WO2014017497A1 - L'invention a pour objectif de fournir un procédé pour juger simplement l'état de différenciation, bon ou mauvais, de cellules souches pluripotentes, sans nécessiter le jugement d'un expert qualifié. l'invention a également pour objectif de fournir un procédé permettant l'application d'une détermination automatique des cellules souches pluripotentes ayant débuté une différenciation. ainsi, selon le procédé de l'invention, la bonne ou la mauvaise qualité de cellules souches pluripotentes est évaluée sur la base d'une différence de motifs de coloration des cellules souches pluripotentes. - Google Patents

L'invention a pour objectif de fournir un procédé pour juger simplement l'état de différenciation, bon ou mauvais, de cellules souches pluripotentes, sans nécessiter le jugement d'un expert qualifié. l'invention a également pour objectif de fournir un procédé permettant l'application d'une détermination automatique des cellules souches pluripotentes ayant débuté une différenciation. ainsi, selon le procédé de l'invention, la bonne ou la mauvaise qualité de cellules souches pluripotentes est évaluée sur la base d'une différence de motifs de coloration des cellules souches pluripotentes. Download PDF

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WO2014017497A1
WO2014017497A1 PCT/JP2013/069939 JP2013069939W WO2014017497A1 WO 2014017497 A1 WO2014017497 A1 WO 2014017497A1 JP 2013069939 W JP2013069939 W JP 2013069939W WO 2014017497 A1 WO2014017497 A1 WO 2014017497A1
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group
liquid crystal
side chain
integer
coo
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PCT/JP2013/069939
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English (en)
Japanese (ja)
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耕平 後藤
隆之 根木
喜弘 川月
瑞穂 近藤
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日産化学工業株式会社
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Priority to JP2014526945A priority Critical patent/JP6268089B2/ja
Priority to KR1020157004092A priority patent/KR102058769B1/ko
Priority to CN201380049349.8A priority patent/CN104937480B/zh
Publication of WO2014017497A1 publication Critical patent/WO2014017497A1/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
    • C09K19/542—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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • G02F1/133726—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films made of a mesogenic material

Definitions

  • the present invention relates to a polymer and a liquid crystal aligning agent suitable for a method for producing a highly efficient liquid crystal aligning film using light, and a liquid crystal aligning film and a liquid crystal display element.
  • the liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years.
  • the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
  • an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
  • the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
  • the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
  • alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
  • the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
  • This is a method of aligning liquid crystals. Since this rubbing method can easily and relatively realize a liquid crystal alignment state, it has been used in the manufacturing process of a conventional liquid crystal display element.
  • an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
  • Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
  • a decomposition type photo-alignment method is known as a main photo-alignment method.
  • the polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).
  • photocrosslinking type and photoisomerization type photo-alignment methods are also known.
  • polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1).
  • the alignment treatment method of the liquid crystal alignment film by the photo-alignment method uses a reaction by light such as a photocrosslinking reaction or a photoisomerization reaction. Therefore, the material used for forming the liquid crystal alignment film is required to have photoreactivity that enables it.
  • a reaction by light such as a photocrosslinking reaction or a photoisomerization reaction.
  • the material used for forming the liquid crystal alignment film is required to have photoreactivity that enables it.
  • Non-Patent Document 1 described above polyvinyl cinnamate is used as the material of the liquid crystal alignment film.
  • the liquid crystal alignment film is required to have excellent reliability as described above. Therefore, as described above, a polyimide organic film having excellent reliability such as heat resistance and electrical characteristics has been used for the liquid crystal alignment film by the conventional rubbing treatment. Therefore, the liquid crystal alignment film by the photo-alignment method is required to satisfy both photoreactivity and reliability.
  • a technique for obtaining a highly reliable polymer material such as an acrylic-siloxane hybrid material in which an acrylic polymer and a siloxane polymer are separately polymerized and mixed is known ( For example, see Patent Documents 5 to 9).
  • Patent Documents 5 to 9 for example, see Patent Documents 5 to 9.
  • the introduction of such highly reliable hybrid materials has not progressed.
  • Japanese Unexamined Patent Publication No. 2007-304215 Japanese Unexamined Patent Publication No. 2007-232934 Japanese Unexamined Patent Publication No. 2008-276149 Japanese Unexamined Patent Publication No. 7-243173 Japanese Unexamined Patent Publication No. 9-208642 Japanese Laid-Open Patent Publication No. 4-261454 Japanese Unexamined Patent Publication No. 2003-313233 Japanese Unexamined Patent Publication No. 1-168971
  • the photo-alignment method eliminates the rubbing process itself and has a great advantage as compared with the rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements.
  • an alignment process can be performed on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.
  • the alignment control ability can be controlled by changing the irradiation amount of polarized light in the photo-alignment method.
