WO2013141262A1 - Agent d'alignement à cristaux liquides, film d'alignement à cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement à cristaux liquides, film d'alignement à cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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WO2013141262A1
WO2013141262A1 PCT/JP2013/057900 JP2013057900W WO2013141262A1 WO 2013141262 A1 WO2013141262 A1 WO 2013141262A1 JP 2013057900 W JP2013057900 W JP 2013057900W WO 2013141262 A1 WO2013141262 A1 WO 2013141262A1
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group
liquid crystal
atoms
single bond
polyimide
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PCT/JP2013/057900
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English (en)
Japanese (ja)
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亮一 芦澤
佳和 原田
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日産化学工業株式会社
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Priority to JP2014506255A priority Critical patent/JP6160610B2/ja
Priority to CN201380026443.1A priority patent/CN104350418B/zh
Priority to KR1020147029104A priority patent/KR102057443B1/ko
Publication of WO2013141262A1 publication Critical patent/WO2013141262A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display element.
  • An organic material film made of a polymer material has been widely used as an interlayer insulating film, a protective film, and the like in electronic devices because of its ease of formation and insulation performance.
  • a polymer material such as an acrylic resin, an epoxy resin, and a polyimide resin, but polyimide resins having high heat resistance are widely used in applications that require high durability.
  • a film made of polyimide is used as a liquid crystal alignment film.
  • the liquid crystal alignment film is a constituent member of a liquid crystal display element widely used as a display device, and is formed on the surface of a substrate that sandwiches a liquid crystal layer.
  • the liquid crystal alignment film has a role of aligning liquid crystal molecules constituting the liquid crystal layer in a certain direction, and in addition, has a role of controlling the pretilt angle of the aligned liquid crystal molecules.
  • polyimide-based organic films that are excellent in durability and suitable for controlling the pretilt angle of liquid crystals are widely used as liquid crystal alignment films that are currently used industrially.
  • This polyimide-based liquid crystal alignment film is usually formed using a resin composition called a liquid crystal aligning agent or the like.
  • the resin composition is prepared as a polymer containing a polymer synthesized using a diamine compound having a desired structure and a tetracarboxylic acid derivative.
  • the polymer to be contained include polyamic acid that is a polyimide precursor (sometimes referred to as polyamic acid), polyimide formed by imidizing polyamic acid, and the like.
  • the liquid crystal alignment film is formed as a cured film made of polyimide by forming a coating film using such a resin composition and heating the coating film to cure the coating film.
  • polyimide has the characteristics of high heat resistance and excellent durability, there is a problem that polyimide itself and its precursor polyamic acid are usually difficult to dissolve in a solvent. Therefore, a resin composition containing a polymer such as polyimide and polyamic acid is required to improve applicability, for example, when applied to a substrate or the like. Further, in order for the cured film made of polyimide to realize a desired alignment state of the liquid crystal molecules and to function as a liquid crystal alignment film, it is necessary to perform an alignment process on the cured film.
  • a rubbing treatment is known in which a surface of a cured film made of polyimide is rubbed in a certain direction using a cloth.
  • the rubbing treatment has various problems such as generation of dust by rubbing the cured film and the possibility of causing scratches on the surface of the formed liquid crystal alignment film to cause uneven alignment of liquid crystal molecules. ing.
  • attention has been paid to a photo-alignment processing technique that does not require rubbing in the formation of the liquid crystal alignment film of the liquid crystal display element.
  • liquid crystal molecules respond by applying a voltage to an electrode provided between a substrate and a liquid crystal alignment film, and display a desired image using the change in the alignment of the liquid crystal molecules.
  • the liquid crystal display element has various display methods in which the initial alignment state of liquid crystal molecules and the form of alignment change by voltage application are different.
  • VA vertical alignment
  • liquid crystal display element display methods a vertical alignment (VA) type liquid crystal display element in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate has been used in large-screen liquid crystal televisions and the like. Widely used for high-definition mobile applications (digital camera and mobile phone display).
  • this VA mode liquid crystal display element it is required that the orientation change so that the liquid crystal molecules are tilted in a desired fixed direction parallel to the substrate by voltage application. Therefore, in the VA liquid crystal display element, the liquid crystal molecules need to be slightly inclined from the normal direction of the substrate toward one direction in the substrate surface as the initial alignment state of the liquid crystal molecules before voltage application. .
  • a liquid crystal alignment film is used, and the liquid crystal molecules are aligned in the initial direction of the substrate from the normal direction of the substrate with a pretilt angle as the initial alignment state before voltage application.
  • a slightly tilted alignment state can be realized.
  • VA liquid crystal display elements protrusions for controlling the direction in which the liquid crystal tilts are formed on the TFT substrate or color filter substrate, and a slit is formed on the ITO (Indium Tin Oxide) electrode on the substrate.
  • a PVA (Patterned Vertical Alignment) system is known that controls the direction in which the liquid crystal falls by an electric field.
  • a patent A photo-alignment method disclosed in Document 1, Patent Document 2, and the like is known.
  • Patent Document 1 and Patent Document 2 a highly durable polyimide is used, and the molecular structure of the polyimide is suitably designed, and the vertical alignment property and light of the liquid crystal molecules required for the liquid crystal alignment film used for the VA liquid crystal display element. Orientation is realized.
  • a diamine compound having a cinnamate structure having photodimerization in the molecule and a linear hydrophobic side chain structure is used.
  • the polyamic acid which is a polyimide precursor is synthesize
  • Polyimide is a high heat-resistant polymer material that has high reliability and is suitable for use as a liquid crystal alignment film.
  • polyimide and its precursor polyamic acid or the like usually have a problem of low solubility in a solvent.
  • polyimide used for a liquid crystal aligning agent for VA liquid crystal display elements often has an alicyclic structure, an alkyl group, a fluorine atom, etc. in its side chain.
  • repelling, film thickness unevenness, and the like are likely to occur during application to the coating (see Patent Document 3). Therefore, the polyamic acid and polyimide formed from the diamine compound described in Patent Document 1 are also required to improve the solubility in a solvent and the coating property to a substrate.
  • the diamine compound described in Patent Document 1 has photoreactivity based on the intramolecular cinnamate structure. Therefore, for example, in the process of forming the liquid crystal alignment film, attention must be paid to the handling of the diamine compound, such as the need for light shielding during the process. That is, when obtaining a polyimide precursor and a polyimide from a diamine compound having a photoreactive group described in Patent Document 1 or the like, it is necessary to take measures so that an undesired photoreaction does not proceed. Similarly, when forming a liquid crystal aligning film using the obtained polyimide precursor or polyimide, it is necessary to suppress unwanted photoreactions.
  • a diamine compound having a structure rich in photoreactivity in the molecule such as a cinnamic acid ester structure described in Patent Document 1 and the like, and a polyimide precursor and a polyimide obtained using the diamine compound are used at the time of use. Therefore, attention to light and the like is required, and the liquid crystal alignment film forming process is complicated.
  • the molecular structure of polyimide is designed and controlled so as to have characteristics suitable as a liquid crystal alignment film, and is used for a liquid crystal alignment film.
  • Control of a desired molecular structure in polyimide is realized by controlling the molecular structure of a diamine compound or the like used for forming a polyimide.
  • the molecular structure of a diamine compound or the like is controlled, and a polyimide precursor or a polymer such as polyimide is synthesized using the diamine compound.
  • a cured film made of polyimide having a desired molecular structure is formed, and formation of a liquid crystal alignment film having desired characteristics is realized.
  • the molecular structure of a diamine compound or the like used for forming a polyimide precursor or a polymer such as polyimide plays an important role in realizing desired properties in polyimide and is very important.
  • a characteristic molecular structure for realizing desired characteristics is introduced into the molecule at the stage of the diamine compound used for forming the polyimide, there may be a problem in the process for producing the polyimide.
