Classifications

• • 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
• • 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
• • 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
  • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
• • 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
  • G02F1/133765—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers without a surface treatment

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal display element obtained using them, and a method for producing the same.
• the liquid crystal alignment film is made of a polyamic acid formed on an electrode substrate and / or a surface of a film made of polyimide obtained by imidizing this with cotton, nylon, It is produced by carrying out a so-called rubbing process that rubs in one direction with a cloth such as polyester.
• the method of rubbing the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method that is simple and excellent in productivity.
• Patent Document 1 proposes that a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment method.
• a polyimide film using this photo-alignment method is adopted as a liquid crystal alignment film, its usefulness is expected because high heat resistance is obtained.
• Such a polyimide film having an alicyclic structure such as a cyclobutane ring is a liquid crystal alignment film that exhibits high anisotropy and is excellent in liquid crystal alignment by irradiating short-wave ultraviolet rays, particularly polarized ultraviolet rays around 254 nm. Is obtained.
• ultraviolet rays in the vicinity of 254 nm have high energy and require a large amount of power for irradiation, so that not only the cost for performing the photo-alignment treatment is high, but also the load on the environment is large.
• ultraviolet rays having a higher wavelength and higher energy are used, there is a possibility of damaging electrodes and thin film transistors (hereinafter also referred to as TFTs) formed on the substrate.
• the photo-alignment method using photoisomerization or photodimerization can provide anisotropy by irradiating polarized ultraviolet rays having a wavelength of 300 nm or more.
• a liquid crystal alignment film obtained by a photo-alignment method using photoisomerization or photodimerization has a weak alignment regulating force and has a problem that an afterimage occurs when used in a liquid crystal display element.
• An in-plane switching (IPS) type liquid crystal display element that switches liquid crystal molecules by applying an electric field in a horizontal direction (lateral direction) to a substrate is known. This lateral electric field drive type liquid crystal display element is useful because it has a wide viewing angle, but it is easily affected by the alignment state of the liquid crystal.
• a liquid crystal display element that responds by an electric field to liquid crystal molecules that are aligned perpendicular to the substrate
• ultraviolet light is applied while applying a voltage to the liquid crystal molecules during the manufacturing process.
• a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
• a technique for increasing the response speed of liquid crystal for example, see Patent Document 2 and Non-Patent Document 2 is known (PSA liquid crystal display element).
• the tilting direction of the liquid crystal molecules in response to the electric field is controlled by a protrusion provided on the substrate, a slit provided in the display electrode, or the like.
• a photopolymerizable compound to the liquid crystal composition and irradiating ultraviolet rays while applying a voltage to the liquid crystal cell, the polymer structure in which the tilted direction of the liquid crystal molecules is stored on the liquid crystal alignment film. Formed.
• the response speed of the liquid crystal display element is faster than the method of controlling the tilt direction of the liquid crystal molecules only by the protrusions and slits.
• An object of the present invention is to provide a liquid crystal aligning agent that has high alignment regulating power, and can improve the response speed of a liquid crystal display element without adding a photopolymerizable compound to the liquid crystal, particularly in the case of a vertical alignment method, and It is in providing the novel diamine compound which can be used for the liquid crystal display element obtained using this, its manufacturing method, and also the manufacture of the said liquid crystal aligning agent.
• the present inventor conducted extensive research to achieve the above object, and as a result, a specific compound having a benzophenone structure represented by the following formula [1] (wherein R 1 and R 2 are defined later)
• the liquid crystal aligning agent containing a polymer using as a starting material a polymer component that imparts liquid crystal alignment ability can improve the response speed of a liquid crystal display device having a liquid crystal alignment film obtained therefrom, We have found that the objective can be achieved.
• the present invention is based on the above findings and has the following gist.
• Diamine compound represented by the following formula [1] (wherein R 1 is a group represented by the following formula [2], a group represented by the following formula [3], an amino group, an aminophenyl group or a diaminophenyl group) And when R 1 is a group represented by the following formula [2] or a diaminophenyl group, R 2 is the number of carbon atoms to which a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a (meth) acryloyloxy group is bonded.
• R 1 is a group represented by the following formula [3], an amino group or an aminophenyl group, R 2 is an aminophenyl group or an aminobiphenyl group) and tetra
• a polyimide precursor obtained by reacting with carboxylic dianhydride, and at least one polymer selected from polyimides obtained by ring-closing the polyimide precursor;
• a (meth) acrylate compound represented by the following formula [1] wherein R 1 is a group represented by the following formula [4], R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or , A phenyl group or a biphenyl group, and one or a plurality of hydrogen atoms in the phenyl group or the biphenyl group may be replaced by a halogen group or an organic group.
• a liquid crystal aligning agent characterized by containing as a polymer component that imparts performance.
• R 3 is a single bond, —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH— or —CO—.
• R 4 has 1 to 30 alkylene groups, or a divalent carbocyclic or heterocyclic ring, wherein one or more hydrogen atoms in the alkylene group, divalent carbocyclic or heterocyclic ring are replaced by fluorine atoms or organic groups
• —CH 2 — in R 4 may be replaced by any of the following groups when they are not adjacent to each other: —O—, —NHCO—, — CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—
• R 5 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO— , -NH- or -CO-.
• R 6 is an alkylene group having 1 to 30 carbon atoms, or a divalent carbocycle or heterocycle, and one or more hydrogen atoms in the alkylene group, divalent carbocycle or heterocycle are fluorine atoms. Or —CH 2 — in R 6 may be replaced by any of these groups when any of the following groups is not adjacent to each other; O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO— R 7 represents —CH 2 —, —O—, —CONH—, —NHCO— , -COO-, -OCO-, -NH- or -CO-, and R 8 is a hydrogen atom or a methyl group.
• the diamine compound represented by the formula [1] is at least one compound selected from the group consisting of [1-A], [1-B], [1-C] and [1-D] described later.
• the liquid crystal aligning agent according to 1 above, wherein the (meth) acrylate compound represented by the formula [1] is a compound of the formula [1-E] described later. 4).
• the liquid crystal aligning agent according to 2 above which contains, as a polymer component, at least one polymer selected from polyimides obtained by ring-closing a body. 5.
• the diamine compound having a side chain for vertically aligning the liquid crystal is a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group or a steroid group, or a part of hydrogen atoms of these groups or 5.
• the liquid crystal aligning agent according to 4 above which is a diamine compound having a group in which all the fluorine atoms are replaced as side chains. 6). 6.
• liquid crystal aligning agent according to 4 or 5 above, wherein the diamine compound having a side chain for vertically aligning the liquid crystal is 5 mol% to 70 mol% in the diamine component. 7). 7. A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of 1 to 6 above. 8). 8. A liquid crystal display device comprising the liquid crystal alignment film as described in 7 above.
• a liquid crystal alignment film is formed by applying the liquid crystal aligning agent according to any one of the above 1 to 6 to a substrate and baking it, and the liquid crystal alignment film is subjected to alignment treatment, and two substrates having the liquid crystal alignment film are used.
• a method for producing a liquid crystal display element wherein a liquid crystal cell is produced by sandwiching liquid crystal, and the photopolymerizable group in the liquid crystal and / or the liquid crystal alignment film is reacted by irradiating the liquid crystal cell with light. 10.
• a liquid crystal alignment film is formed by applying the liquid crystal alignment agent according to any one of the above 1 to 4 to a substrate and baking it, and a liquid crystal layer is formed by sandwiching the liquid crystal between the two substrates having the liquid crystal alignment film. Then, a liquid crystal cell is produced by irradiating with ultraviolet rays while applying a voltage to the liquid crystal layer.
• R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a biphenyl group (provided that a phenyl group Or in biphenyl group One or more hydrogen atoms can also be) replaced by halogen group or an organic group compound.
• R 3 is a single bond, —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH— or —CO—.
