, after bonding together so that the other board | substrate and liquid crystal aligning film surface might face each other, it hardened | cured by heating the sealing compound at 150 degreeC for 150, and produced the empty cell. By utilizing capillary action, nematic liquid crystal (ZLI-4792 manufactured by Merck & Co., Inc.) was injected into the empty cell at 105 ° C., which is higher than the isotropic phase temperature of the liquid crystal, to obtain a liquid crystal cell.
偏光された紫外線の照射量を500mJとしたこと以外は、上述の実施例10と同様の方法に従い液晶セルを製造した。 <Example 11>
A liquid crystal cell was produced according to the same method as in Example 10 except that the irradiation amount of polarized ultraviolet rays was 500 mJ.
偏光された紫外線の照射量を50mJとしたこと以外は、上述の実施例10と同様の方法に従い液晶セルを製造した。 <Comparative Example 5>
A liquid crystal cell was produced according to the same method as in Example 10 except that the irradiation amount of polarized ultraviolet rays was 50 mJ.
実施例1で得られた液晶配向処理剤(I)を用いて液晶配向膜を作製し、その液晶配向膜を用いた液晶セルを製造した。液晶セルは、実施例10と同様に平行配向の液晶セルとした。 <Comparative Example 6>
A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agent (I) obtained in Example 1, and a liquid crystal cell using the liquid crystal alignment film was manufactured. The liquid crystal cell was a parallel alignment liquid crystal cell as in Example 10.
偏光された紫外線の照射量を250mJとしたこと以外は、比較例10と同様の方法に従い液晶セルを製造した。 <Comparative Example 7>
A liquid crystal cell was produced in the same manner as in Comparative Example 10 except that the irradiation amount of polarized ultraviolet rays was 250 mJ.
偏光された紫外線の照射量を500mJとしたこと以外は、比較例10と同様の方法に従い液晶セルを製造した。
実施例10、11及び比較例5~8において作製された液晶セルの液晶配向膜の作製条件を表3にまとめて示す。 <Comparative Example 8>
A liquid crystal cell was produced in the same manner as in Comparative Example 10 except that the irradiation amount of polarized ultraviolet rays was 500 mJ.
Table 3 summarizes the conditions for producing the liquid crystal alignment films of the liquid crystal cells produced in Examples 10 and 11 and Comparative Examples 5 to 8.
実施例10、11及び比較例5~8で得られた液晶セルの液晶配向膜について、偏光顕微鏡(ニコン社製)を用いた液晶の配向状態の評価を行った。 [Evaluation of liquid crystal display elements]
The liquid crystal alignment films of the liquid crystal cells obtained in Examples 10 and 11 and Comparative Examples 5 to 8 were evaluated for the alignment state of the liquid crystals using a polarizing microscope (Nikon Corporation).
一方、比較例5~8で得られた液晶セルでは、多数の欠陥が観察され、液晶の均一な配向が形成されていないことがわかった。紫外線照射量が500mJである比較例6の液晶セルでも液晶の均一配向は実現されず、十分な配向処理がなされていないことがわかった。 As shown in FIG. 4, no defects were observed in the liquid crystal cells obtained in Examples 10 and 11. And when it rotated under the crossed Nicols of a polarizing microscope, it was confirmed that clear brightness and darkness were produced, and it was confirmed that the liquid crystal is parallel-aligned uniformly. It can be seen that sufficient alignment treatment was performed even in the liquid crystal cell of Example 6 in which the amount of ultraviolet irradiation was 250 mJ.
On the other hand, in the liquid crystal cells obtained in Comparative Examples 5 to 8, many defects were observed, and it was found that a uniform alignment of the liquid crystal was not formed. It was found that even in the liquid crystal cell of Comparative Example 6 having an ultraviolet irradiation amount of 500 mJ, liquid crystal uniform alignment was not realized and sufficient alignment treatment was not performed.
以上の評価結果から、本発明の液晶配向膜の製造方法を用い、少ない紫外線照射量によって作製された本発明の液晶配向膜は、液晶表示素子を提供できることがわかった。
[実施例B] Next, using the liquid crystal cells obtained in Examples 10 and 11, each was sandwiched between a pair of polarizing plates arranged in a crossed Nicol configuration, thereby forming a liquid crystal display element. In the obtained liquid crystal display elements, it was confirmed that by applying a voltage between the ITO electrodes on the substrate, the change in the alignment of the liquid crystal was caused and the amount of transmitted light could be changed.
From the above evaluation results, it was found that the liquid crystal alignment film of the present invention produced by using the method for producing a liquid crystal alignment film of the present invention with a small amount of ultraviolet irradiation can provide a liquid crystal display element.
[Example B]
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
p-PDA:p-フェニレンジアミン
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
APHFP:
ジアミン[1]~[7]:下記式で表されるジアミン[1]~[7] The meanings of the abbreviations used in the examples are as follows.
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride p-PDA: p-phenylenediamine
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve APHFP:
Diamine [1] to [7]: Diamine [1] to [7] represented by the following formula
合成例における1H-NMRの測定条件は、以下の通りである。
装置:フーリエ変換型超伝導核磁気共鳴装置(FT-NMR)INOVA-400(Varian社製)400MHz
溶媒:重水素化ジメチルスルホキシド(DMSO-d6)及び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) <Measurement of 1 H-NMR>
The measurement conditions of 1 H-NMR in the synthesis examples are as follows.