  • the formation of a liquid crystal alignment film made of polyimide is, as described above, a resin composition containing a polymer such as polyamic acid formed from a diamine compound (synonymous with a liquid crystal alignment agent, hereinafter also referred to as a liquid crystal alignment agent). And the resin composition is used to form a liquid crystal alignment film.
  • the diamine compound having a characteristic molecular structure may affect the properties of the polymer and the resin composition, and may affect the formation of a liquid crystal alignment film made of polyimide.
  • the diamine compound disclosed in Patent Document 1 has photoreactivity based on a cinnamic acid ester structure in order to realize photoalignment of the liquid crystal alignment film. Therefore, in the process of forming the liquid crystal alignment film, care must be taken in handling the diamine compound, such as the need for light shielding during the process. That is, when trying to obtain a polymer such as a polyimide precursor and a polyimide from a diamine compound having a photoreactive group disclosed in Patent Document 1, etc., light is blocked so that an undesired photoreaction does not proceed. It is necessary to take measures. Moreover, even when preparing a resin composition using the obtained polymer, it is necessary to suppress an undesired photoreaction. Furthermore, even when forming a cured film using a resin composition, it is necessary to suppress unwanted photoreactions.
  • a diamine compound that does not require measures such as shading
  • a polymer such as a polyimide precursor and polyimide. It is done.
  • the formed polyimide precursor and polyimide do not require light shielding and the like, are easy to handle, have excellent solubility in solvents, and have excellent coating properties for forming a polyimide film. Is required to be prepared.
  • the liquid crystal alignment film formed using the prepared resin composition can realize vertical alignment and photo-alignment in which the liquid crystal molecules are slightly tilted in a certain direction by photo-alignment treatment. It is required to be.
  • the object of the present invention is to prepare a liquid crystal aligning agent that can be easily formed, has excellent coating properties, and can form a vertical alignment type photo-alignment liquid crystal alignment film, and the liquid crystal aligning agent. It is to provide a polyimide precursor and a diamine compound to be used for producing a polyimide, a liquid crystal alignment film having a vertical alignment type photo-alignment property, and a liquid crystal display element having the liquid crystal alignment film.
  • the present invention has the following gist.
  • a liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyimide precursor having a ⁇ -hydroxyester structure and a polyimide having a ⁇ -hydroxyester structure.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring having 8 to 10 atoms. And an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from the group consisting of a system and a tricyclic ring system having 13 or 14 atoms.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring having 8 to 10 atoms.
  • X 2 represents a single bond
  • X 3 represents a linear alkyl group having 3 to 20 carbon atoms or a fatty acid having 4 to 40 carbon atoms, and represents at least one divalent linking group selected from the group consisting of benzene, ether, ester, amide, and urethane.
  • X 1 is a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, a bicyclic ring system having 8 to 10 atoms, And an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from the group consisting of a tricyclic ring system having 13 or 14 atoms
  • X 2 represents a single bond or an ether
  • X 3 represents a straight-chain alkyl group having 3 to 20 carbon atoms or an alicyclic group having 4 to 40 carbon atoms, which is at least one divalent linking group selected from the group consisting of ester, amide, and urethane.
  • X 5 represents a single bond, an oxygen atom, * —OCO— or * —OCH 2 — (where a bond marked with “*” is bonded to X 4 ), provided that X 4 is a single bond When it is a bond, X 5 is a single bond.)
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring having 8 to 10 atoms.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring having 8 to 10 atoms.
  • X 2 represents a single bond or And at least one divalent linking group selected from the group consisting of ether, ester, amide, and urethane
  • X 6 represents a divalent organic group having a single bond or an alicyclic skeleton having 4 to 40 carbon atoms
  • X 7 represents a single bond or a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms
  • X 8 represents a linear alkyl group having 1 to 20 carbon atoms.
  • X 1 is a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, a bicyclic ring system having 8 to 10 atoms, And an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from the group consisting of a tricyclic ring system having 13 or 14 atoms
  • X 2 represents a single bond or an ether
  • X 6 represents at least one divalent linking group selected from the group consisting of ester, amide, and urethane
  • X 6 represents a divalent organic group having a single bond or an alicyclic skeleton having 4 to 40 carbon atoms.
  • X 7 represents a single bond or a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms
  • X 8 represents a linear alkyl group having 1 to 20 carbon atoms
  • X 9 is Represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, provided that the alkylene group is a hydroxyl group. Therefore substituted .
  • X 10 represents a single bond, an oxygen atom, * - OCO -, * - OCH 2 -, * - COO -, * - NHCO-, or * -CONH- (where "*" bond marked with binds to X 9.) represents a. However, X 10 when X 9 is a single bond is a single bond.)
  • a polymer having a ⁇ -hydroxyester structure in the molecule obtained by using the diamine compound according to any one of (8) to (10) above.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, 5 or 6 An unsubstituted or substituted selected from the group consisting of two adjacent monocyclic rings of 6; bicyclic ring systems of 8 to 10 atoms; and tricyclic ring systems of 13 or 14 atoms Represents a carbocyclic or heterocyclic aromatic group, and X 2 represents a single bond or at least one divalent linking group selected from the group consisting of ether, ester, amide, and urethane.
  • X 6 represents a single bond or a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms
  • X 7 represents a divalent organic group having a single bond or an alicyclic skeleton having 4 to 40 carbon atoms the representative .
  • X 8 is .
  • X 9 representing a linear alkyl group having 1 to 20 carbon atoms, a single bond, methylene group or a of 2 to 6 carbon atoms Represents a Killen group provided that the alkylene group may .
  • X 10 be substituted by a hydroxyl group, a single bond, an oxygen atom, * -.
  • the diamine compound which can be easily handled and can form polymers such as a polyimide precursor excellent in solubility, and a polyimide
  • a liquid crystal aligning agent that is easy to handle, has excellent coating properties, and can form a vertical alignment type photo-alignment liquid crystal alignment film, is formed from the liquid crystal aligning agent, and is vertically
  • An alignment-type photo-alignment liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film can be provided, and can be used as a display element that displays a high-definition image.
  • a polyimide film having high heat resistance and high strength is often used as a liquid crystal alignment film for aligning liquid crystal molecules.
  • the method of using the following liquid crystal aligning agents is used suitably.
  • a liquid crystal aligning agent containing a polyimide precursor such as polyamic acid is prepared.
  • a method of forming a coating film using the obtained liquid crystal aligning agent and imidizing on a substrate to obtain a polyimide film is known.
  • previously imidized polyimide is dissolved in a solvent to prepare a solvent-soluble liquid crystal aligning agent, and a coating film is formed using the liquid crystal aligning agent.
  • the method for forming a polyimide film to be a liquid crystal alignment film is the same for the VA liquid crystal display element.
  • the VA liquid crystal display element requires a vertical alignment type liquid crystal alignment film in which liquid crystal molecules are slightly inclined from the normal direction of the substrate toward one direction in the substrate surface.
  • a polyimide film that aligns liquid crystal molecules in the normal direction of the substrate is obtained using a liquid crystal alignment agent containing a polyimide precursor or polyimide.
  • this polyimide film is subjected to an alignment treatment so that the liquid crystal molecules are slightly inclined from the normal direction of the substrate toward one direction in the substrate surface, thereby forming a desired vertical alignment type liquid crystal alignment film. is doing.
  • a rubbing treatment is known in which the surface of a polyimide film is rubbed in a certain direction using a cloth.
  • the rubbing treatment has various problems because it generates dust by rubbing the polyimide film and may cause scratches on the surface of the liquid crystal alignment film to cause uneven alignment of liquid crystal molecules. Therefore, in the manufacture of a VA liquid crystal display element, a liquid crystal alignment film photo-alignment technique that does not require a rubbing process has been used. That is, development of a vertical alignment type photo-alignment liquid crystal alignment film is underway.
  • the vertical alignment type photo-alignment liquid crystal alignment film has a structure for realizing vertical alignment of liquid crystal molecules and a structure for realizing photo-alignment inside.