  • An object of the present invention is to provide a highly efficient liquid crystal alignment film manufacturing method using light, to provide a liquid crystal alignment film, and to provide a liquid crystal display element having the obtained liquid crystal alignment film.
  • Another object of the present invention is to provide a polymer suitable for a method for producing a highly efficient liquid crystal alignment film using light, and a liquid crystal aligning agent containing the polymer.
  • a method for producing a liquid crystal alignment film comprising:
  • step [III] ranges from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film exhibits liquid crystallinity to a temperature 10 ° C. lower than the upper limit of the liquid crystal temperature range.
  • the manufacturing method of the liquid crystal aligning film as described in said (1) which is inside.
  • the side chain polymer film is composed of at least one selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, acrylate, methacrylate, maleimide, ⁇ -methylene- ⁇ -butyrolactone and siloxane.
  • (1) comprising a structure having a main chain and at least one side chain selected from the group consisting of the following formulas (1) to (5), formula (7), and formula (8): A method for producing a liquid crystal alignment film according to any one of (6) to (6).
  • a 1 and B 1 each independently represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • Y 1 represents a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, Independently, it may be substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group, wherein X 1 is a single bond, — COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —, wherein l1 represents an integer of 1 to 12
  • a 2 , B 2 , and D 1 are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO. -Represents.
  • Y 2 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and the hydrogen atoms bonded thereto are each independently , —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • X 2 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • l2 represents an integer of 1 to 12
  • m2 represents an integer of 1 to 3
  • n2 represents an integer of 1 to 12.
  • a 3 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • l3 represents an integer of 1 to 12
  • m3 represents an integer of 1 to 3.
  • l4 represents an integer of 1 to 12.
  • a 4 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 4 represents —COO—.
  • Y 3 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, or a combination thereof, and a hydrogen atom bonded thereto is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • l5 represents an integer of 1 to 12
  • m4 represents an integer of 1 to 3.
  • a 5 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, or an alkyloxy group having 1 to 6 carbon atoms. Or a group consisting of a combination thereof.
  • l6 represents an integer of 1 to 12.
  • the hydrogen atom bonded to the benzene ring in formula (7) is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyl group. It may be substituted with an oxy group.
  • a 6 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • B 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • W 1 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and each hydrogen atom bonded thereto is independently , —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • l7 represents an integer of 1 to 12
  • m 5 and m 6 each independently represents an integer of 1 to 3.
  • the side chain type polymer film comprises a polysiloxane (a) having a radical polymerizable group and a monomer (b) having a liquid crystalline and photosensitive group and a radical polymerizable group.
  • the liquid crystalline and photosensitive group of the monomer (b) is at least one selected from the group consisting of azobenzene, stilbene, cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan and phenylbenzoate.
  • (11) A liquid crystal display device having the liquid crystal alignment film according to (10).
  • polysiloxane (a) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane of the following formula (10).
  • R 13 s1 Si (OR 14 ) s2 (10) (In Formula (10), R 13 represents an alkyl group substituted with an acryl group, a methacryl group, a styryl group, or an aryl group.
  • R 14 represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • the liquid crystalline and photosensitive group of the monomer (b) is at least one selected from the group consisting of azobenzene, stilbene, cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan and phenylbenzoate.
  • the monomer (b) includes a polymerizable group composed of at least one selected from the group consisting of hydrocarbons, acrylates, methacrylates, maleimides and ⁇ -methylene- ⁇ -butyrolactone, and the following formula (1): Any one of the above (12) to (14), which is a monomer having at least one side chain selected from the group consisting of formula (5), formula (7), and formula (8) The polymer described.
  • a 1 and B 1 each independently represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • Y 1 represents a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, Independently, it may be substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group, wherein X 1 is a single bond, — COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —, wherein l1 represents an integer of 1 to 12
  • a 2 , B 2 , and D 1 are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO. -Represents.
  • Y 2 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and the hydrogen atoms bonded thereto are each independently , —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • X 2 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • l2 represents an integer of 1 to 12
  • m2 represents an integer of 1 to 3
  • n2 represents an integer of 1 to 12.
  • a 3 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • l3 represents an integer of 1 to 12
  • m3 represents an integer of 1 to 3.
  • l4 represents an integer of 1 to 12.
  • a 4 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 4 represents —COO—.
  • Y 3 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, or a combination thereof, and a hydrogen atom bonded thereto is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • l5 represents an integer of 1 to 12
  • m4 represents an integer of 1 to 3.
  • a 5 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, or an alkyloxy group having 1 to 6 carbon atoms. Or a group consisting of a combination thereof.
  • l6 represents an integer of 1 to 12.
  • the hydrogen atom bonded to the benzene ring in formula (7) is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyl group. It may be substituted with an oxy group.
  • a 6 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • B 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • W 1 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and each hydrogen atom bonded thereto is independently , —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group.