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 ) and deuterated chloroform (CDCl 3 )
Standard substance: Tetramethylsilane (TMS)
ポリマー(ポリアミック酸等)の分子量の測定条件は、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、及び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(リットル)、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル: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、及び30,000)、及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、及び1,000)。 <Measurement of molecular weight of polymer>
The measurement conditions of the molecular weight of the polymer (polyamic acid or the like) are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Column manufactured by Shodex (KD-803 and KD-805)
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, and 30,000), and polymer laboratory polyethylene glycol ( Molecular weights of about 12,000, 4,000, and 1,000).
(合成例1)
ジアミン[1]((E,E)-Bis-(4'-aminophenyl) 1,4-benzenediacrylate)の合成 <Synthesis of diamine>
(Synthesis Example 1)
Synthesis of Diamine [1] ((E, E) -Bis- (4'-aminophenyl) 1,4-benzenediacrylate)
1H-NMR(400MHz, DMSO-d6, δppm):12.4(2H, brs), 7.74(4H, s), 7.60(2H, d), 6.61(2H, d). To a 2 L four-necked flask, terephthalaldehyde [A] (40.00 g, 298 mmol), pyridine (46 g), and piperidine (7.0 g) were added, and the reaction solution was heated to 100 ° C. with stirring. Next, a pyridine solution (500 g) of malonic acid [B] (140.0 g, 1.34 mol) was dropped into the reaction solution. After confirming the completion of the reaction by HPLC (high performance liquid chromatography), the reaction solution was cooled to 40 ° C., and the reaction solution was poured into distilled water (1 L). Next, concentrated hydrochloric acid was added until the reaction solution became acidic, and then the solid was filtered. Thereafter, it was washed with water, further washed with methanol, and dried under reduced pressure to obtain compound [C] (yield: 60.3 g, yield: 93%). The 1 H-NMR measurement result of the obtained compound [C] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 12.4 (2H, brs), 7.74 (4H, s), 7.60 (2H, d), 6.61 (2H, d).
1H-NMR(400MHz, DMSO-d6, δppm):8.36-8.31(4H, m), 7.92(2H, d), 7.68(4H, s), 7.40-7.37(4H, m), 6.70(2H, d). Next, in a 1 L four-necked flask, compound [C] (30.00 g, 138 mmol), 4-nitrophenol [D] (42.08 g, 303 mmol), 1-ethyl-3- (3-dimethylaminopropyl) Carbodiimide hydrochloride (hereinafter abbreviated as EDC) (68.53 g, 358 mmol), 4-N, N-dimethylaminopyridine (hereinafter abbreviated as DMAP) (3.56 g, 27.5 mmol), and tetrahydrofuran (hereinafter referred to as THF) And (600 g) was added, and the mixture was stirred at 23 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a mixed solution of ethyl acetate (500 mL) / distilled water (1 L), and the solid was filtered. Then, it wash | cleaned with the ethyl acetate / methanol 1: 1 mixed solution, and it dried under reduced pressure, and obtained compound [E] (yield: 60.6g, yield: 96%). The results of 1 H-NMR measurement of the obtained compound [E] are shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 8.36-8.31 (4H, m), 7.92 (2H, d), 7.68 (4H, s), 7.40-7.37 (4H, m), 6.70 (2H, d).
1H-NMR(400MHz, DMSO-d6, δppm):7.83(4H, s), 7.79(2H, d), 6.89(2H, d), 6.81-6.78(4H, m), 6.56-6.53(4H, m), 5.04(4H, brs). Next, compound [E] (63.30 g, 138 mmol), tin chloride (182.5 g, 962 mmol), THF (630 g), and distilled water (440 g) were added to a 2 L four-necked flask and heated at 70 ° C. Stirring was performed. After confirming the completion of the reaction by HPLC, N, N-dimethylacetamide (1 L) was added, and then the reaction solution was diluted with ethyl acetate (2.5 L), and carbonic acid was added until no by-product tin hydroxide was precipitated. Sodium hydride was added. Thereafter, the supernatant was filtered, the filtrate was separated, and the aqueous layer was removed. Thereafter, the organic layer was washed sequentially with 1 L of saturated aqueous sodium hydrogen carbonate solution (twice) and brine (twice), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with an evaporator to obtain a crude product, methanol (200 mL) was added, and the mixture was stirred at room temperature (23 ° C.) for 30 minutes. Thereafter, the mixture was filtered again, washed with methanol, and dried under reduced pressure to obtain diamine [1] (yield: 24.0 g, yield: 44%). The 1 H-NMR measurement result of the obtained diamine [1] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 7.83 (4H, s), 7.79 (2H, d), 6.89 (2H, d), 6.81-6.78 (4H, m), 6.56-6.53 (4H, m), 5.04 (4H, brs).