• R 4 has 1 to 30 alkylene groups, or a divalent carbocycle or heterocycle, wherein one or more hydrogen atoms in the alkylene group, divalent carbocycle or heterocycle are replaced by fluorine atoms or organic groups
• —CH 2 — in R 4 may be replaced by any of the following groups when they are not adjacent to each other: —O—, —NHCO—, — CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—
• R 5 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO— , -NH- or -CO-.
• R 6 is an alkylene group having 1 to 30 carbon atoms, or a divalent carbocycle or heterocycle, and one or more hydrogen atoms in the alkylene group, divalent carbocycle or heterocycle are fluorine atoms. Or —CH 2 — in R 6 may be replaced by any of these groups when any of the following groups is not adjacent to each other; O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO— R 7 represents —CH 2 —, —O—, —CONH—, —NHCO— , -COO-, -OCO-, -NH- or -CO-, and R 8 is a hydrogen atom or a methyl group.
• a liquid crystal display element which has been subjected to alignment treatment by rubbing or photo-alignment method, in particular alignment treatment by photo-alignment, has a liquid crystal alignment film with high alignment regulation force, and generation of afterimages is suppressed. I can do it. Further, according to the present invention, it is possible to provide a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display element, particularly a vertical alignment type liquid crystal display element, without adding a photopolymerizable compound to the liquid crystal. .
• the liquid crystal aligning agent is not limited to a vertical alignment type liquid crystal display element, but can be used for a liquid crystal display element that performs alignment processing by irradiating polarized ultraviolet rays, for example, and has a good liquid crystal alignment and an alternating current (AC).
• a liquid crystal alignment film effective in improving the afterimage can be provided.
• the novel compound used for the production of the liquid crystal aligning agent of the present invention is a diamine compound represented by the following formula [1] or a (meth) acrylate compound represented by the following formula [1].
• the compound of formula [1] is a diamine compound
• the combination of R 1 and R 2 is selected to have two amino groups. That is, when R 1 is a group represented by the following formula [2] or a diaminophenyl group, R 2 is the number of carbon atoms to which a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a (meth) acryloyloxy group is bonded.
• R 1 is a group represented by the following formula [3], an amino group, or an aminophenyl group
• R 2 is an aminophenyl group or an aminobiphenyl group.
• R 3 is a single bond, —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH— or —CO—.
• R 4 is carbon.
• the organic group include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), a halogen group (—Cl, —Br, —I), and a cyano group. (—CN), dialkylamino group (—NR 2 ), ester group (—COOR), nitro group (—NO 2 ), etc.
• —CH 2 — in R 4 is any of the following: In the case where the radicals of To be replaced; -O -, - NHCO -, - CONH -, - COO -, - OCO -, - NH -, - NHCONH -, - CO-.R 5 is -CH 2 -, - O -, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-.
• R 1 is a group represented by the following formula [4]
• R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group Alternatively, it is a biphenyl group, and one or more hydrogen atoms in the phenyl group or biphenyl group may be replaced with a halogen group (—Cl, —Br, —I) or an organic group.
• Examples of the organic group include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), a cyano group (—CN), a dialkylamino group (—NR 2 ), and an ester group (—COOR). And a nitro group (—NO 2 ).
• R 6 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms in the alkylene group, divalent carbocycle or heterocycle are
• the organic group may be substituted with a fluorine atom or an organic group, for example, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), a halogen group (—Cl, — Br, —I), cyano group (—CN), dialkylamino group (—NR 2 ), ester group (—COOR), nitro group (—NO 2 ), etc.
• R 7 is -CH 2 -, - O -, - CONH -, - NHCO -, - COO -, - OCO -, - NH- or -CO- is .
• R 8 is a hydrogen atom or a methyl group is there.
• Examples of the compound represented by the formula [1] include the following formula [1-A], the formula [1-B], the formula [1-C], the formula [1-D], and the following formula [1-E]. It is done.
• R 12 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• R 3 to R 8 are as defined above, R 9 is a single bond or phenylene, and R 10 is a carbon number.
• R 11 is a hydrogen atom or a methyl group
• R 13 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a biphenyl group, in the phenyl group or biphenyl group.
• One or more hydrogen atoms may be replaced with a halogen group or an organic group, which includes an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), And a cyano group (—CN), a dialkylamino group (—NR 2 ), an ester group (—COOR), and a nitro group (—NO 2 ).)
• a halogen group or an organic group which includes an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), And a cyano group (—CN), a dialkylamino group (—NR 2 ), an ester group (—COOR), and a nitro group (—NO 2 ).
• R 3 -R 4 -R 5 represents R 1 from the structure represented by the formula [1] which is a group that causes photodimerization with the diaminobenzene skeleton in the side chain. It is a spacer site that connects the removed monovalent group, and R 3 is a linking group to the diaminobenzene skeleton at this spacer site.
• This linking group R 3 is a single bond, —CH 2 — (methylene), —O— (ether), —CONH— (amide), —NHCO— (reverse amide), —COO— (ester), —OCO— (Reverse ester), —NH— (amino) and —CO— (carbonyl).
• These linking groups R 3 can be formed by a general organic synthetic method. From the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO— or —NH— preferable.
• R 4 in the formula [1-A] is a central part of the spacer moiety, and is an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring.
• any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group.
• the hydrogen atom to be replaced may be one place or a plurality of places.
• one or more —CH 2 — of the alkylene group, divalent carbocyclic ring or heterocyclic ring is replaced by these linking groups when any of the following linking groups is not adjacent to each other.
• R 4 may include a configuration of an alkylene group, a divalent carbocycle or a heterocycle-the linking group-alkylene group, a divalent carbocycle or a heterocycle.
• R 3 is —CH 2 —
• R 5 is —CH 2 —
• R 5 it means that the terminal on the R 5 side in R 4 may be the linking group.
• R 4 is the linking group-alkylene group, divalent carbocycle or heterocycle-the linking group. Or R 4 may be any of the linking groups. Note that —CH 2 — replaced by the linking group may be at one location, and may be at multiple locations if the linking groups are not adjacent to each other. Specific examples of the divalent carbocycle or heterocycle include the following structures, but are not limited thereto.
• R 5 in the formula [1-A] represents a linking group with a monovalent group obtained by removing R 1 from the structure represented by the formula [1] in the spacer moiety.
• This linking group R 5 is selected from the group consisting of —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH— and —CO—.
• These linking groups R 5 can be formed by ordinary organic synthetic techniques, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO— or —NH— Is preferred.
• R 9 represents a single bond or a phenylene group.
• Specific examples of the compound represented by the formula [1-B] include the following compounds.
• R 9 represents a single bond or a phenylene group.
• Specific examples of the compound represented by the formula [1-C] include the following compounds.
• R 3 -R 4 -R 5 is the same as that in the compound of the formula [1-A].
• R 6 is a central part of the spacer moiety, and is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle.
• any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group.
• the hydrogen atom to be replaced may be one place or a plurality of places.
• one or more —CH 2 — of the alkylene group, divalent carbocyclic ring or heterocyclic ring is replaced by these linking groups when any of the following linking groups is not adjacent to each other.
• R 6 may include a configuration of an alkylene group, a divalent carbocycle or a heterocycle-the linking group-alkylene group, a divalent carbocycle or a heterocycle.
• R 7 when R 7 is —CH 2 —, it means that the terminal on the R 5 side in R 7 may be the linking group. Note that —CH 2 — replaced by the linking group may be at one location, and may be at multiple locations if the linking groups are not adjacent to each other. Examples of the divalent carbocycle or heterocycle include the same rings as those described for R 4 above.
• R 7 in the formula [1-E] represents a linking group with a monovalent group obtained by removing R 1 from the structure represented by the formula [1] in the spacer moiety.
• This linking group R 7 is selected from the group consisting of —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—.