  • the liquid crystal aligning agent is composed of a polyimide film
  • a diamine compound or a tetracarboxylic acid derivative for forming the polyimide film contains a specific structure for realizing such vertical alignment and photoalignment. It is preferable to use it.
  • the formed polyimide can realize a liquid crystal alignment film having vertical alignment and photo alignment.
  • Patent Documents 1 and 2 a polyimide film is formed using a diamine compound having a cinnamate structure having photodimerization and a linear hydrophobic side chain structure in the molecule. Next, the polyimide film is subjected to a photo-alignment treatment, thereby realizing a vertical alignment type photo-alignment liquid crystal alignment film.
  • the diamine compound for forming polyimide has a cinnamic acid ester structure in the molecule, and has a structure rich in photoreactivity. Therefore, attention such as shading is indispensable for the handling. That is, in the polyimide precursor forming step and the polyimide forming step, attention and measures for suppressing unwanted photoreactions are required.
  • the diamine compound of the present invention is a novel compound having a characteristic molecular structure, and can be suitably used for the synthesis of polymers such as polyimide precursors and polyimides.
  • the diamine compound of the present invention does not have photoreactivity by itself, a cured film obtained from a polymer formed using the diamine compound can have photoreactivity. That is, it can be suitably used to provide a liquid crystal alignment film made of polyimide having a structure suitable for photo-alignment processing. In particular, it can be used to provide a vertical alignment type photo-alignment liquid crystal alignment film suitable for forming a VA liquid crystal display element.
  • the diamine compound of the present invention has a ⁇ -hydroxyester structure in the molecule.
  • the liquid crystal alignment film formed using the diamine compound has a structure suitable for realizing vertical alignment of liquid crystal molecules.
  • the ⁇ -hydroxyester structure in the molecule undergoes a dehydration reaction by heating to form a photoreactive double bond.
  • the diamine compound having a ⁇ -hydroxyester structure of the present invention can react with a tetracarboxylic acid derivative to provide a polymer such as a polyimide precursor and polyimide.
  • the coating film formed using the obtained liquid crystal aligning agent containing the polymer can produce
  • a polyimide precursor can be synthesized from a diamine compound having a ⁇ -hydroxyester structure, and a liquid crystal aligning agent containing the obtained polyimide precursor can be prepared.
  • the coating film of the liquid crystal aligning agent is heated to imidize the polyimide precursor component, and at the same time, a dehydration reaction takes place at the ⁇ -hydroxy ester structure, resulting in a photoreactive double bond in the molecule. Can be introduced.
  • a cured film in which a cured film portion having photoreactivity and a portion having a polyimide precursor not having photoreactivity are mixed can be prepared. That is, it is possible to make a part having a photoreactive group and a part having no photoreactivity on the same film.
  • the conventional process of forming a negative pattern by covering the resin surface with a mask or the like and irradiating the resin with a mask or the like can be made by only the heating process without a mask.
  • a polyimide is synthesized from a diamine compound having a ⁇ -hydroxyester structure, and a liquid crystal aligning agent containing the obtained polyimide can be prepared.
  • the coating film of the liquid crystal aligning agent can be heated to form a polyimide film, and at the same time, a dehydration reaction can be caused in the ⁇ -hydroxyester structure and a photoreactive double bond can be introduced into the molecule.
  • the polyimide precursor and the polymer such as polyimide according to the present invention form a cured film made of polyimide and, for example, cinnamic acid in the molecule.
  • Photoreactive sites such as ester structures can be introduced.
  • the cured film formed from the polymer can exhibit photoreactivity. That is, in a liquid crystal alignment film formed using these cured films, photoalignment can be realized.
  • the diamine compound according to the present invention has a molecular structure suitable for aligning liquid crystal molecules in the normal direction of the substrate when a liquid crystal alignment film is formed.
  • the cured film obtained by synthesizing from the diamine compound having a ⁇ -hydroxyester structure of the present invention and formed from at least one of a polyimide precursor and a polyimide is a vertically aligned photoreactive liquid crystal. It can be used as an alignment film.
  • the diamine compound having a ⁇ -hydroxyester structure of the present invention does not have a photoreactive structure in the molecule and is stable to light. Therefore, no care or countermeasure is required for its handling.
  • the diamine compound having a ⁇ -hydroxy ester structure of the present invention can synthesize a polyimide precursor and a polymer such as polyimide having a ⁇ -hydroxy ester structure.
  • the obtained polymer does not have a photoreactive structure in the molecule, and does not have photoreactivity before introducing a double bond. Therefore, the polymer of the present invention is stable with respect to light, and conventional handling, measures, etc. are not required for its handling.
  • the photoreactive double bond can be introduced into the structure after the cured film using the polymer is formed.
  • the polyimide precursor and the polymer such as polyimide of the present invention have a ⁇ -hydroxyester structure in the molecule and have a high solubility in a solvent by having a hydroxy group derived from the structure in the molecule. . Therefore, the liquid crystal aligning agent of this invention has high solubility with polymers, such as a polyimide precursor to contain and a polyimide, and has the outstanding applicability
  • the polymer itself since the polymer itself has a hydroxy group at the side chain site, the polymer itself has high hydrophilicity and excellent coating property to the substrate.
  • the diamine compound of the present invention has a ⁇ -hydroxyester structure and a linear hydrophobic side chain structure in the molecule.
  • the diamine compound of the present invention can react with a tetracarboxylic acid derivative to provide a polymer such as a polyimide precursor or polyimide.
  • the polymer of the present invention can be dissolved in a solvent or the like to form a liquid crystal aligning agent, and after forming a coating film, a cured film can be formed.
  • the cured film of the present invention is derived from the ⁇ -hydroxyester structure of the diamine compound, has a photoreactive double bond in the molecule, and has a linear hydrophobic side chain structure. Therefore, the cured film of the present invention can form a liquid crystal alignment film, is suitable for a photo-alignment treatment in the liquid crystal alignment film, and provides a vertical alignment type photo-alignment liquid crystal alignment film. it can.
  • the present inventors have developed a polyimide and a polyimide precursor having a novel structure for use in a vertical alignment type photo-alignment liquid crystal alignment film.
  • the polyimide and the polyimide precursor of the present invention each have a ⁇ -hydroxy ester structure in the molecule, and also have a structure for realizing vertical alignment of liquid crystal molecules.
  • Various methods can be used to form the polyimide and the polyimide precursor used for the vertical alignment type photo-alignment liquid crystal alignment film having the novel structure of the present invention. In particular, it has been found that a method using a diamine compound having a novel structure is suitable.
  • the diamine compound of the present invention has a ⁇ -hydroxy ester structure in the molecule, and also has a structure for realizing vertical alignment of liquid crystal molecules.
  • the polyimide precursor of the present invention and the polyimide obtained by imidizing it have a ⁇ -hydroxyester structure in the molecule.
  • a method for obtaining a polyimide precursor having a ⁇ -hydroxy ester structure in the molecule can be realized by a method using a diamine compound having a ⁇ -hydroxy ester structure in the molecule. Further, it can be realized by a method using a tetracarboxylic acid derivative having a ⁇ -hydroxyester structure in the molecule.
  • a polyimide precursor is obtained by polymerizing a diamine compound and a tetracarboxylic acid derivative
  • a compound having a ⁇ -hydroxyester structure in the molecule is used in combination as an additive, and ⁇ -hydroxy is added to the formed polyimide precursor.
  • the method using the diamine compound of the present invention having a ⁇ -hydroxyester structure in the molecule is particularly preferable.
  • the present invention using a diamine compound having a ⁇ -hydroxyester structure in the molecule will be described in detail.
  • the polyimide precursor includes polyamic acid, polyamic acid ester, and the like.
  • the diamine compound of the present invention is a diamine compound having a ⁇ -hydroxyester structure.
  • the ⁇ -hydroxyester structure can be represented by the following formula (HE).