ジアミン[2]((E,E)-Bis-(4'-aminophenylethyl) 1,4-benzenediacrylate)の合成 (Synthesis Example 2)
Synthesis of Diamine [2] ((E, E) -Bis- (4'-aminophenylethyl) 1,4-benzenediacrylate)
1H-NMR(400MHz, DMSO-d6, δppm):7.66(2H, d), 7.73(4H, s), 7.60(2H, d), 6.90-6.88(4H, m), 6.66(2H, d), 6.45-6.46(4H, m), 4.88(4H, brs), 4.21(4H, t), 2.75(4H, t). Next, compound [G] (71.48 g, 138 mmol), tin chloride (183.4 g, 969 mmol), THF (715 g), and distilled water (500 g) are added to a 2 L four-necked flask and heated at 70 ° C. Stirring was performed. After confirming the completion of the reaction by HPLC, N, N-dimethylacetamide (1 L) was added, and then the reaction solution was diluted with ethyl acetate (2.5 L), and carbonic acid was added until no by-product tin hydroxide was precipitated. Sodium hydride was added. Thereafter, the supernatant was filtered, the filtrate was separated, and the aqueous layer was removed. Thereafter, the organic layer was washed sequentially with 1 L of saturated aqueous sodium hydrogen carbonate solution (twice) and brine (twice), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with an evaporator to obtain a crude product, methanol (200 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was filtered again, washed with methanol, and dried under reduced pressure to obtain diamine [2] (yield: 30.6 g, yield: 48%). The 1 H-NMR measurement result of the obtained diamine [2] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 7.66 (2H, d), 7.73 (4H, s), 7.60 (2H, d), 6.90-6.88 (4H, m), 6.66 (2H, d) , 6.45-6.46 (4H, m), 4.88 (4H, brs), 4.21 (4H, t), 2.75 (4H, t).
ジアミン[3]((E,E)-Bis-(4'-aminophenyl) 1,3-benzenediacrylate)の合成 (Synthesis Example 3)
Synthesis of Diamine [3] ((E, E) -Bis- (4'-aminophenyl) 1,3-benzenediacrylate)
1H-NMR(400MHz, DMSO-d6, δppm):12.4(2H, brs), 8.07(1H, s), 7.72(2H, dd), 7.61(2H, d), 7.46(1H, t). Isophthalaldehyde [H] (50.00 g, 373 mol), pyridine (78 g), and piperidine (9.5 g) were added to a 2 L four-necked flask, and the reaction solution was heated to 100 ° C. with stirring. Then, a pyridine solution (600 g) of malonic acid [B] (169.5 g, 1.68 mol) was dropped into the reaction solution. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 40 ° C., and the reaction solution was poured into distilled water (1 L). Next, concentrated hydrochloric acid was added until the reaction solution became acidic, and then the solid was filtered. Then, it washed with water and the crude product of compound [I] was obtained. This crude product was stirred with an ethyl acetate / methanol 1: 1 mixed solution at room temperature for 30 minutes. Thereafter, the mixture was filtered, washed with ethyl acetate, and dried under reduced pressure to obtain compound [I] (yield: 80.2 g, yield: 99%). The results of 1 H-NMR measurement of the obtained compound [I] are shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 12.4 (2H, brs), 8.07 (1H, s), 7.72 (2H, dd), 7.61 (2H, d), 7.46 (1H, t).
1H-NMR(400MHz, DMSO-d6, δppm):8.37(1H, s), 8.32-8.29(4H, m), 7.92(2H, d), 7.88(2H, dd), 7.56-7.51(5H, m), 7.08(2H, d). Next, in a 1 L four-necked flask, compound [I] (30.00 g, 138 mmol), 4-nitrophenol [D] (40.17 g, 289 mmol), EDC (63.26 g, 330 mmol), DMAP (3. 36 g, 27.5 mmol) and THF (600 g) were added, and the mixture was stirred at 23 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a mixed solution of ethyl acetate (500 mL) / distilled water (1 L), and the solid was filtered. Then, it was washed with ethyl acetate and dried under reduced pressure to obtain compound [J] (yield: 62.1 g, yield: 98%). The 1 H-NMR measurement result of the obtained compound [J] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 8.37 (1H, s), 8.32-8.29 (4H, m), 7.92 (2H, d), 7.88 (2H, dd), 7.56-7.51 (5H, m), 7.08 (2H, d).
1H-NMR(400MHz, DMSO-d6, δppm):8.27(1H, s), 7.82-7.77(4H, m), 7.49(1H, t), 6.96(2H, d), 6.82-6.78(4H, m), 6.56-6.53(4H, m), 5.04(4H, brs). Next, the compound [J] (62.1 g, 135 mmol), tin chloride (182.5 g, 962 mmol), THF (630 g), and distilled water (630 g) are added to a 2 L four-necked flask, and heated at 70 ° C. Stirring was performed. After confirming the completion of the reaction by HPLC, the reaction solution was diluted with ethyl acetate (2 L), and sodium bicarbonate was added until no by-product tin hydroxide was precipitated. Thereafter, the supernatant was filtered, the filtrate was separated, and the aqueous layer was removed. Thereafter, the organic layer was washed sequentially with 1 L of saturated aqueous sodium hydrogen carbonate solution (twice) and brine (twice), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with an evaporator to obtain a crude product, methanol (200 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was filtered again, washed with methanol, and dried under reduced pressure to obtain diamine [3] (yield: 34.1 g, yield: 54%). The 1 H-NMR measurement result of the obtained diamine [3] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 8.27 (1H, s), 7.82-7.77 (4H, m), 7.49 (1H, t), 6.96 (2H, d), 6.82-6.78 (4H, m), 6.56-6.53 (4H, m), 5.04 (4H, brs).