• These linking groups R 7 can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO— or —NH— Is preferred, and —O— is particularly preferred.
• R 8 in the formula [1-E] represents a hydrogen atom or a methyl group.
• R 13 in the formula [1-E] represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a biphenyl group, and one or more hydrogen atoms in the phenyl group or the biphenyl group are a halogen group (—Cl, —Br, —I) or an organic group may be substituted.
• Examples of the organic group include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group (—OH), an alkoxy group (—OR), a cyano group (—CN), a dialkylamino group (—NR 2 ), and an ester group (—COOR). And a nitro group (—NO 2 ).
• Specific examples of the compound represented by the formula [1-E] include the following compounds.
• the liquid crystal aligning agent of the present invention contains at least one polymer selected from a polyimide precursor and a polyimide obtained by imidizing it as a polymer component
• the diamine component as a raw material thereof has the formula [1 -A] to at least one diamine compound selected from [1-D].
• the method for synthesizing the diamine compounds represented by the above formulas [1-A] to [1-D] is not particularly limited.
• dinitro compounds represented by the following formulas [1a-A] to [1a-D] It can be obtained by reducing the nitro group and converting it to an amino group.
• the reduction is performed using a catalyst that does not hydrogenate the double bond.
• the reduction reaction is preferably carried out using zinc, tin, tin chloride, iron or the like together with ammonium chloride, hydrogen chloride or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or alcohol.
• the dinitro compound represented by the above formula [1a-A] can be obtained by a method in which —R 4 —R 5 —X 1 which is a side chain moiety is bonded to dinitrobenzene via R 3 .
• R 3 is an amide bond (—CONH—)
• a method of reacting dinitrobenzene acid chloride with an amino compound containing —R 4 —R 5 —X 1 in the presence of an alkali can be mentioned.
• R 3 is a reverse amide bond (—HNCO—)
• a method in which an amino group-containing dinitrobenzene and an acid chloride containing —R 4 —R 5 —X 1 are reacted in the presence of an alkali can be mentioned.
• R 3 is an ester bond (—COO—)
• a method of reacting dinitrobenzene acid chloride with an alcohol compound containing —R 4 —R 5 —X 1 in the presence of an alkali can be mentioned.
• R 3 is an inverted ester bond (—OCO—)
• —OCO— there is a method in which a hydroxy group-containing dinitrobenzene and an acid chloride compound containing —R 4 —R 5 —X 1 are reacted in the presence of an alkali.
• R 3 is an ether bond (—O—)
• a method of reacting a halogen group-containing dinitrobenzene with an alcohol compound containing —R 4 —R 5 —X 1 in the presence of an alkali can be mentioned.
• R 3 is an amino bond (—NH—)
• a method of reacting a halogen group-containing dinitrobenzene with an amino compound containing —R 4 —R 5 —X 1 in the presence of an alkali can be mentioned.
• R 3 is a carbonyl bond (—CO—)
• an aldehyde group-containing dinitrobenzene and a boronic acid compound containing —R 4 —R 5 —X 1 are subjected to a coupling reaction in the presence of palladium or a copper catalyst.
• the method of performing is mentioned.
• R 3 is a carbon bond (—CH 2 —)
• a method using a Sonogashira cross-coupling reaction
• Examples of the dinitrobenzene acid chloride include 3,5-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid chloride, 2,6-dinitrobenzoic acid chloride, 3,5-dinitrobenzyl chloride, and 2,4-dinitrobenzyl. Chloride.
• Examples of the amino group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline and the like.
• Examples of the hydroxy group-containing nitrobenzene include 2,4-dinitrophenol, 3,5-dinitrophenol, 2,6-dinitrophenol and the like.
• Examples of the halogen group-containing dinitrobenzene include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, 2,4-dinitroiodobenzene, 3,5-dinitroiodobenzene, 2, Examples thereof include 6-dinitroiodobenzene.
• Examples of the aldehyde group-containing dinitrobenzene include 2,4-dinitrobenzaldehyde, 3,5-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde and the like.
• Examples of a method for synthesizing the side chain moiety —R 4 —R 5 —X 1 include a method of synthesizing by the following method. For example, when R 5 is an amide bond (—CONH—), a method of reacting an acid chloride compound containing —R 4 with X 1 —NH 2 in the presence of an alkali can be mentioned.
• R 5 is a reverse amide bond (—HNCO—)
• a method in which an amino compound containing —R 4 and an acid chloride compound containing X 1 are reacted in the presence of an alkali can be mentioned.
• R 5 is an ester bond (—COO—)
• a method of reacting an acid chloride compound containing —R 4 with X 1 —OH in the presence of an alkali can be mentioned.
• R 5 is an inverted ester bond (—OCO—)
• a method of reacting an alcohol compound containing —R 4 and an acid chloride compound containing X 1 in the presence of an alkali can be mentioned.
• R 5 is an ether bond (—O—)
• a method of reacting a halogen compound containing —R 4 with X 1 —OH in the presence of an alkali can be mentioned.
• R 5 is an amino bond (—NH—)
• a method of reacting a halogen compound containing —R 4 with X 1 —NH 2 in the presence of an alkali can be mentioned.
• R 5 is a carbonyl bond (—CO—)
• a method of reacting an aldehyde compound containing —R 4 with a boronic acid compound containing —X 1 in the presence of an alkali can be mentioned.
• Substituent X 1 can be formed by reacting a halogenated benzophenone halogen group with an acrylic acid derivative such as an acrylic ester, as represented by the following formula, for example. (Wherein X 2 represents CH 2 Cl, OH, NO 2 , NH 2 , COOH, etc.)
• the compound represented by the formula [1a-B] hydrolyzes the t-butyl group by reacting 4-nitro-4′-halogenobenzophenone with t-butyl acrylate and treating with acid. And then reacting with nitrophenol or nitrophenylphenol. Hydrolysis can be performed by using hydrochloric acid, formic acid, trifluoroacetic acid or the like as the acid.
• the compound represented by the formula [1a-C] is obtained by reacting t-butyl acrylate with 4-4′-dihalogenobenzophenone as a raw material in the same manner as described above, and treating with t. It can be obtained by decomposing and then reacting with nitrophenol or nitrophenylphenol. Hydrolysis can be performed by using hydrochloric acid, formic acid, trifluoroacetic acid or the like as the acid.
• This compound can be produced, for example, by the method shown in the following scheme. This compound is a novel compound not described in the literature.
• the raw material (meth) acrylate contains a compound represented by the above formula [1-E].
• This compound can be obtained, for example, by reacting the compound represented by the above formula [5] with (meth) acrylic acid chloride in the presence of an alkali.
• the method for producing a liquid crystal display element for driving a horizontal electric field using the liquid crystal aligning agent of the present invention forms a liquid crystal aligning film by applying the liquid crystal aligning agent of the present invention to a substrate and firing it, and the liquid crystal aligning film is subjected to an alignment treatment. Then, two substrates having the liquid crystal alignment film are placed opposite to each other so that the liquid crystal alignment film faces each other with the liquid crystal interposed therebetween, and a liquid crystal cell is manufactured.
• a liquid crystal display element for driving a horizontal electric field is produced by reacting a photopolymerizable group in the liquid crystal alignment film.
• the manufacturing method of the liquid crystal display element for vertical alignment using the liquid crystal aligning agent of this invention forms a liquid crystal aligning film by apply
• a liquid crystal layer is formed by sandwiching liquid crystal between two substrates, and then ultraviolet rays are irradiated while applying a voltage to the liquid crystal layer.
• the liquid crystal aligning agent and / or liquid crystal used in the production method of the present invention contains a photopolymerizable group.
• a liquid crystal containing a photopolymerizable group can be obtained by adding a compound containing a photopolymerizable group (hereinafter also referred to as a polymerizable compound) to the liquid crystal.