  • the diamine compound of the present invention preferably has a structure represented by the following formula (HE-1).
  • HE-1 a structure represented by the following formula (HE-1).
  • HE-1 an excellent photoreaction in the molecule when heated.
  • a double bond having a property can be formed.
  • the polyimide precursor in which the double bond is formed and the polyimide obtained by imidizing the polyimide precursor are used for the formation of a liquid crystal alignment film, it can exhibit excellent optical alignment performance.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring having 8 to 10 atoms. And an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from the group consisting of a system and a tricyclic ring system having 13 or 14 atoms.
  • a particularly preferable structure is a structure represented by the following formula (HE-1-1).
  • polyimide precursors and polyimides formed using a diamine compound having a structure represented by the following formula (HE-1-1) when heated, a double bond having photoreactivity in the molecule Can be formed.
  • the polyimide precursor in which the double bond is formed and the polyimide imidized from the polyimide precursor can exhibit particularly excellent photo-alignment performance when used for forming a liquid crystal alignment film.
  • the diamine compound of the present invention preferably has a structure of the following formula (HE-2) having a ⁇ -hydroxyester structure and a structure for realizing vertical alignment of liquid crystal molecules.
  • HE-2 a structure of the following formula (HE-2) having a ⁇ -hydroxyester structure and a structure for realizing vertical alignment of liquid crystal molecules.
  • X 1 has the same meaning as in the above formula (HE-1).
  • X 2 represents a single bond or at least one divalent linking group selected from the group consisting of ether, ester, amide, and urethane.
  • X 2 is preferably a single bond, an ether group, an ester group or an amide group, more preferably a single bond, an ether group or an ester group.
  • X 3 represents a linear alkyl group having 3 to 20 carbon atoms or a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. However, the hydrogen atom of this alkyl group may be replaced with a fluorine atom.
  • X 3 includes, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, spiro [5.5] undecyl group, bicyclo [2.2.2] octyl group, bicyclo [2.2.1] heptyl group, cyclohexyl-n-heptyl group
  • Preferable examples of the diamine compound of the present invention include compounds represented by the following formula (DA).
  • DA formula (DA)
  • X 1 has the same definition as in the above formula (HE-1), and the same applies to the preferred examples.
  • X 2 has the same definition as in formula (HE-2) above, and the same applies to the preferred examples.
  • X 3 has the same definition as in formula (HE-2), and the same applies to the preferred examples.
  • X 4 represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. However, this alkylene group may be substituted with a hydroxyl group.
  • X 4 is preferably a single bond, a methylene group, an ethylene group, an n-propylene group or an n-butylene group, more preferably a single bond or an ethylene group.
  • X 5 represents a single bond, an oxygen atom, * —OCO— or * —OCH 2 — (wherein a bond marked with “*” is bonded to X 4 ). However, when X 4 is a single bond, X 5 is a single bond.
  • X 5 is preferably a single bond, an oxygen atom, or * —OCH 2 —, and more preferably * —OCH 2 — or an oxygen atom.
  • diamine compound represented by the above formula (DA) include diamine compounds represented by the following formulas (DA-1) to (DA-8).
  • R a is an alkyl group having 3 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
  • X a represents a linear alkyl group having 3 to 16 carbon atoms, such as n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group or n-hexadecyl group are preferred, n-octyl group, n- A nonyl group, an n-decyl group, an n-undecyl group, or
  • R b is an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
  • Xb is a linear alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl is preferred, n-propyl, n-butyl, n-pentyl, n-hexyl or n- A heptyl group is more preferred.
  • the diamine compound of the present invention is a diamine compound having a ⁇ -hydroxyester structure, and has a structure of the following formula (HE-3) having a structure for realizing vertical alignment of liquid crystal molecules. Is preferred.
  • X 1 represents a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, or a bicyclic ring system having 8 to 10 atoms. And an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from the group consisting of 13 or 14 tricyclic ring systems.
  • X 1 includes benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, anthracene ring, furan ring, thiophene ring, pyrrole ring, pyridine ring, pyridazine ring, benzofuran ring, indole ring, quinoline ring, benzimidazole ring , A quinoxaline ring, a carbazole ring, a fluorene ring, or a xanthene ring, and a benzene ring or a naphthalene ring is more preferable.
  • X 2 represents a single bond or at least one divalent linking group selected from the group consisting of ethers, esters, amides, and urethanes.
  • X 2 is preferably a single bond, an ether group, an ester group or an amide group, more preferably a single bond, an ether group or an ester group.
  • X 6 represents a divalent organic group having a single bond or an alicyclic skeleton having 4 to 40 carbon atoms.
  • X 6 is cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, spiro [5.5] undecyl, bicyclo [2.2.2] octyl, bicyclo [2 2.1]
  • a heptyl group, a phenyl group, a naphthyl group, or an anthracenyl group is preferable, and a cyclohexyl group or a phenyl group is more preferable.
  • X 7 represents a divalent organic group having a single bond or an alicyclic skeleton having 4 to 40 carbon atoms.
  • X 7 includes a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a spiro [5.5] undecyl group, a bicyclo [2.2.2] octyl group, and a bicyclo [2 2.1]
  • a heptyl group, a phenyl group, a naphthyl group, and an anthracenyl group are preferable, and a cyclohexyl group or a phenyl group is more preferable.
  • X 8 represents a linear alkyl group having 1 to 20 carbon atoms.
  • X 8 is a linear alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, An n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, or an n-dodecyl group is preferable, and an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, or An n-heptyl group is more preferred.
  • the linear alkyl group having 1 to 20 carbon atoms has a function as
  • DIA diamine compound represented by the following formula (DIA).
  • X 1 has the same definition as in formula (HE-3), and the same applies to the preferred examples.
  • X 2 has the same definition as in formula (HE-3), and the same applies to the preferred examples.
  • X 6 has the same definition as in formula (HE-3), and the same applies to the preferred examples.
  • X 7 has the same definition as in formula (HE-3), and the same applies to the preferred examples.
  • X 8 has the same definition as in formula (HE-3), and the same applies to the preferred examples.
  • X 9 represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. However, this alkylene group may be substituted with a hydroxyl group.
  • X 9 is preferably a single bond, a methylene group, an ethylene group, an n-propylene group, or an n-butylene group, and more preferably a single bond or an ethylene group.
  • X 10 represents a single bond, an oxygen atom, * —OCO—, * —OCH 2 —, * —COO—, * —NHCO—, or * —CONH— (where the bond marked with “*” is X 9 It is combined with.) However, when X 9 is a single bond, X 10 is a single bond. X 10 is preferably a single bond, an oxygen atom, * —OCO—, * —OCH 2 —, or * —COO—, and more preferably —OCH 2 — or an oxygen atom.
  • Examples of the diamine compound represented by the formula (DIA) include diamine compounds represented by the following formulas (DIA-1) to (DIA-7).
  • a diamine compound having a ⁇ -hydroxyester structure in addition to the diamine compound having a ⁇ -hydroxyester structure, as a preferable diamine compound, for example, a diamine compound having a ⁇ -hydroxyketone structure as represented by the following formula (HK-1) Can be illustrated.
  • the diamine compound having the ⁇ -hydroxyketone structure can be used for the synthesis of a polymer such as a polyimide precursor or a polyimide of the present invention.
  • this diamine compound itself does not have photoreactivity, a cured film formed from a polymer synthesized using the diamine compound introduces a photoreactive double bond structure into the molecule by heating or the like. And has photoreactivity.
  • liquid crystal alignment film made of polyimide having a structure suitable for optical alignment treatment.
  • it can be used to provide a vertical alignment type photo-alignment liquid crystal alignment film suitable for forming a VA liquid crystal display element.
  • Examples of the diamine compound represented by the formula (HK-1) include diamine compounds represented by the following formulas (DIA-8) to (DIA-11).
  • the method for forming the ⁇ -hydroxyester structure in the diamine compound of the present invention is not particularly limited.