ジアミン[4]((E,E)-Bis-(4'-aminophenylethyl) 1,3-benzenediacrylate)の合成 (Synthesis Example 4)
Synthesis of Diamine [4] ((E, E) -Bis- (4'-aminophenylethyl) 1,3-benzenediacrylate)
1H-NMR(400MHz, DMSO-d6, δppm):8.17-8.14(4H, m), 8.11(1H, s), 7.70(2H, dd), 7.62(1H, s), 7.59-7.56(5H, m), 7.42(1H, t), 6.71(2H, d), 4.41(4H, t), 3.10(4H, t). In a 1 L four-necked flask, compound [I] (54.92 g, 252 mmol), 2- (4-nitrophenyl) ethanol [F] (92.58 g, 554 mmol), EDC (125.4 g, 654 mmol), DMAP ( 6.15 g, 50.3 mmol) and THF (1.1 Kg) were added, and the mixture was stirred at 23 ° C. After confirming the completion of the reaction by HPLC, ethyl acetate (1 L) / hexane (500 mL) / distilled water (1 L) was added to the reaction solution, and the aqueous layer was removed by a liquid separation operation. Thereafter, the organic layer was washed three times with brine (1 L), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with an evaporator to obtain a crude product of compound [K]. Methanol (300 g) was added to the crude product and stirred at room temperature for 30 minutes. Then, it filtered and dried under reduced pressure and compound [K] was obtained (yield: 82.2 g, yield: 63%). The 1 H-NMR measurement result of the obtained compound [K] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 8.17-8.14 (4H, m), 8.11 (1H, s), 7.70 (2H, dd), 7.62 (1H, s), 7.59-7.56 (5H, m), 7.42 (1H, t), 6.71 (2H, d), 4.41 (4H, t), 3.10 (4H, t).
1H-NMR(400MHz, CDCl3, δppm):7.66(2H, d), 7.63(1H, s), 7.54-7.39(1H, m), 7.07-7.04(4H, m), 6.68-6.65(4H, m), 6.45(2H, d), 5.04(4H, brs), 4.37(4H, t), 2.91(4H, t). Next, compound [K] (82.21 g, 139 mmol), tin chloride (211.3 g, 1.11 mol), THF (820 g), and distilled water (820 g) were added to a 2 L four-necked flask at 70 ° C. The mixture was heated and stirred. After confirming the completion of the reaction by HPLC, the reaction solution was diluted with ethyl acetate (2.5 L), and sodium bicarbonate was added until no by-product tin hydroxide was precipitated. Thereafter, the supernatant was filtered, the filtrate was separated, and the aqueous layer was removed. Thereafter, the organic layer was washed sequentially with 1 L of saturated aqueous sodium hydrogen carbonate solution (twice) and brine (twice), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with an evaporator to obtain a crude product, methanol (200 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was filtered again, washed with methanol, and dried under reduced pressure to obtain diamine [4] (yield: 46.1 g, yield: 73%). The 1 H-NMR measurement result of the obtained diamine [4] is shown below.
1 H-NMR (400 MHz, CDCl3, δ ppm): 7.66 (2H, d), 7.63 (1H, s), 7.54-7.39 (1H, m), 7.07-7.04 (4H, m), 6.68-6.65 (4H, m), 6.45 (2H, d), 5.04 (4H, brs), 4.37 (4H, t), 2.91 (4H, t).
ジアミン[5]((E)-4-aminophenethyl 3-(4-aminophenyl)acrylate)の合成 (Synthesis Example 5)
Synthesis of Diamine [5] ((E) -4-aminophenethyl 3- (4-aminophenyl) acrylate)
1H-NMR(400MHz, DMSO-d6, δppm):7.46(1H, d), 7.37 (2H, d), 6.92(2H, d), 6.56-6.47(4H, m), 6.20(1H, d), 5.78(2H,s), 4.89(2H,s), 4.18(2H,t), 2.74(2H, t). Subsequently, the compound [N] obtained above (22.4 g, 65.5 mmol), tin (II) chloride (80 g, 458.7 mmol), 200 g of THF, and 100 g of distilled water were added to a 500 mL reaction vessel. The mixture was heated and stirred at ° C. After completion of the reaction, the reaction solution was neutralized with sodium hydrogen carbonate and extracted with ethyl acetate. After the solvent of the extract was distilled off, the obtained yellow crystals were dried to obtain diamine [5] (yield: 14.0 g, yield: 76%). The 1 H-NMR measurement result of the obtained diamine [5] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 7.46 (1H, d), 7.37 (2H, d), 6.92 (2H, d), 6.56-6.47 (4H, m), 6.20 (1H, d) , 5.78 (2H, s), 4.89 (2H, s), 4.18 (2H, t), 2.74 (2H, t).