• a polymerizable compound may be added to the liquid crystal aligning agent, or a photopolymerizable group may be added to the side chain of the polymer contained in the liquid crystal aligning agent. It may be introduced or both.
• the liquid crystal aligning film obtained using such a liquid crystal aligning agent contains a photopolymerizable group.
• the addition ratio may be, for example, 0.1 to 30 (mass)% of the polymerizable compound, preferably 0.1 to 15% with respect to the liquid crystal.
• the addition ratio thereof is, for example, 0.1 to 30 (mass)% of the polymerizable compound with respect to the liquid crystal aligning agent, preferably 0.1 to 15%.
• the photopolymerizable group is a group that undergoes a polymerization reaction by light such as ultraviolet rays, for example, a group that is polymerized by light such as ultraviolet rays (hereinafter also referred to as a photopolymerizable group) or a photocrosslinkable group (hereinafter also referred to as a photocrosslinkable group). If it says), it will not specifically limit, However, The structure shown below is used preferably.
• the polymerizable compound examples include a compound having a photopolymerizable group at each of two ends as represented by the following formula (I), and a photopolymerizable group represented by the following formula (II).
• examples thereof include a compound having a terminal having a terminal having a photocrosslinkable group and a compound having a group to be photocrosslinked at each of two terminals represented by the following formula (III).
• R 12 is H or an alkyl group having 1 to 4 carbon atoms
• Z 1 is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
• Q 1 has a ring structure such as a phenylene group (—C 6 H 4 —), a biphenylene group (—C 6 H 4 —C 6 H 4 —), a cyclohexylene group (—C 6 H 10 —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.
• V is a single bond or —R 1 O—.
• R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably a linear or branched alkylene group having 2 to 6 carbon atoms.
• W is a single bond or —OR 2 —.
• R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably a linear or branched alkylene group having 2 to 6 carbon atoms.
• V and W may be the same or different, but the same is preferable in that synthesis is easy.
• the acryloyloxy group or methacryloyloxy group is not a ⁇ -methylene- ⁇ -butyrolactone group but a polymerizable compound having an acryloyloxy group or a methacryloyloxy group as a photopolymerizable group or a photocrosslinking group. If it is a polymerizable compound having a structure bonded to a phenylene group via a spacer site composed of an oxyalkylene group or the like, similarly to the polymerizable compound having an ⁇ -methylene- ⁇ -butyrolactone group at both ends, The afterimage characteristics due to AC stress can be greatly improved.
• the polymerizable compound has a structure in which an acryloyloxy group or a methacryloyloxy group is bonded to a phenylene group through a spacer site composed of an oxyalkylene group, the stability against heat is improved, For example, it can sufficiently withstand a firing temperature of 200 ° C. or higher.
• polymerizable compound represented by the formula (I) include polymerizable compounds of the following formula. (In the formula, the definitions of R 12 , V and W are the same as above.)
• the method for producing such a polymerizable compound is not particularly limited, and for example, it can be produced according to the synthesis examples described later.
• the polymerizable compound represented by the above formula (I-1) can be synthesized by combining techniques in organic synthetic chemistry. For example, P.I.
• R ′ represents a monovalent organic group.
• 2- (bromomethyl) acrylic acid is represented by the following reaction formula.
• Ramarajan et al., “Organic” Synthesis (1983), Vol. 61, 56-59, can be synthesized by the method proposed.
• a polyimide precursor As the polymer contained in the liquid crystal aligning agent used in the present invention, a polyimide precursor, a polyimide obtained by imidizing it, or poly (meth) acrylate is preferably used.
• the polyimide precursor refers to polyamic acid (also referred to as polyamic acid) or polyamic acid ester.
• these different polymers may be simultaneously contained in the liquid crystal aligning agent, and the content ratio thereof is variously selected according to the characteristics of the liquid crystal display element.
• the total amount of the polymer contained in the liquid crystal aligning agent is preferably 0.1 to 20 (mass)%.
• the polymer such as a polyimide precursor, polyimide, and poly (meth) acrylate contained in the liquid crystal aligning agent of the present invention needs to be soluble in a solvent contained in the liquid crystal aligning agent.
• a photoreactive group that exhibits liquid crystal alignment ability is introduced into the polymer contained in the liquid crystal aligning agent by using polarized ultraviolet rays. There is a need.
• a photoreactive group may be introduced into the main chain of the polymer or may be introduced into the side chain.
• Photoreaction includes photolysis, photodimerization, and photoisomerization.
• examples of the structure in which the photodimerization reaction proceeds include structures represented by the following formulas (A-3), (A-4), and (A-5).
• Examples of the structure in which the photoisomerization reaction proceeds include structures represented by the following formulas (A-6) and (A-7).
• Examples of the structure in which the photodecomposition reaction proceeds include structures represented by the following formulas (A-1) and (A-2).
• the photoreactive group having a structure selected from the following formulas (A-1) to (A-7) is an arbitrary number of hydrogen atoms (from the structures of the formulas (A-1) to (A-7)) ( A group in which N is a bond in formulas (A-1) to (A-2), a group in which O is a bond in formula (A-3), A group bonded to a structure (for example, an alkylene group).
• the polyimide precursor contained in the liquid crystal aligning agent of the present invention includes a diamine component (a diamine represented by the formula [1-A] to [1-D], a diamine having a photopolymerizable side chain described later, a photoreactive property.
• a diamine having a group, a diamine having a side chain for vertically aligning liquid crystals, or other diamine compounds and a tetracarboxylic dianhydride component (for example, tetracarboxylic dianhydride, tetracarboxylic diester dichloride or tetra described below) Obtained by reaction with a carboxylic acid diester or the like).
• a polyamic acid is obtained by reaction of a diamine component and tetracarboxylic dianhydride.
• the polyamic acid ester is obtained by reacting a diamine component and a tetracarboxylic acid diester dichloride in the presence of a base, or reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or base.
• Polyimide can be obtained by dehydrating and ring-closing this polyamic acid or by heating and ring-closing the polyamic acid ester. Any of such polyamic acid, polyamic acid ester, and polyimide is useful as a polymer for obtaining a liquid crystal alignment film.
• This compound includes a photopolymerizable side containing at least one selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, a maleimide group, an itaconyl group and an ⁇ -methylene- ⁇ -butyrolactone group.
• diamines with chains More specifically, for example, diamines represented by the following general formula (2) can be exemplified, but the invention is not limited thereto.
• R 13 is a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N.
• R 14 is a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom
• the alkylene group —CH 2 — may be optionally replaced by —CF 2 — or —CH ⁇ CH—, and in the case where any of the following groups is not adjacent to each other, May be substituted: —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, divalent carbocyclic ring, divalent heterocyclic ring
• R 15 represents methacrylic group, acrylic Group, vinyl group, allyl group, styryl group, maleimide Represents a itaconyl group or ⁇ - methylene - ⁇ - butyrolactone group.
• R 13 in the above formula (2) can be formed by a general organic synthetic method
• divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH 2 — in R 14 include the following structures, but are not limited thereto. Is not to be done.
• R 15 is preferably a methacryl group, an acryl group, a styryl group, an itaconyl group or an ⁇ -methylene- ⁇ -butyrolactone group from the viewpoint of photopolymerization.
• the abundance of the photopolymerizable side chain is preferably in a range where the orientation can be fixed by reacting with irradiation of light such as ultraviolet rays to form a covalent bond, and in order to further improve the AC afterimage characteristics, As much as possible is preferable as long as other characteristics are not affected.
• Such a photopolymerizable side chain containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group, a maleimide group, an itaconyl group, and an ⁇ -methylene- ⁇ -butyrolactone group.
• the method for producing at least one polymer selected from polyimide precursors having the following and polyimide obtained by imidizing this polyimide precursor is not particularly limited.