  • l7 represents an integer of 1 to 12
  • m 5 and m 6 each independently represents an integer of 1 to 3.
  • the side chain type polymer film of the present invention may be used in combination with a side chain structure having no photoreactivity as long as liquid crystallinity and photoreactivity are not lost.
  • a side chain structure that does not have photoreactivity includes a structure represented by the following formula (6).
  • E 1 represents a single bond, —O—, —CH 2 —, —COO, —OCO—, —CONH—, or —NH—CO—.
  • Z represents a single bond, —COO, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • k1 represents an integer of 1 to 12, and p1 and q1 each independently represents an integer of 0 to 3.
  • R 4 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyloxy group having 1 to 6 carbon atoms, a carboxyl group, or a combination thereof. Represents a group.
  • a liquid crystal alignment film can be obtained by realizing a highly efficient alignment process using light by a method for producing a liquid crystal alignment film that enables a highly efficient alignment process.
  • a liquid crystal display element is obtained.
  • the polymer which can be used suitably for the above liquid crystal aligning films, and the liquid crystal aligning agent containing this polymer are obtained.
  • FIG. 1 It is a figure which illustrates typically the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film of the 1st form of this invention
  • (a) is a figure which shows the state of the side chain type polymer film before polarized light irradiation
  • B is a view showing the state of the side chain polymer film after irradiation with polarized light
  • (c) is a view showing the state of the side chain polymer film after heating
  • (d ) Is a diagram showing a state of the side chain polymer film in which the orientation is fixed by performing a second heat treatment after heating.
  • FIG. 1 It is a figure which illustrates typically the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film of the 1st form of this invention
  • (a) is a figure which shows the state of the side chain type polymer film before polarized light irradiation
  • B is a view showing the state of the side chain polymer film after irradiation with polarized light
  • (c) is a view showing the state of the side chain polymer film after heating
  • (d ) Is a diagram showing a state of the side chain polymer film in which the orientation is fixed by performing a second heat treatment after heating.
  • the method for producing a liquid crystal alignment film of the present invention uses a method in which an alignment treatment is performed by irradiation with polarized light without using a rubbing treatment, using a photosensitive side chain polymer film capable of exhibiting liquid crystallinity.
  • the photosensitive side chain polymer film capable of exhibiting liquid crystallinity includes a polysiloxane (a) having a radical polymerizable group, a monomer having a liquid crystalline and photosensitive group, and a radical polymerizable group ( b) and a polymer obtained by radical polymerization.
  • a step of heating the side chain polymer film is provided to produce a liquid crystal alignment film.
  • a heating process is made into two steps, the 1st heating process and 2nd heating process from which temperature differs. Furthermore, by optimizing the irradiation amount of polarized light and the heating temperature in the first heating step after the polarized light irradiation, highly efficient alignment processing is realized in the liquid crystal alignment film. Thereafter, in the second heating step, the alignment state formed in the liquid crystal alignment film is fixed. As a result, in the present invention, it is possible to achieve high alignment and good alignment control ability in the liquid crystal alignment film. The present invention will be described in detail below.
  • the photosensitive side chain polymer film that can exhibit liquid crystallinity used in the method for producing a liquid crystal alignment film of the present invention is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, that is, It is a polymer film.
  • bonded with the principal chain of a polymer has photosensitivity, and can raise
  • the photosensitive group bonded to the main chain is not particularly limited, but a structure that causes a crosslinking reaction or photofleece rearrangement in response to light is desirable. In this case, the realized orientation control ability can be stably maintained for a long period of time even when exposed to external stress such as heat.
  • the structure of the photosensitive side chain polymer film that can exhibit liquid crystallinity in a predetermined temperature range used in the method for producing a liquid crystal alignment film of the present invention is not particularly limited as long as it satisfies such characteristics.
  • the side chain structure of the side chain polymer preferably has a rigid mesogen component. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used for the liquid crystal alignment film.
  • Examples of such a side chain polymer structure include a main chain and a side chain bonded to the main chain, and the side chain is a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene group, or the like.
  • the structure has a mesogenic component and a photosensitive group bonded to the tip, which undergoes a crosslinking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded to the main chain, and the side chain is
  • a structure having a phenylbenzoate group that also serves as a mesogenic component and undergoes a photo-Fries rearrangement reaction can be obtained.
  • the photosensitive side chain polymer film capable of exhibiting liquid crystallinity used in the method for producing a liquid crystal alignment film of the present invention will be described.
  • photosensitive side chain polymer film capable of exhibiting liquid crystallinity of the present invention include acrylate, methacrylate, maleimide, ⁇ -methylene- ⁇ -butyrolactone, siloxane, itaconate, fumarate, maleate, styrene, vinyl,
  • a 1 and B 1 each independently represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • Y 1 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and the hydrogen atoms bonded to them are independent of each other.
  • —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group may be substituted.