ジアミン[6]((2E,2'E)-pentane-1,5-diyl bis(3-(4-aminophenyl)acrylate))の合成 (Synthesis Example 6)
Synthesis of Diamine [6] ((2E, 2'E) -pentane-1,5-diyl bis (3- (4-aminophenyl) acrylate))
1H-NMR(400MHz, DMSO-d6, δppm):7.47(2H,d), 7.36(4H,d), 6.55(4H,d), 6.22(2H,d), 5.76(4H,s), 4.10(4H,t), 1.99-1.63(4H, m), 1.46-1.40(2H,m). Subsequently, the compound [P] obtained above (15 g, 33.0 mmol), tin (II) chloride (43.8 g, 231.0 mmol), 150 g of THF, and 150 g of distilled water were added to a 500 mL reaction vessel, and The mixture was stirred with heating. After completion of the reaction, the reaction solution was neutralized with sodium bicarbonate and extracted with ethyl acetate. After the solvent of the extract was distilled off, the resulting yellow crystals were washed with ethyl acetate and hexane in order to obtain diamine [6] (yield: 11.9 g, yield: 91%). The 1 H-NMR measurement result of the obtained diamine [6] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 7.47 (2H, d), 7.36 (4H, d), 6.55 (4H, d), 6.22 (2H, d), 5.76 (4H, s), 4.10 (4H, t), 1.99-1.63 (4H, m), 1.46-1.40 (2H, m).
ジアミン[7]((E)-4-aminophenyl 3-(4-aminophenyl)acrylate)の合成 (Synthesis Example 7)
Synthesis of Diamine [7] ((E) -4-aminophenyl 3- (4-aminophenyl) acrylate)
1H-NMR(400MHz, DMSO-d6, δppm):7.60(1H,d), 7.43(2H,d), 6.78(2H,d), 6.77-6.36(4H,m), 6.10(1H,d), 5.85(2H,s), 5.02(2H,s). Next, in a 2 L reaction vessel, the compound [Q] obtained above (30 g, 95.5 mmol), reduced iron (21.0 g, 382 mmol), ammonium chloride (40.8 g, 762.8 mmol), N, 200 g of N-dimethylformaldehyde, 200 g of ethyl acetate, and 400 g of distilled water were added, and the mixture was heated and stirred at 70 ° C. After completion of the reaction, the mixture was extracted with ethyl acetate and treated with activated carbon. Then, it filtered and the crude crystal was obtained by distilling a solvent off further. The obtained crude crystals were purified by suspending in order with methanol and hexane to obtain diamine [7] (yield: 19.4 g, yield: 80%). The 1 H-NMR measurement result of the obtained diamine [7] is shown below.
1 H-NMR (400 MHz, DMSO-d6, δ ppm): 7.60 (1H, d), 7.43 (2H, d), 6.78 (2H, d), 6.77-6.36 (4H, m), 6.10 (1H, d) , 5.85 (2H, s), 5.02 (2H, s).
ジアミンDA-1の合成
日本特公表2001-517719号公報の実施例1に従って、ジアミンDA-1を合成した。 (Comparative Synthesis Example 1)
Synthesis of Diamine DA-1 Diamine DA-1 was synthesized according to Example 1 of Japanese Patent Publication No. 2001-517719.
(液晶配向処理剤A1)
ジアミン[1](1.20g、3.0mmol)にNMP(5.0g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.53g、2.8mmol)とNMP(5.0g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A1を得た。このポリアミック酸の数平均分子量は6000であり、重量平均分子量は10500であった。 <Preparation of liquid crystal aligning agent>
(Liquid crystal aligning agent A1)
NMP (5.0 g) was added to diamine [1] (1.20 g, 3.0 mmol), and the mixture was stirred and completely dissolved at room temperature, and then CBDA (0.53 g, 2.8 mmol) and NMP (5. 0 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A1. The number average molecular weight of this polyamic acid was 6000, and the weight average molecular weight was 10500.
ジアミン[2](1.37g、3.0mmol)にNMP(5.4g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.55g、2.8mmol)とNMP(5.4g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A2を得た。このポリアミック酸の数平均分子量は3800であり、重量平均分子量は5000であった。 (Liquid crystal aligning agent A2)
NMP (5.4 g) was added to diamine [2] (1.37 g, 3.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.55 g, 2.8 mmol) and NMP (5. 4 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A2. The number average molecular weight of this polyamic acid was 3800, and the weight average molecular weight was 5000.
ジアミン[3](1.20g、3.0mmol)にNMP(5.0g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.55g、2.8mmol)とNMP(5.0g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A3を得た。このポリアミック酸の数平均分子量は8100であり、重量平均分子量は16000であった。 (Liquid crystal aligning agent A3)
NMP (5.0 g) was added to diamine [3] (1.20 g, 3.0 mmol), and the mixture was stirred and completely dissolved at room temperature, and then CBDA (0.55 g, 2.8 mmol) and NMP (5. 0 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A3. The number average molecular weight of this polyamic acid was 8100, and the weight average molecular weight was 16000.