• a diamine having a photopolymerizable side chain containing at least one selected from the group consisting of methacryl group, acrylic group, vinyl group, allyl group, styryl group, maleimide group, itaconyl group and ⁇ -methylene- ⁇ -butyrolactone groups may be copolymerized.
• Binding positions of the two amino group (-NH 2) in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
• a diamine having a photopolymerizable side chain containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group, a maleimide group, an itaconyl group and an ⁇ -methylene- ⁇ -butyrolactone group Specific examples of the compound include, but are not limited to, the following compounds.
• X is a single bond, —O—, —COO—, —NHCO— or —NH—
• Y is a single bond or an alkylene having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom. Group.
• a photopolymerizable side chain containing at least one selected from the group consisting of the methacryl group, acryl group, vinyl group, allyl group, styryl group, maleimide group, itaconyl group and ⁇ -methylene- ⁇ -butyrolactone group.
• the photopolymerizable side containing at least one selected from the group consisting of such methacryl group, acryl group, vinyl group, allyl group, styryl group, maleimide group, itaconyl group and ⁇ -methylene- ⁇ -butyrolactone group.
• the content of the diamine having a chain is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%, based on the total amount of diamine components used for the synthesis of the polyamic acid. is there.
• ⁇ Diamine with photoreactive group> In the production method of the present invention, when polarized ultraviolet rays are used in the alignment treatment, a photoreactive group needs to be introduced into the polymer contained in the liquid crystal aligning agent.
• the structure of the above formulas (A-3) to (A-7) is contained in the main chain or side chain.
• a method using tetracarboxylic dianhydride or diamine it is preferable to use a diamine containing the structure of the above formulas (A-3) to (A-7) in the side chain from the viewpoint of ease of synthesis.
• the side chain of diamine is a structure branched from a structure connecting two amino groups of diamine. Specific examples of such diamines include, but are not limited to, compounds represented by the following formulae.
• X represents a single bond or a bonding group selected from —O—, —COO—, —NHCO—, —NH—
• Y represents a single bond, unsubstituted or substituted by a fluorine atom.
• R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which is unsubstituted or substituted by a fluorine atom, or an alkyl ether group.
• the diamine component which the liquid crystal aligning agent of this invention contains may contain the diamine compound which has the side chain which aligns a liquid crystal perpendicularly other than the diamine compound represented by the said Formula [1].
• the diamine compound having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a steroid group, and a part of hydrogen atoms of these groups.
• diamines having groups in which all fluorine atoms are replaced as side chains for example, diamines represented by the following formulas [A-1] to [A-24] can be exemplified, but the invention is not limited thereto. is not.
• a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
• a 2 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—.
• a 3 is (It is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.)
• a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O —, —OCH 2 — or —CH 2 —, wherein A 5 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
• a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O —, —OCH 2 —, —CH 2 —, —O— or —NH—
• a 7 represents fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy or hydroxyl .
• a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
• a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• diamine compound having a side chain for vertically aligning the liquid crystal examples include diamines represented by the following formulas [A-25] to [A-30].
• a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
• a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• diamines represented by the following formulas [A-31] to [A-32] can also be given as specific examples of the diamine compound having a side chain for vertically aligning liquid crystals.
• Adiamine of [A-25], [A-26], [A-27], [A-28], [A-29] or [A-30] is preferred.
• the above diamines may be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
• a side chain for vertically aligning liquid crystals contained in a diamine component which is a raw material of at least one polymer selected from a polyimide precursor contained in the liquid crystal aligning agent of the present invention and a polyimide obtained by imidizing the polyimide precursor
• the ratio of the diamine having is not particularly limited, but is 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, particularly preferably 20 mol% to 50 mol% in the diamine component used for the synthesis of the polyimide precursor. It is preferable to use such an amount.
• the amount of the diamine having a side chain for vertically aligning the liquid crystal is 5 mol% to 70 mol% in the diamine component used for the synthesis of the polyimide precursor, the response speed is improved and the liquid crystal alignment fixing ability is improved. Especially excellent.
• the diamine component which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing it, is as long as the effects of the present invention are not impaired.
• the diamine compound represented by the formula [1] and a diamine having a side chain for vertically aligning the liquid crystal other diamines may be included.
• diamines examples include p-phenylene diamine, 2,3,5,6-tetramethyl-p-phenylene diamine, 2,5-dimethyl-p-phenylene diamine, m-phenylene diamine, and 2,4-dimethyl.
• the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, accumulated charge, etc. when the liquid crystal alignment film is used.
• tetracarboxylic dianhydride component In order to obtain the polyamic acid contained in the liquid crystal aligning agent of this invention, the tetracarboxylic dianhydride made to react with a diamine component is not specifically limited. Specific examples are given below.
• Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
• Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclo
• the use of aromatic tetracarboxylic dianhydride improves the liquid crystal alignment and reduces the accumulated charge in the liquid crystal cell. This is preferable.
• Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid And dianhydrides and 2,3,6,7-naphthalenetetracarboxylic dianhydride.
• the tetracarboxylic dianhydride can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
• the tetracarboxylic acid dialkyl ester to be reacted with the diamine component to obtain the polyamic acid ester contained in the liquid crystal aligning agent used in the present invention is not particularly limited. Specific examples are given below.
• aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy- , 2,3,4-Tetrahydro-1-na
• aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalenetetracarboxylic acid dialkyl
• the polyamic acid that is a polyimide precursor can be synthesized by the following method. Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.
• the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These are used alone or in combination. May be.
• the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight body is easily obtained.
• the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
• a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
• the polyamic acid ester which is a polyimide precursor can be synthesized by the following methods (1) to (3).
• the polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
• the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
• the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
• the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of polymer solubility. These may be used alone or in combination of two or more. Good.
• the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
• Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
• pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
• the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
• the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
• the polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
• the polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine. Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized by reacting.
• condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
• Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
• the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
• tertiary amines such as pyridine and triethylamine can be used.
• the addition amount of the base is preferably 2 to 4 times mol with respect to the diamine component from the viewpoint of easy removal and high molecular weight.
• the reaction proceeds efficiently by adding Lewis acid as an additive.
• Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
• the synthesis method (1) or (2) is particularly preferable.
• the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
• a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
• the polyimide can be produced by imidizing the polyamic acid or polyamic acid ester.
• chemical imidization in which a basic catalyst is added to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester powder in an organic solvent is convenient.
• Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
• Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
• a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
• the temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
• the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group.
• the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below and redissolved in an organic solvent to obtain a liquid crystal aligning agent. It is preferable.
• Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
• a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has an appropriate basicity for proceeding with the reaction.
• the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double.
• the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
• the liquid crystal aligning agent of the present invention is preferable.
• the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
• the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
• the method for obtaining the poly (meth) acrylate used as the polymer component in the liquid crystal aligning agent of the present invention is not particularly limited.
• a monomer such as an acrylic ester compound or a methacrylic ester compound, a monomer having a photopolymerizable group or a photoreactive group, if desired, and a polymerization initiator, if desired, in a solvent at 50 ° C. to 110 ° C. It can be obtained by polymerizing at a temperature.
• the solvent used in that case will not be specifically limited if a monomer and the polymer obtained are dissolved.
• acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and t-butyl.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, t-butyl.
• the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate 2-hydroxy-3-methylbutanoic acid , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-
• the polymer solution obtained as described above is poured into methanol, ethanol, water and the like under stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then at normal or reduced pressure at room temperature.
• the desired polymer powder can be obtained by heating and drying. By such an operation, the polymerization initiator and unreacted monomer coexisting with the polymer can be removed, and as a result, a purified polymer powder can be obtained. If sufficient purification cannot be achieved by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the liquid crystal aligning agent of the present invention contains, as a polymer component, at least one selected from polyimide precursors such as polyamic acid and polyamic acid ester and polyimide obtained by ring-opening the polyimide precursor, polyimide precursor
• the molecular weight of the polyimide is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and even more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, still more preferably 5,000 to 50,000.