  • it can be formed by preparing zinc enolate from the corresponding ⁇ -haloester by a Reformatsky reaction and reacting with an aldehyde.
  • a method of reacting an ⁇ -haloester with an aldehyde in the presence of a metal alkoxide, performing Darzens condensation for synthesizing an epoxide, and then deriving the ⁇ -hydroxyester by hydrolysis is also included.
  • Another method is to selectively reduce only the ketone moiety in the presence of ester from ⁇ -ketoester, which is the precursor of ⁇ -hydroxy ester, using sodium borohydride, sodium cyanoborohydride, or the like. Even so, ⁇ -hydroxyesters can be synthesized. Also known is a method of obtaining the target ⁇ -hydroxy ester by reducing the ketone moiety under a metal catalyst such as Ru.
  • the target ⁇ -ketoester or ⁇ -hydroxyester can be obtained by cross-Claisen condensation when one ester does not have acidic ⁇ hydrogen.
  • Examples thereof include a synthesis method, a method in which an alkyl cyanoformate (Mander reagent) is reacted with a ketone enolate, a method in which an acid imidazolide is produced from carbonyldiimidazole and a carboxylic acid, and a monoalkylmagnesium malonate is reacted.
  • a preferred method for synthesizing a diamine compound having a ⁇ -hydroxyester structure is as follows. First, Meldrum's acid derivative is synthesized from carboxylic acid chloride having a target skeleton by reacting Meldrum's acid in the presence of a base catalyst. Next, the Meldrum's acid derivative is reacted with an alcohol having a corresponding structure having a nitro group that is subsequently reduced to an amino group, thereby synthesizing a target ⁇ -ketoester. Thereafter, by reducing the nitro group in the molecule by hydrogenation and reducing the ketone with sodium borohydride, a ⁇ -hydroxyester structure can be formed, and a diamine compound having a novel structure can be synthesized.
  • the method for synthesizing a diamine compound having a ⁇ -hydroxyester structure of the present invention it is desirable to select a production method that avoids the use of a strong base. For example, even when dinitrobenzyl alcohol is used as a raw material, the synthesis of the target compound can be achieved with high efficiency by suppressing the side reaction.
  • the main steps of the method for producing a diamine compound represented by the above formula (DIA) are as follows.
  • DA diamine for reacting with a tetracarboxylic acid derivative to synthesize a polyimide precursor and a polyimide that can be contained in the liquid crystal aligning agent of the present invention
  • a diamine represented by the above formula (DA) or formula (DIA) A compound may be used alone.
  • Y 1 is a divalent organic group, and two or more kinds may be mixed.
  • R 1 and R 2 represent a hydrogen atom or a monovalent organic group. More specifically, in the above formula (AM), R 1 and R 2 are each independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group having 1 to 10 carbon atoms. It is a group.
  • alkyl group having 1 to 10 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, and a cyclopentyl group. , A cyclohexyl group, a bicyclohexyl group, and the like.
  • alkenyl group having 1 to 10 carbon atoms which may have a substituent include those in which one or more CH 2 —CH 2 structures present in the above alkyl group are replaced with a CH ⁇ CH structure.
  • vinyl group More specifically, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group And cyclohexenyl group.
  • alkynyl group having 1 to 10 carbon atoms which may have a substituent examples include those obtained by replacing one or more CH 2 —CH 2 structures present in the alkyl group with a C ⁇ C structure. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group and the like can be mentioned.
  • the above alkyl group, alkenyl group and alkynyl group may have a substituent as long as it has 1 to 10 carbon atoms as a whole, and may further form a ring structure by the substituent.
  • the formation of a ring structure by a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
  • substituents include halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls.
  • halogen group examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a phenyl group is mentioned as an aryl group which is a substituent. This aryl group may be further substituted with the other substituent described above.
  • the organooxy group that is a substituent can have a structure represented by OR.
  • R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Specific examples of the organooxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
  • organothio group which is a substituent
  • R examples include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above.
  • Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
  • the organosilyl group as a substituent can have a structure represented by —Si— (R) 3 .
  • R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
  • the acyl group as a substituent can have a structure represented by —C (O) —R.
  • R include the alkyl groups, alkenyl groups, and aryl groups described above. These Rs may be further substituted with the substituent described above.
  • Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
  • ester group which is a substituent a structure represented by —C (O) O—R or OC (O) —R can be shown.
  • R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above.
  • thioester group a structure represented by —C (S) O—R or OC (S) —R can be shown.
  • R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above.
  • the phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) 2 .
  • R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the substituent amide group include —C (O) NH 2 , —C (O) NHR, —NHC (O) R, —C (O) N (R) 2 , —NRC (O) R.
  • the structure represented by can be shown.
  • R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the aryl group as a substituent include the same aryl groups as described above.
  • the aryl group may be further substituted with the other substituent described above.
  • Examples of the alkyl group as a substituent include the same alkyl groups as described above.
  • the alkyl group may be further substituted with the other substituent described above.
  • Examples of the alkenyl group as a substituent include the same alkenyl groups as described above.
  • the alkenyl group may be further substituted with the other substituent described above.
  • Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above.
  • the alkynyl group may be further substituted with the other substituent described above.
  • R 1 and R 2 a hydrogen atom or a carbon atom that may have a substituent is 1
  • An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.
  • examples of specific structures of Y 1 include Y-1 to Y-106 shown below, but are not limited thereto.
  • the tetracarboxylic acid derivative used for the reaction with the diamine compound described above and for synthesizing the polyimide precursor or polyimide that can be contained in the liquid crystal aligning agent of the present invention is not particularly limited.
  • Examples of the tetracarboxylic acid derivative include tetracarboxylic dianhydride (represented by the following formula (CB1)), tetracarboxylic monoanhydride (represented by the following formula (CB2)), and tetracarboxylic acid (represented by the following formula (CB1)).
  • dicarboxylic acid dialkyl ester represented by the following formula (CB4)
  • dicarboxylic acid chloride dialkyl ester represented by the following formula (CB5)
  • the like a dicarboxylic acid dialkyl ester (represented by the following formula (CB4)), a dicarboxylic acid chloride dialkyl ester (represented by the following formula (CB5)), and the like.
  • the tetracarboxylic acid derivative one kind may be used alone, or two or more kinds may be used in combination.
  • R 3 represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.
  • Z 1 include the following formulas (Z-1) to (Z-46).
  • the polyimide precursor contained in the liquid crystal aligning agent of the present invention was synthesized by using a diamine component containing a diamine compound having the ⁇ -hydroxyester structure, such as the above formula (DA) or the above formula (DIA), as an essential component.
  • a diamine component containing a diamine compound having the ⁇ -hydroxyester structure such as the above formula (DA) or the above formula (DIA)
  • PA structural unit represented by the following formula
  • Z is an example of the above-described tetracarboxylic acid derivative, tetracarboxylic dianhydride, tetracarboxylic monoanhydride, tetracarboxylic acid, dicarboxylic acid dialkyl ester, and dicarboxylic acid chloride dialkyl ester. It is a group derived from the Z 1 group.
  • R C is a hydrogen atom or a monovalent organic group derived from the above-described tetracarboxylic acid derivative or esterifying agent described later, preferably having 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms. Represents an alkyl group.
  • Y is a group derived from Y 1 groups corresponding other diamine compound represented by the group and the formula (AM) of the diamine compound having the above-described ⁇ - hydroxy ester structure.
  • a 1 and A 2 represent a hydrogen atom or a monovalent organic group derived from the R 1 group and the R 2 group of the other diamine compound represented by the above formula (AM).
  • the polyamic acid which is the polyimide precursor of the present invention includes, for example, a diamine component (hereinafter referred to as a diamine component having a ⁇ -hydroxy ester structure of a diamine compound such as the above formula (DA) or the above formula (DIA) as an essential component. It is simply referred to as a diamine component.) And a tetracarboxylic dianhydride that is a tetracarboxylic acid derivative.