  • X 1 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • l1 represents an integer of 1 to 12
  • m1 represents an integer of 1 to 3
  • n1 represents an integer of 1 to 12.
  • a 2 , B 2 , and D 1 are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—.
  • Y 2 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and the hydrogen atoms bonded thereto are independent of each other.
  • —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group may be substituted.
  • X 2 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • l2 represents an integer of 1 to 12
  • m2 represents an integer of 1 to 3
  • n2 represents an integer of 1 to 12.
  • a 3 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —, and R 2 represents a hydrogen atom or a carbon number.
  • l4 represents an integer of 1 to 12.
  • a 4 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • X 4 represents —COO—.
  • Y 3 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, or a combination thereof, and a hydrogen atom bonded thereto is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group may be substituted.
  • l5 represents an integer of 1 to 12
  • m4 represents an integer of 1 to 3.
  • a 5 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, or an alkyloxy group having 1 to 6 carbon atoms. Or a group consisting of a combination thereof.
  • l6 represents an integer of 1 to 12.
  • the hydrogen atom bonded to the benzene ring in formula (7) is independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyl group. It may be substituted with an oxy group.
  • a 6 represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • B 3 represents a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • W 1 is a group selected from a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof, and the hydrogen atoms bonded thereto are independent of each other.
  • —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkyloxy group may be substituted.
  • l7 represents an integer of 1 to 12
  • m 5 and m 6 each independently represents an integer of 1 to 3.
  • the side chain represented by the above formula (1) to formula (5), formula (7), and formula (8) has a structure having a group such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, or azobenzene as a mesogenic component Is provided. And at the tip, it has a photosensitive group that undergoes a dimerization reaction in response to light and undergoes a crosslinking reaction, or has a main chain and a side chain bonded thereto, and the side chain also becomes a mesogenic component. And a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction, or at least one group.
  • the photosensitive side-chain polymer film capable of exhibiting liquid crystallinity according to the present invention includes the group consisting of the above formulas (1) to (5), (7), and (8) together with the above-described main chain.
  • a side chain structure having no photoreactivity may be used in combination as long as liquid crystallinity and photoreactivity are not lost.
  • An example of a side chain structure that does not have photoreactivity includes a structure represented by the following formula (6).
  • E 1 represents a single bond, —O—, —CH 2 —, —COO, —OCO—, —CONH—, or —NH—CO—.
  • Z represents a single bond, —COO, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, or C 6 H 4 —.
  • k1 represents an integer of 1 to 12, and p1 and q1 each independently represents an integer of 0 to 3.
  • R 4 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyloxy group having 1 to 6 carbon atoms, a carboxyl group, or a combination thereof. Represents a group.
  • the polysiloxane (a) used as the material for the side chain polymer film is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (10).
  • R 13 is an alkyl group substituted with an acryl group, a methacryl group, a styryl group, or an aryl group.
  • R 14 represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • S1 is 1 or 2
  • S2 is 2 or 3.
  • R 13 of the alkoxysilane represented by the above formula (10) (hereinafter also referred to as a second specific organic group) is at least one selected from the group consisting of an acryl group, a methacryl group, a styryl group, and an aryl group.
  • An alkyl group substituted with The number of substituted hydrogen atoms is one or more, preferably one.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. More preferably, it is 1-10.
  • the alkyl group may be linear or branched, but is more preferably linear.
  • R 14 of the alkoxysilane represented by the above formula (10) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
  • alkoxysilane represented by the said Formula (10) examples include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N-styrylmethyl- 2-aminoethylamino) propyltrimethoxysilane.
  • the effects of the present invention are not impaired in the production of the polysiloxane (a) for the purpose of improving the adhesion to the substrate and the affinity with the liquid crystal molecules.
  • the alkoxysilane represented by following formula (11) can also use 1 type or multiple types. Since the alkoxysilane represented by the following formula (11) can impart various characteristics to the polysiloxane, one or more kinds can be selected and used according to the required characteristics.
  • R 18 is a hydrogen atom or a carbon atom having 1 to 10 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. It is a hydrogen group.
  • R 19 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.
  • n is an integer of 0 to 3, preferably 0 to 2.
  • R 18 of the alkoxysilane represented by the above formula (11) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (hereinafter also referred to as a third specific organic group).
  • Examples of the third specific organic group include an aliphatic hydrocarbon group; a hydrocarbon group having a ring structure such as an aliphatic ring, an aromatic ring and a heterocyclic ring; a hydrocarbon group having an unsaturated bond; and an oxygen atom, It is a hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom such as a nitrogen atom or a sulfur atom, and may have a branched structure.
  • the third specific organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
  • alkoxysilane represented by the above formula (11) are given below, but the invention is not limited thereto.
  • 3- (2-aminoethylaminopropyl) trimethoxysilane 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxy Silane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyl
  • the alkoxysilane in which n is 0 is tetraalkoxysilane.