• the molecular weight of the polysiloxane is preferably 2,000 to 500,000, more preferably 5,000 to 300,000 in terms of weight average molecular weight, and 10,000 to 100. Is more preferred.
• the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
• the molecular weight of the poly (meth) acrylate is preferably 2,000 to 500,000 in terms of weight average molecular weight, and 5,000 to 300,000. Is more preferable, and 10,000 to 100,000 is more preferable.
• the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
• the organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer and the polymerizable compound contained in the liquid crystal aligning agent are uniformly dissolved.
• Specific examples thereof include N, N-dimethylformamide in the case where at least one selected from a polyimide precursor and a polyimide obtained by ring-opening the polyimide precursor is used as a polymer component of a liquid crystal aligning agent, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, Examples thereof include dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like.
• polysiloxane is used as the polymer component of the liquid crystal aligning agent
• polyhydric alcohol compounds such as ethylene glycol and 1,2-propylene glycol
• amide compounds such as N-methylformamide and N, N-dimethylformamide Etc.
• poly (meth) acrylate is used as the polymer component of the liquid crystal aligning agent
• alcohol compounds, ketone compounds, amide compounds or ester compounds or other aprotic compounds can be used. You may use these 1 type or in mixture of 2 or more types.
• it is a solvent which cannot dissolve a polymer component and a polymerizable compound uniformly by itself, it may be mixed with the above organic solvent as long as the polymer component and the polymerizable compound do not precipitate.
• the liquid crystal aligning agent of this invention may contain the solvent for improving the coating-film uniformity at the time of apply
• a solvent a solvent having a surface tension lower than that of the organic solvent is generally used.
• ethyl cellosolve examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like. Two types of
• a dielectric other than the above-mentioned polymer and a dielectric for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film are provided as long as the effects of the present invention are not impaired.
• an imidization accelerator or the like that efficiently progresses imidization of the polyimide precursor may be further added.
• the liquid crystal alignment film used in the production method of the present invention is obtained by applying the liquid crystal aligning agent to a substrate, drying it as necessary, and then performing an alignment treatment on the coating surface obtained by baking.
• the substrate on which the liquid crystal alignment agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
• a substrate on which an ITO (Indium TinxOxide) electrode or the like is formed is preferable from the viewpoint of simplification of the process.
• an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
• Examples of the method for applying the liquid crystal aligning agent described in the present invention include a spin coating method, a printing method, and an ink jet method.
• the drying and baking steps after applying the liquid crystal aligning agent can be selected at any temperature and time. Usually, it is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes and then calcined at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes in order to sufficiently remove the contained organic solvent.
• the thickness of the baked coating film is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
• the alignment treatment used in the production method of the present invention includes an alignment treatment by rubbing and an alignment treatment by so-called photo-alignment method by irradiating polarized ultraviolet rays.
• the surface of the coating film is irradiated with ultraviolet rays polarized in a certain direction including ultraviolet rays having a wavelength of 200 nm to 400 nm, preferably 210 nm to 380 nm, for example, 300 nm to 350 nm.
• a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
• the coated substrate may be irradiated with ultraviolet rays while being heated at 50 to 250 ° C. Irradiation amount of the ultraviolet rays is preferably in the range of 1 ⁇ 10,000mJ / cm 2, and particularly preferably in the range of 1 ⁇ 2,000mJ / cm 2.
• the film irradiated with the polarized ultraviolet light may be contact-treated with water or a solution containing a specific organic solvent.
• the organic solvent is not particularly limited, but water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate Methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
• a liquid crystal alignment film having high anisotropy and no unevenness can be easily obtained, so that 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate And at least one selected from the group consisting of diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. In particular, at least one selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate is preferable.
• the contact treatment between the film irradiated with polarized ultraviolet rays and the solution containing the organic solvent is performed by a treatment such that the film and the liquid are sufficiently in contact, such as an immersion treatment or a spraying treatment.
• a treatment such as an immersion treatment or a spraying treatment.
• a method of immersing the film in a solution containing an organic solvent for 10 seconds to 1 hour, preferably 1 minute to 30 minutes is preferable.
• the contact treatment may be carried out at room temperature or preferably at 10 to 80 ° C., more preferably at 20 to 50 ° C.
• the treatment which raises a contact using means, such as an ultrasonic wave can be given as needed.
• the temperature for drying is preferably 80 to 250 ° C, more preferably 80 to 150 ° C.
• the liquid crystal alignment film obtained as described above can stably align liquid crystal molecules in a certain direction.
• the liquid crystal display element for driving a horizontal electric field manufactured by the manufacturing method of the present invention is a liquid crystal cell for driving a horizontal electric field produced by a known method after obtaining the substrate with the above-mentioned liquid crystal alignment film.
• a liquid crystal display element for driving a horizontal electric field is obtained using the liquid crystal cell.
• an in-plane switching (IPS) liquid crystal display element is a liquid crystal display element that switches liquid crystal molecules by applying an electric field in a horizontal direction (lateral direction) with respect to a substrate.
• the horizontal electric field driving liquid crystal display element manufactured by the manufacturing method of the present invention is an active matrix horizontal electric field driving liquid crystal in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting image display. It may be a display element.
• the substrate used in the liquid crystal display element for lateral electric field driving manufactured in the present invention is not particularly limited as long as it is a highly transparent substrate, but usually a substrate on which a transparent electrode for driving liquid crystal is formed. It is. As a specific example, the thing similar to the board
• the liquid crystal alignment film is formed by applying the liquid crystal aligning agent on the substrate and baking it, and irradiating with radiation such as rubbing treatment or polarized ultraviolet rays as necessary.
• the other substrate is overlaid on one substrate so that the liquid crystal alignment film faces each other, and the periphery is bonded with a sealant.
• a spacer is usually mixed in the sealing material.
• a liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening provided in the sealing material.
• the liquid crystal material include liquid crystal “MLC-2041” (manufactured by Merck & Co., Inc.).
• the opening is sealed with an adhesive.
• a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used. Thereby, a liquid crystal cell for driving a horizontal electric field is manufactured.
• the liquid crystal cell for driving the horizontal electric field is irradiated with light such as ultraviolet rays.
• the irradiation amount of ultraviolet rays is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the lower the irradiation amount of ultraviolet rays, the lower the reliability caused by the destruction of the members constituting the liquid crystal display element. This is preferable because the production efficiency is improved by reducing the ultraviolet irradiation time.
• the wavelength of the irradiated ultraviolet light is, for example, 200 nm to 400 nm.
• the photopolymerizable group located on the surface where the liquid crystal alignment film and the liquid crystal are in contact reacts.
• the alignment of the liquid crystal positioned on the surface of the liquid crystal alignment film is fixed.
• the alignment regulating force of the liquid crystal alignment film is strengthened, and as a result, the electric characteristics such as the afterimage phenomenon caused by the liquid crystal alignment disorder are improved. It becomes a liquid crystal display element.
• a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer. Through the above steps, a lateral electric field driving liquid crystal display element is obtained.
• the horizontal electric field driving liquid crystal display element manufactured by the method of manufacturing a horizontal electric field driving liquid crystal display element of the present invention has a strong alignment regulating force of the liquid crystal alignment film and the occurrence of afterimages is suppressed, It can be suitably used for large-screen and high-definition liquid crystal televisions.
• FFSA Fringe Field Stabilized Alignment
• the FFSA method is a technique for improving the response speed of the liquid crystal display element by introducing a photoreactive group into the liquid crystal alignment film.
• the FFSA type liquid crystal display element is formed by two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and the liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
• a liquid crystal display element comprising a liquid crystal cell having the liquid crystal alignment film.