  • a reaction method of the diamine component and tetracarboxylic dianhydride for obtaining the polyamic acid contained in the liquid crystal aligning agent of the present invention a known method can be used.
  • the reaction method is a method in which a diamine component and tetracarboxylic dianhydride are reacted in an organic solvent.
  • the reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent is not particularly limited as long as the generated polyamic acid dissolves. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol,
  • the above organic solvents may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the organic solvent as long as the generated polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
  • the diamine component or tetracarboxylic dianhydride when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
  • the reaction (polymerization reaction) temperature can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Accordingly, the total concentration of the diamine component and tetracarboxylic dianhydride in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio between the total number of moles of tetracarboxylic dianhydride and the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.
  • the polyamic acid ester which is a polyimide precursor includes, for example, a diamine component and a tetracarboxylic acid derivative containing a diamine compound having a ⁇ -hydroxy ester structure of a diamine compound such as the above formula (DA) or the above formula (DIA) as an essential component.
  • DA above formula
  • DIA above formula
  • the polyamic acid obtained from a diamine component and tetracarboxylic dianhydride can be synthesized by esterification. Specifically, it is synthesized by reacting a polyamic acid and an esterifying agent in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. can do.
  • 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 10 molar equivalents, more preferably 2 to 6 molar equivalents, per 1 mol of the polyamic acid repeating unit.
  • the organic solvent used in the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone from the viewpoint of polymer solubility. These may be used alone or in combination. May be.
  • the concentration of the polyamic acid during the reaction is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the organic solvent is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the viewpoint of the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the polymer concentration during the reaction 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.
  • 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 condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, 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 can be used.
  • the addition amount of the condensing agent is preferably 2 to 10 mol times, more preferably 2 to 3 mol times with
  • tertiary amines such as pyridine and triethylamine can be used.
  • the addition amount of the base is preferably 2 to 10 times by mole and more preferably 2 to 4 times by mole with respect to the diamine component from the viewpoint of easy removal and easy obtaining of a high molecular weight product.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0.1 to 3.0 mol times, more preferably 0.1 to 1.0 mol times based on the diamine component.
  • a high molecular weight polyamic acid ester is obtained, and therefore the synthesis method (1) or (2) is particularly preferable.
  • the solution of the polyamic acid ester obtained by the above-described method can precipitate a polymer by being poured into a poor solvent while being well stirred. After dissolving and precipitating several times and washing with a poor solvent, purified polyamic acid ester powder can be obtained by drying at room temperature or by heating.
  • a poor solvent Water, methanol, ethanol, isopropyl alcohol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned, Methanol, ethanol, and isopropyl alcohol are preferable.
  • the liquid crystal aligning agent of this invention contains the at least 1 sort (s) of polymer chosen from the group which consists of the polyimide precursor mentioned above and a polyimide.
  • a polyimide it can be set as the polyimide obtained by carrying out dehydration ring closure of the polyamic acid as a polyimide precursor mentioned above. That is, polyamic acid as a polyimide precursor synthesized using a diamine component containing a diamine compound having a ⁇ -hydroxyester structure of a diamine compound such as the above formula (DA) or the above formula (DIA) as an essential component is dehydrated. Obtained by ring closure.
  • the obtained polyimide is useful as a polymer for obtaining the liquid crystal alignment film of the present invention, and is dissolved in a solvent to constitute a liquid crystal aligning agent.
  • a cured film made of polyimide is obtained.
  • the dehydration ring closure rate (imidation rate) of an amic acid group does not necessarily need to be 100%, It can adjust arbitrarily according to a use and the objective. it can.
  • Examples of the method for imidizing a polyamic acid include thermal imidization in which a polyamic acid solution is heated as it is, and catalytic imidation in which a catalyst is added to a polyamic acid solution.
  • the polyamic acid used for imidation has a ⁇ -hydroxy ester structure derived from a diamine compound having a ⁇ -hydroxy ester structure used at the time of synthesis. Therefore, as a method for polyimidizing the polyamic acid, catalytic imidation that can be reacted at a relatively low temperature is desirable so that the ⁇ -hydroxyester structure inside the polyamic acid can be maintained.
  • Catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. As mentioned above, although the component which can be contained in the liquid crystal aligning agent of this invention was demonstrated, the liquid crystal aligning agent of this invention prepared using those components is demonstrated next.
  • the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt
  • the resin component includes at least one polymer selected from the group consisting of the polyimide precursor and polyimide described above.
  • the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 3 to 10% by mass.
  • the resin component may be all the above-described polymers, or other polymers may be mixed. At that time, the content of the polymer other than the above-mentioned polymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • the organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component containing the polymer etc. which were mentioned above is dissolved. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl e
  • the liquid crystal aligning agent of this invention may contain components other than the above.
  • examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
  • the following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
  • These poor solvents may be used alone or in combination.
  • the above solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • the compound for improving the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • the amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the liquid crystal alignment of the liquid crystal alignment film to be formed may be lowered.
  • the liquid crystal aligning agent of the present invention has a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired. Further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal alignment film of the present invention and the liquid crystal display element having the liquid crystal alignment film will be described.
  • the liquid crystal aligning agent of the present invention is a polyimide precursor synthesized using a diamine component containing, as an essential component, a diamine compound having a ⁇ -hydroxyester structure of a diamine compound such as the above formula (DA) or the above formula (DIA). And at least one polymer selected from the group consisting of polyimide and polyimide.
  • the liquid crystal aligning agent is preferably filtered before being applied to the substrate, then applied, dried by pre-baking, and then heated and fired to form a polyimide film.
  • the polyimide precursor and / or polyimide contained in the liquid crystal aligning agent of the present invention has a ⁇ -hydroxy ester structure in the molecule, so that a photoreactive double bond is formed in the molecule. Can be formed.
  • the coating film of the liquid crystal aligning agent of the present invention when the coating film of the liquid crystal aligning agent is heated and baked to perform the imidization reaction of the polyimide precursor component, a dehydration reaction is simultaneously performed in the ⁇ -hydroxyester structure part, A photoreactive double bond can be introduced into the polyimide film.
  • the coating film obtained by applying and drying the liquid crystal aligning agent is heated and fired to form a polyimide film, and at the same time, dehydration is performed in the ⁇ -hydroxyester structure. The reaction takes place and photoreactive double bonds can be introduced into the polyimide film.
  • the liquid crystal aligning agent of the present invention can form a polyimide film and introduce a double bond by heating and baking the coating obtained by applying and drying the liquid crystal aligning agent.
  • a photoreactive site such as a cinnamic acid ester structure can be introduced.
  • substrate can be used as a board
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used in addition to a glass substrate.
  • the liquid crystal aligning agent of this invention in manufacture of a liquid crystal display element, it is preferable to form a liquid crystal aligning film using the board
  • an opaque substrate such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum is used for the electrode. You can also
  • substrate Industrially, screen printing, offset printing, flexographic printing, the inkjet method etc. are common. As other coating methods, there are a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and these may be used according to the purpose.
  • the liquid crystal aligning agent of the present invention has good coating properties even when the above coating method is used.
  • a drying step by pre-baking after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to heating and baking is not constant for each substrate, or if heating and baking is not performed immediately after application, drying is performed. It is preferable to include a process.
  • the drying by this pre-bake should just evaporate the solvent to such an extent that a coating-film shape does not deform
  • the drying means by pre-baking is not particularly limited. As a specific example, a method of drying on a hot plate at 50 to 120 ° C., preferably 80 to 120 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes is preferable.
  • the substrate coated with the liquid crystal aligning agent can be baked at a temperature of 120 to 350 ° C. by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven.
  • the baking temperature is a temperature suitable for forming a polyimide film, and a temperature at which a dehydration reaction proceeds is selected in the polyimide precursor and / or the ⁇ -hydroxyester structure of the polyimide contained in the liquid crystal aligning agent.