  • Tetraalkoxysilane is preferable for obtaining the polysiloxane (a) used in the present invention because it easily condenses with the alkoxysilane represented by the formula (10).
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the alkoxysilane represented by the formula (10) is contained in 1 to 30 mol%, particularly preferably 5 to 20 mol% in the total alkoxysilane used for the production of the polysiloxane (a). preferable.
  • the monomer (b) used for the formation of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity used in the method for producing a liquid crystal alignment film of the present invention is a liquid crystalline and photosensitive group. And a radically polymerizable group.
  • the liquid crystalline and photosensitive group of the monomer (b) is derived from at least one selected from the group consisting of azobenzene, stilbene, cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan and phenylbenzoate. It is a group.
  • the monomer (b) includes a polymerizable group composed of at least one selected from the group consisting of hydrocarbon, acrylate, methacrylate, maleimide and ⁇ -methylene- ⁇ -butyrolactone, and the above formulas (1) to It is preferable that it is a monomer which has at least 1 sort (s) of side chain selected from the group which consists of (5), Formula (7), and Formula (8).
  • the monomer (b) can be used together with the above-described polysiloxane (a) to form a polymer, and can be used for forming the side chain polymer film of the present invention.
  • the side chain polymer in the side chain polymer film of the present invention comprises the above-described polysiloxane (a) and a monomer (b) having a liquid crystalline and photosensitive group and a radical polymerizable group.
  • a polymer obtained by radical polymerization is included.
  • the polymer is, for example, in a solvent in which a polysiloxane (a), a monomer (b) having a liquid crystalline and photosensitive group and a radical polymerizable group, and a polymerization initiator coexist. It can be obtained by polymerization reaction at a temperature of 50 to 110 ° C.
  • the amount of the monomer (b) used is preferably 0.5 to 50 mol, and more preferably 1 to 10 mol, relative to 1 mol of alkoxysilane when the polysiloxane (a) is obtained.
  • the solvent used is a polysiloxane (a), a monomer (b) having a liquid crystalline and photosensitive group and a radical polymerizable group, and a polymerization initiator added as necessary. If it dissolves etc., it will not be specifically limited.
  • the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate.
  • Examples of the polymerization initiator described above include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- ( Organic peroxides such as azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane And hydrogen peroxide.
  • AIBN 2,2′-azobisisobutyronitrile
  • AIBN azobisisobutyronitrile
  • the content of the polymerization initiator is preferably 3 to 50 mol%, more preferably 5 to 30 mol%, relative to 1 mol of the monomer (b) described above.
  • the method for producing a liquid crystal alignment film of the present invention forms a coating film on a substrate using the above-mentioned side chain polymer, and then irradiates polarized ultraviolet rays. Next, high efficiency anisotropy is introduced into the side chain polymer film by performing the first heating, and further fixing by the second heating to provide excellent liquid crystal alignment control ability.
  • the liquid crystal alignment film provided is manufactured.
  • the side chain polymer film is used.
  • a coating film is formed on the substrate using the side chain polymer.
  • the first alignment treatment is performed by irradiating polarized ultraviolet rays, and then the first heating (both the first heat treatment is performed) at a temperature within a range in which the side chain type polymer film exhibits liquid crystallinity.
  • the re-orientation process to be the second alignment process is performed.
  • the second heating (also referred to as second heat treatment) is further performed at a temperature equal to or higher than the temperature of the first heating described above, and the polysiloxane structure portion contained therein Is condensed.
  • the second heat treatment can produce a highly efficient liquid crystal alignment film by fixing the anisotropy introduced into the side chain polymer film by light irradiation and the first heat treatment.
  • a highly reliable liquid crystal alignment film based on a polysiloxane structure can be provided.
  • the method for producing the liquid crystal alignment film of the present invention includes: [I]; a step of forming a photosensitive side chain polymer film exhibiting liquid crystallinity in a predetermined temperature range on a substrate; [II]; a step of irradiating the side chain polymer film obtained in the step [I] with polarized ultraviolet rays; [III] a step of heating the side chain polymer film irradiated with ultraviolet rays polarized in the step [II], and [IV]; a side chain polymer film heated in the step [III] of the step [III]. And further heating at a different temperature from It is comprised.
  • the irradiation with ultraviolet rays in the step [II] is performed by introducing anisotropy into the side chain polymer film.
  • the amount is in the range of 1 to 15% of the ultraviolet irradiation amount that maximizes ⁇ A
  • the side chain type polymer film 1 of the present invention is formed on the substrate.
  • the side chain polymer film 1 formed on the substrate has a structure in which the side chains 2 are randomly arranged.
  • ⁇ A is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of polarized ultraviolet rays in the side chain polymer film of the present invention.
  • the irradiation with ultraviolet rays in the step [II] is performed by introducing anisotropy into the side chain polymer film.