• the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
• a liquid crystal display element including a liquid crystal cell manufactured by sandwiching a liquid crystal layer composed of liquid crystal between two substrates and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
• the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention When the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used, the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays while applying a voltage, and the photopolymerizable group possessed by the polyimide precursor and the polyimide side chain and A photopolymerizable compound is separately added to the liquid crystal aligning agent by reacting a group causing photodimerization, that is, a photopolymerizable group derived from the diamine compound represented by the above formula [1-D] and a group causing photodimerization.
• a group causing photodimerization that is, a photopolymerizable group derived from the diamine compound represented by the above formula [1-D] and a group causing photodimerization.
• the liquid crystal alignment is more efficiently fixed than the liquid crystal alignment film using the liquid crystal aligning agent to which the photopolymerizable compound is added, and the liquid crystal display device is remarkably excellent in response speed.
• a photopolymerizable compound is separately added to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal display element having a response speed equal to or higher than that.
• the substrate used for manufacturing the FFSA liquid crystal display element 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 by manufacture of the said liquid crystal aligning film can be mentioned.
• a conventional substrate provided with an electrode pattern or a protrusion pattern may be used, but in the production method of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film.
• a high-performance element such as a TFT type element
• an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
• a substrate in the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as metal aluminum which reflects light can be used for the electrode formed on the substrate.
• the liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.
• the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and liquid crystal materials used in conventional vertical alignment methods, such as “MLC-6608” and “MLC-6609” manufactured by Merck A negative liquid crystal, “MLC-2041” or the like can be used.
• a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
• a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. And applying ultraviolet rays while maintaining this electric field.
• the voltage applied between the electrodes is, for example, 5 to 80 Vp-p, preferably 5 to 60 Vp-p.
• the ultraviolet irradiation amount is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and It is preferable because the production efficiency is increased by reducing the ultraviolet irradiation time.
• the reaction of the photopolymerizable group of the polyimide precursor or the side chain of the polyimide and the group causing photodimerization proceeds, that is, The cross-linking reaction by the photopolymerizable group derived from the diamine compound represented by the formula [1-D] and the dimerization reaction by the group causing photodimerization proceed, and the liquid crystal molecules are tilted by the resulting cross-linking site or dimerization site.
• the response speed of the obtained liquid crystal display element can be increased.
• liquid crystal aligning agent of the present invention is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a Polymer Sustained Alignment (PSA) type liquid crystal display or an SC-PVA type liquid crystal display. It can also be suitably used for liquid crystal alignment films produced by rubbing or photo-alignment processing.
• PSA Polymer Sustained Alignment
• SC-PVA SC-PVA type liquid crystal display
• Synthesis Example 13 Synthesis of DA-9 To a 1 L four-necked flask, 23.0 g of DA-9-2, 230 mL of ethyl acetate, 230 mL of pure water, 19.9 g of reduced iron, and 15.2 g of ammonium chloride were added and stirred while heating to 60 ° C. After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator.
• Example 6 Synthesis of DA-10 (Synthesis Example 15) Synthesis of DA-10 Precursor DA-10-1 In a 1 L four-necked flask, 42.0 g of 4-bromo-4′-nitrobenzophenone, 300 mL of DMAc, 26.3 g of t-butyl acrylate, 76.2 g of tributylamine, 0.62 g of palladium acetate, tri (O -1.67 g of tolyl) phosphine was added and stirred while heating to 100 ° C. After completion of the reaction, the reaction system was poured into 1 L of ethyl acetate, and extracted with 1N-hydrochloric acid aqueous solution and saturated brine.
• Synthesis Example 17 Synthesis of DA-10 To a 500 mL four-necked flask, 22.3 g of DA-10-2, 30 mL of THF, 200 mL of ethanol, 8.9 g of reduced iron, 56.6 g of 10 wt% ammonium chloride aqueous solution were added and stirred while heating to 60 ° C. . After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator.
• Synthesis Example 19 Synthesis of DA-11 To a 300 mL four-necked flask, 12.3 g of DA-11-1, 80 mL of DMF, 80 mL of ethanol, 6.9 g of reduced iron, 26.5 g of 10 wt% ammonium chloride aqueous solution were added and stirred while heating to 60 ° C. . After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator.
• Example 8 Synthesis of DA-12 (Synthesis Example 18) Synthesis of DA-12 Precursor DA-12-1 In a 500 mL four-necked flask, 18.7 g of 4,4′-dibromobenzophenone, 250 mL of DMAc, 21.2 g of t-butyl acrylate, 47.3 g of tributylamine, 0.49 g of palladium acetate, tri (O-tolyl) ) 1.40 g of phosphine was added and stirred while heating to 100 ° C. After completion of the reaction, the reaction system was poured into 1 L of ethyl acetate, and extracted with 1N-hydrochloric acid aqueous solution and saturated brine.
• Synthesis Example 20 Synthesis of DA-12 To a 500 mL four-necked flask, 9.2 g of DA-12-2, 80 mL of THF, 80 mL of ethanol, 2.3 g of reduced iron, 17.4 g of 10 wt% ammonium chloride aqueous solution were added and stirred while heating to 60 ° C. . After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator.
• Example 9 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA, 0.76 g (0.0020 mol) of DA-2, 4.91 g (0.0080 mol) of DA-8, NMP Reaction was performed in 43.18 g at room temperature for 16 hours to prepare a polyamic acid solution (PAA-1). This polyamic acid had a number average molecular weight of about 8,000. NMP and BCS are added to 10 g of this polyamic acid solution and stirred to prepare a polyamic acid (PAA-1) of 6% by mass, NMP of 54% by mass and BCS of 40% by mass, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 9 was obtained.
• PAA-1 polyamic acid
• NMP 54% by mass
• BCS 40% by mass
• Example 10 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA, 0.76 g (0.0020 mol) of DA-2, 4.69 g (0.0080 mol) of DA-9, NMP The reaction was carried out in 41.91 g at room temperature for 16 hours to prepare a polyamic acid solution (PAA-2). This polyamic acid had a number average molecular weight of about 10,000. NMP and BCS are added to 10 g of this polyamic acid solution and stirred to prepare a polyamic acid (PAA-2) of 6% by mass, NMP of 54% by mass and BCS of 40% by mass, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 10 was obtained.
• PAA-2 polyamic acid solution
• BCS polyamic acid
• Example 11 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA, 0.10 g (0.0010 mol) of DA-1, 0.76 g (0.0020 mol) of DA-2, DA- 9 was reacted in 39.20 g of NMP for 16 hours at room temperature to prepare a polyamic acid solution (PAA-3).
• This polyamic acid had a number average molecular weight of about 11,000.
• NMP and BCS are added to 10 g of this polyamic acid solution and stirred to prepare 6% by mass of polyamic acid (PAA-3), 54% by mass of NMP and 40% by mass of BCS, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 11 was obtained.
• Example 12 Production of Liquid Crystal Alignment Agent 1.15 g (0.0059 mol) of CBDA, 1.15 g (0.0040 mol) of BODA, 0.10 g (0.0010 mol) of DA-1, and DA-2 0.76 g (0.0020 mol) and 4.10 g (0.0070 mol) of DA-9 were reacted in 40.42 g of NMP at room temperature for 16 hours to prepare a polyamic acid solution (PAA-4). This polyamic acid had a number average molecular weight of about 8,000.
• NMP and BCS are added to 10 g of this polyamic acid solution and stirred to prepare a polyamic acid (PAA-4) of 6% by mass, NMP of 54% by mass and BCS of 40% by mass, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 12 was obtained.
• PAA-4 polyamic acid
• Example 13 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 5.16 g (0.010 mol) of DA-6 were reacted in 40.27 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-7) was prepared. This polyamic acid had a number average molecular weight of about 5,000. NMP and BCS are added to 10 g of this polyamic acid solution and stirred, and the mixture is prepared so that the polyamic acid (PAA-7) is 6% by mass, NMP is 64% by mass, and BCS is 30% by mass. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 13 was obtained.