ジアミン[4](1.37g、3.0mmol)にNMP(5.4g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.55g、2.8mmol)とNMP(5.4g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A4を得た。このポリアミック酸の数平均分子量は5200であり、重量平均分子量は7600であった。 (Liquid crystal aligning agent A4)
NMP (5.4 g) was added to diamine [4] (1.37 g, 3.0 mmol) and stirred at room temperature for complete dissolution, then CBDA (0.55 g, 2.8 mmol) and NMP (5. 4 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A4. The number average molecular weight of this polyamic acid was 5200, and the weight average molecular weight was 7600.
ジアミン[5](7.06g、25.0mmol)にNMP(32.3g)を加え、室温で撹拌して完全に溶解させた後、CBDA(4.51g、23.0mmol)とNMP(33.2g)を加え、室温で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(40g)にNMP(40.0g)及びBCS(20.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A5を得た。このポリアミック酸の数平均分子量は10500であり、重量平均分子量は57000であった。 (Liquid crystal aligning agent A5)
NMP (32.3 g) was added to diamine [5] (7.06 g, 25.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (4.51 g, 23.0 mmol) and NMP (33. 2 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A5. The number average molecular weight of this polyamic acid was 10500, and the weight average molecular weight was 57000.
ジアミン[6](1.18g、3.0mmol)にNMP(4.9g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.53g、2.7mmol)とNMP(4.9g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A6を得た。このポリアミック酸の数平均分子量は8800であり、重量平均分子量は35000であった。 (Liquid crystal aligning agent A6)
NMP (4.9 g) was added to diamine [6] (1.18 g, 3.0 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.53 g, 2.7 mmol) and NMP (4. 9 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A6. The number average molecular weight of this polyamic acid was 8800, and the weight average molecular weight was 35000.
ジアミン[7](1.14g、4.5mmol)にNMP(5.6g)を加え、室温で撹拌して完全に溶解させた後、CBDA(0.83g、4.2mmol)とNMP(5.6g)を加え、室温で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(10g)にNMP(10.0g)及びBCS(5.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤A7を得た。このポリアミック酸の数平均分子量は13800であり、重量平均分子量は35500であった。
(液晶配向処理剤A8)
ジアミン[5](3.53g、12.5mmol)及びp-PDA(1.35g、12.5mmol)にNMP(27.0g)を加え、室温で撹拌して完全に溶解させた後、CBDA(4.66g、23.8mmol)とNMP(27.0g)を加え、室温で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(40g)にNMP(40.0g)及びBCS(20.0g)を加え、室温で5時間攪拌することにより、液晶配向処理剤A8を得た。このポリアミック酸の数平均分子量は11500であり、重量平均分子量は25000であった。 (Liquid crystal aligning agent A7)
NMP (5.6 g) was added to diamine [7] (1.14 g, 4.5 mmol) and stirred at room temperature for complete dissolution, and then CBDA (0.83 g, 4.2 mmol) and NMP (5.2. 6 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (10.0g) and BCS (5.0g) were added to this polyamic acid solution (10g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent A7. The number average molecular weight of this polyamic acid was 13800, and the weight average molecular weight was 35500.
(Liquid crystal aligning agent A8)
NMP (27.0 g) was added to diamine [5] (3.53 g, 12.5 mmol) and p-PDA (1.35 g, 12.5 mmol), and the mixture was stirred at room temperature until completely dissolved, and then CBDA ( 4.66 g, 23.8 mmol) and NMP (27.0 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and the liquid crystal aligning agent A8 was obtained by stirring at room temperature for 5 hours. The number average molecular weight of this polyamic acid was 11500, and the weight average molecular weight was 25000.
DA-1(5.10g、14.0mmol)にNMP(22.0g)を加え、室温で撹拌して完全に溶解させた後、CBDA(2.66g、13.6mmol)とNMP(22.0g)を加え、室温で5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(40g)にNMP(40.0g)及びBCS(20.0g)を加え、室温にて5時間攪拌することにより、液晶配向処理剤B1を得た。このポリアミック酸の数平均分子量は6500であり、重量平均分子量は26000であった。 (Liquid crystal aligning agent B1)
NMP (22.0 g) was added to DA-1 (5.10 g, 14.0 mmol), and the mixture was stirred and completely dissolved at room temperature. Then, CBDA (2.66 g, 13.6 mmol) and NMP (22.0 g) were added. ) And reacted at room temperature for 5 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic acid solution (40g), and it stirred at room temperature for 5 hours, and obtained liquid crystal aligning agent B1. The number average molecular weight of this polyamic acid was 6500, and the weight average molecular weight was 26000.
液晶配向処理剤A1を用いて、下記に示す手順で液晶セルの作製を行った。
基板は、30mm×40mmの大きさで、厚さが0.7mmのガラス基板であり、ITO膜をパターニングして形成された櫛歯状の画素電極が配置されたものを用いた。画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は3μmであり、電極要素間の間隔は6μmである。各画素を形成する画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字のくの字に似た形状を備える。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有する。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっている。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+10°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-10°の角度(時計回り)をなすように形成されている。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されている。 Example 1
Using the liquid crystal aligning agent A1, a liquid crystal cell was produced according to the procedure shown below.