  • the amount is in the range of 15 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
  • the side chain type polymer film 3 of the present invention is formed on the substrate.
  • the side chain polymer film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chain 4 of the side chain polymer film 3, the mesogenic component and the photosensitive group of the side chain 4 are also randomly oriented, and the side chain polymer film 2 is isotropic.
  • the ultraviolet irradiation amount in the step [II] is 1 to the ultraviolet irradiation amount that maximizes ⁇ A.
  • the side chain polymer film 5 is formed on the substrate.
  • the side chain polymer film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the side chain polymer film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain polymer film 5 is isotropic.
  • the ultraviolet irradiation amount in the step [II] is 1 to the ultraviolet irradiation amount that maximizes ⁇ A.
  • the side chain polymer film 7 is formed on the substrate.
  • the side chain type polymer film 7 of this embodiment formed on the substrate has a structure in which the side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the side chain polymer film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the side chain polymer film 7 is isotropic.
  • the ultraviolet ray irradiation amount in the step [II] is within the range of 1 to 15% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
  • the isotropic side chain polymer film 1 is irradiated with polarized ultraviolet rays.
  • the photosensitive group of the side chain 2a having a photosensitive group is preferentially dimerized.
  • the density of the side chain 2a that has undergone photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, the side chain polymer film 1 is provided with very small anisotropy.
  • the ultraviolet ray irradiation amount in the step [II] is within the range of 15 to 70% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
  • the isotropic side chain polymer film 3 is irradiated with polarized ultraviolet rays.
  • the photosensitive group of the side chain 4a having a photosensitive group is preferentially dimerized.
  • a liquid crystal alignment film using a side chain polymer having a structure having an optical fleece rearrangement group represented by the above formula (7) in the second embodiment of the present invention In the case where the ultraviolet irradiation amount in the step [II] is in the range of 1 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, the isotropic side chain polymer film 5 is Irradiate polarized ultraviolet light. Then, as shown in FIG. 3 (b), among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet light, the photosensitive group of the side chain 6a having a photosensitive group is preferentially subjected to photofleece rearrangement.
  • the density of the side chain 6a subjected to the photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, the side chain type polymer film 5 is given a very small anisotropy.
  • a liquid crystal alignment film using a side chain polymer having a structure having an optical fleece rearrangement group represented by the above formula (8) in the second embodiment of the present invention In the case where the ultraviolet irradiation amount in the step [II] is in the range of 1 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, the isotropic side chain polymer film 7 is Irradiate polarized ultraviolet light. Then, as shown in FIG. 4B, among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet light, the photosensitive group of the side chain 8a having a photosensitive group preferentially undergoes optical Fleece rearrangement.
  • the ultraviolet irradiation amount in the step [II] is in the range of 1 to 15% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • the side chain polymer film 1 after irradiation with polarized light is heated to a liquid crystal state.
  • the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto.
  • this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light. As a result, the very small anisotropy of the side chain polymer film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the side chain polymer film 1. become.
  • the ultraviolet irradiation amount in the step [II] is within the range of 15 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • the side chain polymer film 3 after irradiation with polarized light is heated to a liquid crystal state.
  • the amount of the generated crosslinking reaction is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto.
  • the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the small anisotropy of the side chain polymer film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 3. .
  • a side chain type polymer having a structure having an optical fleece rearrangement group represented by the above formula (7) was used.
  • the ultraviolet irradiation amount in the step [II] is within the range of 1 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, Heat to liquid crystal state.
  • the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. Yes.
  • the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it self-organizes in the direction perpendicular to the polarization direction of the irradiated ultraviolet light.
  • the side chain 6 containing the mesogenic component is reoriented.
  • the very small anisotropy of the side chain polymer film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the side chain polymer film 5. It will be.
  • a side chain type polymer having a structure having an optical fleece rearrangement group represented by the above formula (8) was used.
  • the ultraviolet irradiation amount in the step [II] is in the range of 1 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, Heat to liquid crystal state.
  • the amount of the generated optical fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Yes.
  • the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the side chain 8 containing the mesogenic component is reoriented.
  • the small anisotropy of the side chain polymer film 7 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 7. Become.
  • the side chain polymer has a polysiloxane structure derived from the above-described polysiloxane (a). Therefore, the side chain polymer membrane of the present invention has a polysiloxane structure after anisotropy is induced by mesogen self-assembly as shown in FIG. 1 (c) and FIG. 2 (c).
  • the anisotropy can be fixed by performing the second heat treatment at a temperature at which a thermal reaction (crosslinking reaction) caused by the above occurs. That is, the side chain type polymer film of the present invention was induced in the orientation direction of the side chain 2b and the side chain 4b by the second heat treatment as shown in FIG. 1 (d) and FIG. 2 (d).