• Example 14 Production of liquid crystal aligning agent 1.94 g (0.0099 mol) g of CBDA and 5.02 g (0.010 mol) of DA-7 were reacted in 39.48 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-8) was prepared. This polyamic acid had a number average molecular weight of about 12,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred to prepare a polyamic acid (PAA-8) of 6% by mass, NMP of 64% by mass and BCS of 30% by mass, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 14 was obtained.
• Example 15 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 6.14 g (0.010 mol) of DA-8 were reacted in 45.83 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-9) was prepared. This polyamic acid had a number average molecular weight of about 9,000.
• NMP and BCS are added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-9) is 6% by mass, NMP is 64% by mass, and BCS is 30% by mass, the membrane having a pore diameter of 1 ⁇ m is prepared. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 15 was obtained.
• Example 16 Production of liquid crystal aligning agent 1.94 g (0.0099 mol) g of CBDA and 5.86 g (0.010 mol) of DA-9 were reacted in 44.24 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-10) was prepared. This polyamic acid had a number average molecular weight of about 19,000. NMP and BCS are added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-10) is 6% by mass, NMP is 64% by mass and BCS is 30% by mass, the membrane having a pore diameter of 1 ⁇ m is prepared. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 16 was obtained.
• Comparative Example 3 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 4.12 g (0.010 mol) of DA-5 were reacted in 34.37 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-11) was prepared. This polyamic acid had a number average molecular weight of about 14,000. NMP and BCS are added to 10 g of this polyamic acid solution and stirred to prepare 6 mass% of polyamic acid (PAA-11), 64 mass% of NMP and 30 mass% of BCS, and then a membrane having a pore diameter of 1 ⁇ m.
• a liquid crystal aligning agent of Comparative Example 3 was obtained by pressure filtration with a filter.
• Example 17 Production of Liquid Crystal Alignment Agent 4.5-2 g (0.010 mol) of MA-2 and 0.082 g (0.0005 mol) of azobisisobutyronitrile were placed in 41.29 g of NMP to perform nitrogen substitution. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to prepare an acrylic polymer solution (PMA-2). This acrylic polymer had a number average molecular weight of about 10,000. BCS was added to 10 g of this acrylic polymer solution and stirred to prepare 6% by mass of acrylic polymer (PMA-2), 54% by mass of NMP, and 40% by mass of BCS, and then a membrane filter having a pore size of 1 ⁇ m. The solution was filtered under pressure to obtain the liquid crystal aligning agent of Example 17.
• PMA-2 acrylic polymer solution
• BCS was added to 10 g of this acrylic polymer solution and stirred to prepare 6% by mass of acrylic polymer (PMA-2), 54% by mass of NMP, and 40% by mass of BCS,
• Example 18 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 3.58 g (0.010 mol) of DA-10 were reacted in 31.31 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-13) was prepared. This polyamic acid had a number average molecular weight of about 8,000. After adding NMP and BCS to 10 g of this polyamic acid solution and stirring the mixture so that the polyamic acid (PAA-13) is 6% by mass, NMP is 64% by mass and BCS is 30% by mass, the membrane having a pore diameter of 1 ⁇ m is prepared. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 18 was obtained.
• Example 19 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 4.34 g (0.010 mol) of DA-11 were reacted in 35.62 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-14) was prepared. This polyamic acid had a number average molecular weight of about 10,000. After adding NMP and BCS to 10 g of this polyamic acid solution and stirring the mixture, the polyamic acid (PAA-14) was prepared to 6 mass%, NMP 64 mass%, and BCS 30 mass%, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 19 was obtained.
• Example 20 Production of liquid crystal aligning agent 1.94 g (0.0099 mol) g of CBDA and 5.04 g (0.010 mol) of DA-12 were reacted in 39.59 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-15) was prepared. This polyamic acid had a number average molecular weight of about 7,000.
• NMP and BCS were added to 10 g of this polyamic acid solution and stirred to prepare a polyamic acid (PAA-15) of 6% by mass, NMP of 64% by mass and BCS of 30% by mass, and then a membrane having a pore diameter of 1 ⁇ m. It filtered under pressure with the filter and the liquid crystal aligning agent of Example 20 was obtained.
• Comparative Example 6 Production of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) g of CBDA and 2.54 g (0.010 mol) of DA-13 were reacted in 25.41 g of NMP at room temperature for 16 hours to obtain a polyamic acid.
• a solution (PAA-16) was prepared. This polyamic acid had a number average molecular weight of about 12,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-16) was 6% by mass, NMP was 64% by mass and BCS was 30% by mass, the membrane having a pore diameter of 1 ⁇ m was prepared.
• the liquid crystal alignment agent of Comparative Example 6 was obtained by pressure filtration with a filter.
• the liquid crystal aligning agent of Example 9 is spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m is formed, and is heated on an 80 ° C. hot plate for 90 seconds. After drying, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
• the liquid crystal aligning agent of Example 9 was spin-coated on the ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 ° C., and then baked for 30 minutes in a hot air circulation oven at 200 ° C. A liquid crystal alignment film having a thickness of 100 nm was formed.
• liquid crystal alignment film After spraying a 6 ⁇ m bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (“XN-1500T” manufactured by Kyoritsu Chemical) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. Liquid crystal “MLC-6608” (trade name, manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (liquid crystal realignment treatment by heating) in an oven at 120 ° C. Produced. Similarly, vertically aligned liquid crystal cells were prepared using the liquid crystal aligning agents prepared in Examples 10 to 12 and Comparative Examples 1 and 2, respectively.
• the response speed immediately after the production of the liquid crystal cells using the obtained liquid crystal aligning agents of Examples 9 to 12 and Comparative Examples 1 and 2 was measured by the following method. Then, with a voltage of 20 Vp-p applied to the liquid crystal cell, UV from the outside of the liquid crystal cell was passed through a 313 nm bandpass filter and 10 J / cm 2 , and UV was passed through a 365 nm bandpass filter. Irradiated with 20 J / cm 2 . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared.
• Table 1 shows the response speed results immediately after the liquid crystal cell was prepared (indicated as “initial” in the table) and after UV irradiation (indicated as “10J @ 313 nm” or “20J @ 365 nm” in the table). Show.
• a liquid crystal cell was arranged between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a pair of polarizing plates in a crossed Nicol state, and a light amount detector.
• the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
• a rectangular wave with a voltage of ⁇ 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained.
• a voltage of 0% and ⁇ 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
• the liquid crystal aligning agent of Example 13 was spin-coated on two glass substrates with transparent electrodes, dried on a 90 ° C. hot plate for 60 seconds, and then baked in a hot air circulation oven at 200 ° C. for 30 minutes. A liquid crystal alignment film having a thickness of 100 nm was formed. When the cell was assembled using the substrate, the alignment direction was anti-parallel, and the coating surface was irradiated with 500 mJ / cm 2 of UV through a band-pass filter of 313 nm and a polarizing plate from directly above.
• the orientation of the liquid crystal cell was improved by using diamine or acrylic having a structure in which a phenyl ketone skeleton was introduced into the benzene ring of the cinnamoyl group.
• the orientation is improved not only when the structure is introduced into the polymic acid or polyimide, but also when introduced into the acrylic polymer. It was also confirmed that it did not depend on the type of ingredients. Further, it was confirmed that the orientation is improved as compared with the case where only the structure of the cinnamoyl skeleton is introduced, regardless of whether the structure is introduced into the main chain or the side chain of the polymer.
• a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and is suitable for a large-screen, high-definition liquid crystal television. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-047155 filed on March 8, 2013 is cited here as the disclosure of the specification of the present invention. Incorporated.

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