The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged. The pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 3 μm, and the distance between the electrode elements is 6 μm. The pixel electrode forming each pixel is configured by arranging a plurality of dog-shaped electrode elements whose central part is bent, so that the shape of each pixel is not rectangular, and is similar to the electrode element in the central part. It has a shape that bends and resembles a bold-faced koji. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of −10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
上記で得られたIPSモード用液晶セルの配向状態を偏光顕微鏡にて観察し、配向欠陥がないものを「良好」、配向欠陥があるものは「不良」とした。結果を表4に示す。 (Liquid crystal alignment performance evaluation)
The alignment state of the liquid crystal cell for IPS mode obtained above was observed with a polarizing microscope, and “good” was obtained when there was no alignment defect, and “bad” when there was an alignment defect. The results are shown in Table 4.
上記で得られたIPSモード用液晶セルを、偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態で光源を点灯させておき、透過光の輝度が最も小さくなるように液晶セルの配置角度を調整した。次いで、画素の第2領域が最も暗くなる角度から第1領域が最も暗くなる角度まで液晶セルを回転させたときの回転角度(配向方位角)を、初期配向方位角として算出した。次いで、室温環境下、周波数30Hzで8VPPの交流電圧を24時間印加した。その後、液晶セルの画素電極と対向電極との間をショートさせた状態にし、そのまま室温に1時間放置した。放置の後、同様にして配向方位角を測定し、交流駆動前後の配向方位角の差、すなわち、(交流駆動前の配向方位角)-(交流駆動後の配向方位角)を、Δ配向方位角(°)として算出した。結果を表4に示す。 (Afterimage evaluation)
The IPS mode liquid crystal cell obtained above is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the light source is turned on with no voltage applied, and the transmitted light has the highest luminance. The arrangement angle of the liquid crystal cell was adjusted so as to be small. Next, the rotation angle (alignment azimuth angle) when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial alignment azimuth. Next, an AC voltage of 8 V PP was applied for 24 hours at a frequency of 30 Hz in a room temperature environment. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour. After standing, the orientation azimuth is measured in the same manner, and the difference in orientation azimuth before and after AC driving, that is, (alignment azimuth before AC driving) − (alignment azimuth after AC driving) is expressed as Δ orientation azimuth. Calculated as an angle (°). The results are shown in Table 4.
液晶配向処理剤A1のかわりに液晶配向処理剤A2を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。 (Example 2)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A2 was used instead of the liquid crystal alignment treatment agent A1.
液晶配向処理剤A1のかわりに液晶配向処理剤A3を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。 (Example 3)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A3 was used instead of the liquid crystal alignment treatment agent A1.
液晶配向処理剤A1のかわりに液晶配向処理剤A4を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。 (Example 4)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A4 was used instead of the liquid crystal alignment treatment agent A1.
液晶配向処理剤A1のかわりに液晶配向処理剤A5を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。 (Example 5)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A5 was used instead of the liquid crystal alignment treatment agent A1.
液晶配向処理剤A1のかわりに液晶配向処理剤A6を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。
(実施例7)
液晶配向処理剤A1のかわりに液晶配向処理剤A7を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。
(実施例8)
液晶配向処理剤A1のかわりに液晶配向処理剤A8を用いた以外は実施例1と同様の操作を行って、液晶配向性能評価及び残像評価を行った。 (Example 6)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A6 was used instead of the liquid crystal alignment treatment agent A1.
(Example 7)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A7 was used instead of the liquid crystal alignment treatment agent A1.
(Example 8)
A liquid crystal alignment performance evaluation and an afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment treatment agent A8 was used instead of the liquid crystal alignment treatment agent A1.
液晶配向処理剤A1を用い、室温にて液晶配向膜面に偏光板を介して313nmの紫外線を20mJ/cm2照射した以外は、実施例1と同様の操作を行って、液晶配向性能評価を行った。
<比較例10>
液晶配向処理剤A1の代わりに液晶配向処理剤A2を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。
<比較例11>
液晶配向処理剤A1の代わりに液晶配向処理剤A3を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。
<比較例12>
液晶配向処理剤A1の代わりに液晶配向処理剤A4を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。
<比較例13>
液晶配向処理剤A1の代わりに液晶配向処理剤A5を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。
<比較例14>
液晶配向処理剤A1の代わりに液晶配向処理剤A7を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。
<比較例15>
液晶配向処理剤A1の代わりに液晶配向処理剤A8を用いた以外は比較例9と同様の操作を行って、液晶配向性能評価を行った。 <Comparative Example 9>
The liquid crystal alignment performance evaluation was performed by performing the same operation as in Example 1 except that the liquid crystal alignment treatment agent A1 was used and the surface of the liquid crystal alignment film was irradiated with 20 mJ / cm 2 of 313 nm ultraviolet light at room temperature via a polarizing plate. went.
<Comparative Example 10>
Liquid crystal alignment performance evaluation was performed by performing the same operation as Comparative Example 9 except that the liquid crystal alignment treatment agent A2 was used instead of the liquid crystal alignment treatment agent A1.
<Comparative Example 11>
Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A3 was used instead of the liquid crystal alignment treatment agent A1.