  • the temperature of the second heat treatment is preferably a temperature at which a thermal reaction of siloxane occurs, and can be, for example, a temperature of 200 ° C. or higher.
  • the side chain type polymer has a polysiloxane structure derived from the above-described polysiloxane (a). Therefore, the side chain type polymer film of the present invention has a polysiloxane structure after anisotropy is induced by mesogen self-assembly as shown in FIG. 3 (c) and FIG. 4 (c).
  • the anisotropy can be fixed by performing the second heat treatment at a temperature at which a thermal reaction (crosslinking reaction) caused by the above occurs. That is, the side chain type polymer film of the present invention is not shown, but the induced large anisotropy can be fixed by the second heat treatment as in the first embodiment.
  • the temperature of the second heat treatment is preferably a temperature at which a thermal reaction of siloxane occurs as in the first embodiment described above, and can be, for example, a temperature of 200 ° C. or higher.
  • the first heat treatment for irradiation and reorientation of polarized ultraviolet rays to the side chain polymer film and the second heat treatment for immobilization are performed.
  • a liquid crystal alignment film having anisotropy introduced with high efficiency can be obtained.
  • the irradiation amount of polarized ultraviolet rays on the side chain polymer film and the heating temperatures in the first heat treatment and the second heat treatment are made to correspond to the respective purposes. To optimize. Thereby, introduction of anisotropy into the side chain type polymer film can be realized with high efficiency.
  • the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the side chain polymer film of the present invention is that the photopolymerization reaction or photoisomerization reaction of the photosensitive group in the side chain polymer film Or, it corresponds to the irradiation amount of polarized ultraviolet rays that optimizes the amount of photofleece rearrangement reaction.
  • the side chain type polymer film of the present invention when the side chain type polymer film of the present invention is irradiated with polarized ultraviolet rays to the structure having the light fleece rearrangement group, the side chain type becomes excessive when the side chain photosensitive group that undergoes the light fleece rearrangement reaction becomes excessive.
  • the liquid crystallinity of the polymer film will be too low. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly due to subsequent overheating.
  • the side chain polymer of the present invention when irradiating polarized ultraviolet light to a structure having a photofleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side chain polymer of the present invention is photodegraded and then self-organized by heating. May interfere with progress.
  • the optimal amount of the side chain photosensitive group that undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction by irradiation with polarized ultraviolet rays is the side chain type.
  • the amount is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol% of the photosensitive group of the polymer film.
  • a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the side chain polymer film.
  • the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption in the vertical direction after irradiation with polarized ultraviolet light are measured.
  • ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
  • ⁇ Amax the maximum value of ⁇ A ( ⁇ Amax) realized in the side chain type polymer film of the present invention and the irradiation amount of polarized ultraviolet rays for realizing it are obtained.
  • a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the irradiation amount of polarized ultraviolet rays that realizes this ⁇ Amax.
  • the irradiation amount of polarized ultraviolet rays to the side chain polymer film is preferably in the range of 1 to 70% of the amount of polarized ultraviolet rays that realizes ⁇ Amax. More preferably, it is in the range of ⁇ 50%.
  • the irradiation amount of polarized ultraviolet light within the range of 1 to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0% of the entire photosensitive group of the side chain type polymer film. 1 to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
  • the side chain polymer film is irradiated with polarized ultraviolet rays, and then the side chain polymer film is heated (first heat treatment).
  • the side chain polymer film of the present invention is a polymer film that can exhibit liquid crystallinity in a predetermined temperature range.
  • the first heat treatment after irradiation with polarized ultraviolet rays can be determined based on the temperature at which the liquid crystallinity of the side chain polymer film is developed. That is, the heating temperature of the first heat treatment after irradiation with polarized ultraviolet rays is set to a temperature within a range in which the side chain polymer film of the present invention exhibits liquid crystallinity.
  • the heating temperature after irradiation with polarized ultraviolet rays ranges from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film of the present invention exhibits liquid crystallinity (hereinafter referred to as a liquid crystal temperature range).
  • the temperature is preferably in the range up to 10 ° C. lower than the upper limit.
  • the side-chain polymer film of the present invention is heated after irradiation with polarized ultraviolet rays to be in a liquid crystal state, and is self-organized and reoriented in a direction parallel to or perpendicular to the polarization direction.
  • the small anisotropy of the side chain polymer film induced by the photocrosslinking reaction, photoisomerization reaction, or photofleece rearrangement reaction is amplified by heat.
  • the side chain polymer film is in a liquid crystal state by heating, if the heating temperature is low, the viscosity of the side chain polymer film in the liquid crystal state is high and realignment due to self-assembly is less likely to occur. End up.
  • the heating temperature is in the range from the lower limit of the liquid crystal temperature range of the side chain polymer film of the present invention to a temperature higher by 10 ° C.
  • the anisotropic amplification effect due to heat in the side chain polymer film can be obtained.