  • the firing temperature is preferably 140 to 300 ° C, more preferably 180 to 250 ° C. However, firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the manufacturing process of the liquid crystal display element such as sealing agent curing.
  • the thickness of the polyimide film obtained after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 50 to 100 nm.
  • the polyimide film formed on the substrate as described above is subjected to photo-alignment treatment, and the liquid crystal alignment film of the present invention is formed.
  • the method of the photo-alignment treatment is not particularly limited, but it is preferable to use polarized ultraviolet rays for obtaining uniform liquid crystal alignment.
  • the method of irradiating polarized ultraviolet rays is not particularly limited. For example, it is possible to irradiate a substrate on which a polyimide film is formed with polarized ultraviolet rays through a polarizing plate from a certain direction. Moreover, you may irradiate twice or more, changing the incident angle of the polarized ultraviolet-ray. Further, if polarized light can be obtained substantially, non-polarized ultraviolet rays may be irradiated at a certain angle from the normal line of the substrate.
  • an ultraviolet ray in the range of generally 100 to 400 nm, preferably 250 to 370 nm can be used, and particularly preferably, an optimum wavelength is obtained through a filter or the like depending on the kind of polyimide to be used. It is preferable to select.
  • the irradiation amount of ultraviolet rays is generally several mJ / cm 2 ⁇ number J / cm 2, preferably in the range of 5mJ / cm 2 ⁇ 500mJ / cm 2.
  • a necessary amount that can provide good orientation is used. It is preferable to select according to the type of polyimide.
  • the liquid crystal aligning agent of the present invention can form a vertical alignment type photo-alignment liquid crystal alignment film on a substrate by the method described above.
  • the formed liquid crystal alignment film can be photo-aligned, and in the rubbing process, which is a conventional alignment processing method, the problem of dust generated when the liquid crystal alignment film is scraped and scratches on the liquid crystal alignment film are liquid crystal.
  • the problem of reducing the display quality of the display element can be reduced.
  • a pair of substrates on which a vertical alignment type liquid crystal alignment film is formed using the liquid crystal alignment agent of the present invention is prepared.
  • it is installed such that the projection direction of the optical axis of the polarized ultraviolet light irradiated to each substrate is, for example, antiparallel, with a spacer of preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m sandwiched therebetween.
  • Fix with sealant preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m sandwiched therebetween.
  • liquid crystal is injected between the substrates and sealed.
  • the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which liquid crystal is injected after reducing the pressure inside the manufactured liquid crystal cell, and a dropping method in which sealing is performed after dropping the liquid crystal.
  • the manufactured liquid crystal display element has the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention, and this liquid crystal display element can comprise a VA system liquid crystal display element.
  • the liquid crystal display element of the present invention has no deterioration in display quality due to scratches on the liquid crystal alignment film, has excellent display quality, and has high reliability.
  • the diamine compound (DA-1-1) is an example of a diamine compound represented by the formula (DA-1) described above.
  • the diamine compound (DAM-1) is a conventional diamine compound having a cinnamic acid ester structure in the molecule. ⁇ Structural formulas and abbreviations>
  • Examples 1 to 6 the compounds [2] to [7] were synthesized according to the reaction formulas (1) to (6) exemplified. The obtained compound [7] was used for the synthesis of a diamine compound (DA-1-1).
  • Example 1 Ethyl 4-hydroxybenzoate [1] (19.9 g, 0.120 mol), 1-bromodecane (22.1 g, 0.100 mol), potassium carbonate (27.6 g, 0.200 mol), and dimethylformamide 120 g.
  • the mixture was added to a four-necked flask, stirred under a nitrogen atmosphere, and heated to 80 ° C. After stirring for 4 hours, disappearance of 1-bromodecane in the reaction solution was confirmed by 1 H-NMR (nuclear magnetic resonance) method. Thereafter, the solvent was distilled off, and a water washing operation was performed with toluene and a 2N NaOH aqueous solution, and the aqueous layer was removed.
  • Example 2 Compound [2] (10.8 g, 0.0354 mol), potassium hydroxide (10.0 g), 118 g of ethanol and 20.0 g of water were added to a four-necked flask and stirred at room temperature for 3 days. Thereafter, the mixture was further heated to 80 ° C. and stirred for 1 hour. The solution was cooled, and disappearance of the raw material was confirmed by HPLC (High performance liquid chromatography: high performance liquid chromatography). Thereafter, 18 ml of 12N hydrochloric acid aqueous solution was added in an ice bath and further stirred. Next, 300 g of water was added to precipitate crystals.
  • HPLC High performance liquid chromatography: high performance liquid chromatography
  • Example 4 Compound [5] (72.7 g), 3,5-dinitrobenzyl alcohol (29.7 g, 0.150 mol) and 450 g of dehydrated acetonitrile were added to a four-necked flask and heated and stirred at 70 ° C. After stirring for 2 hours, it was confirmed by HPLC that the disappearance of the raw materials and the generation of gas (gas containing carbon dioxide) were completed, and then the solvent was concentrated. 450 ml of methanol was added to the concentrate to precipitate crystals, and the crystals were collected by filtration.
  • Example 7 CBDA (0.471 g, 2.40 mmol) and diamine compound (DA-1-1) (1.17 g, 2.5 mmol) were mixed in NMP (8.94 g) and reacted at room temperature for 10 hours to obtain polyamic acid. A solution was obtained. NMP (7.89 g) and BC (7.89 g) were added to the polyamic acid solution and diluted to 6% by mass. Subsequently, the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours. The number average molecular weight of the polyamic acid contained in the liquid crystal aligning agent (A1) was 6700, and the weight average molecular weight was 24400.
  • the molecular weight of the polyamic acid obtained in Example 7, Example 8 and Comparative Example 1 was measured as follows. [Measurement of molecular weight] Measurement was carried out as follows using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex.
  • GPC gel permeation chromatography
  • Example 9 With respect to the cured film formed using the liquid crystal aligning agent (A1) obtained in Example 7, the ultraviolet (UV) absorption spectrum was measured and the coating property was evaluated as described below. Also, each liquid crystal cell having a cured film (polyimide film) formed using the liquid crystal aligning agent (A1) obtained in Example 7 and having linearly polarized light irradiation doses of 0 mJ, 20 mJ, 50 mJ, and 100 mJ, respectively. was prepared by the following method, and the pretilt angle was evaluated.
  • UV absorption spectrum The liquid crystal aligning agent (A1) obtained in Example 7 was spin-coated on a quartz substrate, dried on a hot plate at 80 ° C. for 90 seconds, and then baked in a hot air circulation oven at 200 ° C. for 30 minutes to obtain a film thickness of 100 nm. The polyimide film was formed. At this time, using this substrate, using a UV absorption spectrum measuring device (UV-3600) manufactured by Shimadzu Corporation, before baking in a hot air circulation oven at 200 ° C. for 30 minutes (also referred to as “before baking”). Also called “after firing”. The UV absorption spectrum was measured. In FIG. 1, the measurement result of the UV absorption spectrum before and behind baking was shown.
  • UV-3600 UV absorption spectrum measuring device manufactured by Shimadzu Corporation
  • a substrate after being baked in a hot air circulation oven at 200 ° C. for 30 minutes was irradiated with 300 mJ and 1 J (1000 mJ) of 313 nm linearly polarized light with an irradiation intensity of 11.0 mW / cm ⁇ 2 . .
  • the direction of incident light was inclined by 40 ° with respect to the normal direction of the substrate.
  • the linearly polarized light was adjusted by passing a 313 nm polarizing plate through a 313 nm bandpass filter through the ultraviolet light of a high-pressure mercury lamp.
  • the UV absorption spectrum was measured by the method mentioned above using the board
  • the UV absorption spectrum obtained as described above is labeled “300 mJ” and is shown in FIG. 3 together with the UV absorption spectrum after firing shown in FIG. 1.