<Comparative Example 12>
Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A4 was used instead of the liquid crystal alignment treatment agent A1.
<Comparative Example 13>
Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A5 was used instead of the liquid crystal alignment treatment agent A1.
<Comparative example 14>
Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A7 was used instead of the liquid crystal alignment treatment agent A1.
<Comparative Example 15>
Liquid crystal alignment performance evaluation was performed by performing the same operation as in Comparative Example 9 except that the liquid crystal alignment treatment agent A8 was used instead of the liquid crystal alignment treatment agent A1.
Claims (12)
- 基板上に光反応基を有するポリイミド若しくはポリイミド前駆体を含有する薄膜を形成し、前薄膜面を加熱しながら、偏光した紫外線を照射し、前記基板上にポリイミド前駆体を含有する高分子からなる液晶配向膜を製造することを特徴とする液晶配向膜の製造方法。 A thin film containing a photoreactive group-containing polyimide or polyimide precursor is formed on the substrate, and the front thin film surface is irradiated with polarized ultraviolet rays while being heated, and the substrate is made of a polymer containing a polyimide precursor. A method for producing a liquid crystal alignment film, comprising producing a liquid crystal alignment film.
- 前記光反応基を有するポリイミド前駆体は、下記の式[1]で表される繰り返し単位及び下記の式[2]で表される繰り返し単位を含有することを特徴とする請求項1に記載の液晶配向膜の製造方法。
- 前記光反応基を有するポリイミド前駆体は、下記の式[1]で表される繰り返し単位及び下記の式[3]で表される繰り返し単位を含有することを特徴とする請求項1に記載の液晶配向膜の製造方法。
(式[3]において、R9は2価の有機基を表し、R10は光反応性基を構成する2価の有機基を表す。n3は正の整数を表す。) The polyimide precursor having the photoreactive group contains a repeating unit represented by the following formula [1] and a repeating unit represented by the following formula [3]. A method for producing a liquid crystal alignment film.
(In Formula [3], R 9 represents a divalent organic group, R 10 represents a divalent organic group constituting a photoreactive group, and n 3 represents a positive integer.) - 前記光反応基を有するポリイミド前駆体が、下記の式[4]で表されるジアミンを含むジアミン成分とテトラカルボン酸二無水物とを重縮合反応させて得られることを特徴とする請求項1に記載の液晶配向膜の製造方法。
- 前記薄膜の厚さが、5~300nmであることを特徴とする請求項1~4のいずれか1項に記載の液晶配向膜の製造方法。 The method for producing a liquid crystal alignment film according to any one of claims 1 to 4, wherein the thin film has a thickness of 5 to 300 nm.
- 前記光反応基を有するポリイミド前駆体の含有量が、0.1~30質量%であり、溶剤を含有する液晶配向処理剤を用いて前記薄膜を形成することを特徴とする請求項1~5のいずれか1項に記載の液晶配向膜の製造方法。 6. The thin film is formed using a liquid crystal aligning agent containing a solvent, wherein the content of the polyimide precursor having a photoreactive group is 0.1 to 30% by mass. The manufacturing method of the liquid crystal aligning film of any one of these.
- 前記加熱の温度は、前記光反応基を有するポリイミド前駆体が、ポリイミドに変化しない温度範囲から選択された温度であることを特徴とする請求項1~6のいずれか1項に記載の液晶配向膜の製造方法。 7. The liquid crystal alignment according to claim 1, wherein the heating temperature is selected from a temperature range in which the polyimide precursor having the photoreactive group does not change to polyimide. A method for producing a membrane.
- 前記加熱の温度は、50℃~300℃の範囲内であることを特徴とする請求項1~7のいずれか1項に記載の液晶配向膜の製造方法。 The method for producing a liquid crystal alignment film according to any one of claims 1 to 7, wherein the heating temperature is in the range of 50 ° C to 300 ° C.
- 前記加熱の温度は、80℃~250℃の範囲内であることを特徴とする請求項1~8のいずれか1項に記載の液晶配向膜の製造方法。 The method for producing a liquid crystal alignment film according to any one of claims 1 to 8, wherein the heating temperature is in the range of 80 ° C to 250 ° C.
- 紫外線の照射量が、100~1000mJであることを特徴とする請求項1~9のいずれか1項に記載の液晶配向膜の製造方法。 10. The method for producing a liquid crystal alignment film according to claim 1, wherein the irradiation amount of ultraviolet rays is 100 to 1000 mJ.
- 請求項1~10のいずれか1項に記載の液晶配向膜の製造方法により製造されたことを特徴とする液晶配向膜。 A liquid crystal alignment film manufactured by the method for manufacturing a liquid crystal alignment film according to any one of claims 1 to 10.
- 請求項11に記載の液晶配向膜を有することを特徴とする液晶表示素子。 A liquid crystal display element comprising the liquid crystal alignment film according to claim 11.
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Also Published As
Publication number | Publication date |
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CN103827740A (en) | 2014-05-28 |
TWI554555B (en) | 2016-10-21 |
KR101991140B1 (en) | 2019-06-19 |
KR20140048890A (en) | 2014-04-24 |
CN103827740B (en) | 2017-08-25 |
TW201313790A (en) | 2013-04-01 |
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