  • the substrate used for measurement of the UV absorption spectrum after firing shown in FIG. 1 is not irradiated with linearly polarized light as described above. Therefore, this corresponds to the case where the irradiation amount of linearly polarized light is 0 mJ, and in FIG. 3, “0 mJ” is indicated.
  • the liquid crystal aligning agent (A1) obtained in Example 7 was spin-coated on the ITO electrode surface of a glass substrate with an ITO electrode made of an ITO film, dried on a hot plate at 80 ° C. for 90 seconds, and the coated surface was observed.
  • the applicability of the liquid crystal aligning agent (A1) was evaluated as “bad” when unevenness or repellency occurred on the coated surface and “good” when uniform without repellency or unevenness.
  • liquid crystal cell As a liquid place display element was produced as follows.
  • the liquid crystal aligning agent (A1) obtained in Example 7 was spin coated on the ITO electrode surface of a glass substrate with an ITO electrode made of an ITO film, dried on a hot plate at 80 ° C. for 90 seconds, and then heated at 200 ° C. for circulating hot air. Baking was performed for 30 minutes in a type oven to form a polyimide film having a thickness of 100 nm.
  • This substrate was irradiated with 20 mJ of 313 nm linearly polarized light with an irradiation intensity of 11.0 mW / cm ⁇ 2 .
  • the direction of the incident light was inclined by 40 ° with respect to the normal direction of the substrate, similarly to the irradiation with linearly polarized light.
  • This linearly polarized light was prepared by passing a 313 nm bandpass filter through the ultraviolet light of a high-pressure mercury lamp and then passing it through a 313 nm polarizing plate.
  • Two substrates were prepared, and 6 ⁇ m bead spacers were sprayed on the liquid crystal alignment film of one substrate, and then a sealant was printed thereon.
  • the liquid crystal alignment surfaces of the two substrates are made to face each other, and pressure-bonded so that the projection direction of the optical axis of the linearly polarized light on each substrate is antiparallel, and a sealant (manufactured by Kyoritsu Chemical Co., Ltd.) is taken at 150 ° C. for 105 minutes.
  • XN-1500T was heat cured.
  • a negative liquid crystal having negative dielectric anisotropy (MLC-6608, MLC-6608) having a negative dielectric anisotropy was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell having a linear polarized light irradiation amount of 20 mJ.
  • a liquid crystal cell having a linearly polarized light irradiation amount of 50 mJ was produced in the same manner as described above except that the linearly polarized light irradiation amount was 50 mJ.
  • a liquid crystal cell having a linearly polarized light irradiation amount of 100 mJ was produced in the same manner as described above except that the linearly polarized light irradiation amount was 100 mJ.
  • a liquid crystal cell having a linearly polarized light irradiation amount of 0 mJ was produced in the same manner as described above except that the linearly polarized light was not irradiated.
  • the pretilt angle in the liquid crystal alignment was measured.
  • the pretilt angle was measured by the Mueller matrix method using “Axo Scan” manufactured by Axo Metrix.
  • the pretilt angle is 89.1 degrees, and the liquid crystal molecules are slightly shifted from the normal direction of the substrate toward one direction in the substrate surface. It was tilted and oriented.
  • Example 10 About the cured film obtained using the liquid crystal aligning agent (A2) obtained in Example 2, the ultraviolet (UV) absorption spectrum was measured and the coating property was evaluated in the same manner as in Example 9. A liquid crystal cell was prepared and the pretilt angle was measured according to the same method as in Example 9 except that the liquid crystal aligning agent (A1) was changed to the liquid crystal aligning agent (A2).
  • ⁇ Comparative example 2> The cured film obtained using the liquid crystal aligning agent (A3) obtained in Comparative Example 1 was measured for ultraviolet (UV) absorption spectrum and evaluated for coating properties in the same manner as Example 9. A liquid crystal cell was prepared and the pretilt angle was measured in the same manner as in Example 9 except that the liquid crystal aligning agent (A1) was changed to the liquid crystal aligning agent (A3).
  • FIG. 2 the ultraviolet absorption spectrum of the cured film which consists of a polyimide formed using the liquid crystal aligning agent (A3) of the comparative example 1 is shown.
  • the cured film formed using the liquid crystal aligning agent (A1) of Example 7 formed a polyimide film by baking and generated new absorption in the ultraviolet region. It was.
  • the absorption in the ultraviolet region is based on a comparison with the UV spectrum of the cured film formed using the liquid crystal aligning agent (A3) of Comparative Example 1 shown in FIG. Interpreted as derived.
  • the absorbance of absorption in the ultraviolet region is reduced by irradiating with ultraviolet rays that are linearly polarized light. I was able to confirm. This is interpreted as a part of the double bond structure formed in the cured film was lost due to the irradiation of ultraviolet rays.
  • the liquid crystal aligning agent of the present invention forms a polyimide film by firing and generates new absorption in the ultraviolet region. This absorption in the ultraviolet region is interpreted as originating from the double bond structure formed in the polyimide film.
  • the polyimide film formed from the liquid crystal aligning agent of the present invention decreases the absorbance of newly generated ultraviolet region absorption by irradiation with ultraviolet rays that are linearly polarized light. I was able to. It is interpreted that a part of the double bond structure formed in the polyimide film was lost due to the irradiation of the linearly polarized ultraviolet ray.
  • the polyimide film formed from the liquid crystal aligning agent of the present invention can be used as it is without irradiating linearly polarized light, whereby a liquid crystal aligning film in which liquid crystal molecules are aligned in the normal direction of the substrate. I found it to be composed.
  • the polyimide film formed from the liquid crystal aligning agent of the present invention is a vertical alignment type light in which liquid crystal molecules are slightly tilted from the normal direction of the substrate toward one direction in the substrate plane by irradiation of linearly polarized light. It was found to constitute a reactive liquid crystal alignment film.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be suitably used as a liquid crystal alignment film of a VA liquid crystal display element, and is excellent in terms of coating properties that have been considered as a problem in the past. It was confirmed. It was also found that the film can be used as a vertically aligned photoreactive liquid crystal alignment film having excellent uniformity.
  • the liquid crystal aligning agent of the present invention is excellent in coatability, does not require light-shielding and the like, and can provide a vertical alignment type photo-alignment liquid crystal alignment film, which is excellent in high productivity.
  • a VA liquid crystal display element having display quality can be manufactured. That is, the liquid crystal surface element of the present invention can be suitably used as a liquid crystal display element for a portable information terminal such as a large liquid crystal TV or a smartphone displaying a high-definition image.

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Abstract

L'invention concerne un agent d'alignement à cristaux liquides qui est facile à manipuler, a une excellente aptitude au revêtement et est apte à former un film d'alignement à cristaux liquides ayant des propriétés de photo-alignement pour un alignement vertical; un film d'alignement à cristaux liquides; et un élément d'affichage à cristaux liquides. L'invention concerne un agent d'alignement à cristaux liquides caractérisé en ce qu'il contient au moins un polymère sélectionné à partir des groupes consistant en un précurseur polyimide ayant une structure d'ester β-hydroxy, et en un polyimide ayant une structure d'ester β-hydroxy.
PCT/JP2013/057900 2012-03-21 2013-03-19 Agent d'alignement à cristaux liquides, film d'alignement à cristaux liquides et élément d'affichage à cristaux liquides WO2013141262A1 (fr)

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WO2018212236A1 (fr) * 2017-05-16 2018-11-22 日産化学株式会社 Procédé de production d'oligonucléotide

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JP6160610B2 (ja) * 2012-03-21 2017-07-12 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR102621459B1 (ko) * 2016-04-20 2024-01-05 삼성디스플레이 주식회사 배향막 조성물, 이를 포함하는 액정 표시 장치 및 액정 표시 장치 제조방법
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JP2017105828A (ja) 2017-06-15
JP6160610B2 (ja) 2017-07-12
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