  • the side chain polymer film of the present invention exhibits a liquid crystal state by heating, if the heating temperature is high, the state of the side chain polymer film becomes close to an isotropic liquid state, and self-organization This makes it difficult to reorient in one direction.
  • the heating temperature is higher than the temperature lower by 10 ° C. from the upper limit of the liquid crystal temperature range of the side chain polymer film of the present invention, the anisotropic amplification effect due to heat in the side chain polymer film can be obtained. However, it cannot be enough.
  • the heating temperature of the first heat treatment is higher than the temperature lower by 10 ° C. than the upper limit of the liquid crystal temperature range of the side chain polymer film of the present invention, for example, the reaction of siloxane such as 200 ° C. or higher.
  • the thermal reaction of the siloxane portion may proceed before realignment. In that case, it becomes difficult to reorient the side chain polymer film in one direction due to self-organization.
  • the heating temperature is higher than 200 ° C., the anisotropic amplification effect due to heat in the side chain polymer film cannot be made sufficient.
  • the liquid crystal temperature range of the side chain polymer film and the reaction of the siloxane part are realized in order to realize highly efficient anisotropy into the side chain polymer film.
  • a suitable heating temperature is determined based on the temperature range. As described above, the heating temperature after irradiation with polarized ultraviolet rays is lower than the lower limit of the liquid crystal temperature range of the side chain type polymer film by 10 ° C., and is 200 ° C. or lower, which is higher than the upper limit of the liquid crystal temperature range. The temperature is within a range where the upper limit is a temperature 10 ° C lower.
  • the heating temperature after irradiation with polarized ultraviolet rays is set to 110 to 190.
  • the temperature is set to ° C.
  • the method for producing a liquid crystal alignment film of the present invention includes the following steps [1] to [IV] in the following order. Thereby, a liquid crystal alignment film into which anisotropy is introduced can be manufactured with high efficiency.
  • the side chain polymer film of the present invention is formed on a substrate.
  • the substrate is not particularly limited.
  • a transparent substrate such as a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
  • a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed is used from the viewpoint of simplifying the process of manufacturing a liquid crystal display element. Is also possible.
  • an opaque substrate such as a silicon wafer can also be used. In this case, an electrode using a material that reflects light such as aluminum can be used.
  • the side chain polymer film of the present invention is in the form of a solution dissolved in a desired solvent
  • film formation on the substrate is performed by applying the solution-like side chain polymer film.
  • the coating method is not particularly limited, but industrially, a method performed by screen printing, offset printing, flexographic printing, inkjet method or the like is common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), a spray method, and the like, and these may be used depending on the purpose.
  • the solution-like side chain polymer film of the present invention is coated on the substrate, it is 20 to 180 ° C., preferably 40 to 150 ° C., by a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven.
  • a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven.
  • IR infrared
  • the first alignment treatment is performed by irradiating the side chain polymer film obtained in the step [I] with polarized ultraviolet rays.
  • the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
  • ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of the side chain polymer film to be used.
  • ultraviolet rays having a wavelength in the range of 290 to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the irradiation amount of the polarized ultraviolet ray is preferably in the range of 1 to 70% of the amount of the polarized ultraviolet ray that realizes ⁇ Amax of the side chain polymer film of the present invention to be used. More preferably, it is within the range of 50%.
  • the side chain polymer film irradiated with the ultraviolet rays polarized in the step [II] is heated.
  • heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like is used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the side chain polymer film of the present invention is exhibited. That is, the heating temperature in this step is a temperature at which reorientation occurs in the side chain polymer film.
  • the heating temperature in this step after irradiation with polarized ultraviolet rays in step [II] is 200 ° C. or less, with the temperature being 10 ° C. higher than the lower limit of the liquid crystal temperature range in which the side chain polymer film of the present invention exhibits liquid crystallinity. And it is preferable that it is the temperature of the range which makes temperature 10 degreeC lower than the upper limit of a liquid-crystal temperature range an upper limit.
  • the side chain type polymer film of the present invention can exhibit liquid crystallinity, and is preferably set to 60 ° C. or higher and 180 ° C. or lower as a temperature range that does not cause thermal reaction.
  • step [IV] as the second heat treatment, the side chain polymer film heated in step [III] is further heated at a temperature different from the heating temperature in step [III].
  • Step [III] is a temperature at which the side chain polymer film of the present invention is brought into a liquid crystal state, and a temperature within a range that does not cause a thermal reaction of the siloxane portion is selected and heat treatment (first heat treatment ) Has been made. Therefore, in this step, a heating temperature higher than the heating temperature in step [III] is selected, and the heat treatment (second heat treatment) is performed.
  • the heating temperature in this step is a temperature for fixing the reorientation of the side chain polymer film in step [III].
  • heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like can be used as in the step [III].
  • the heating temperature can be determined in consideration of the reaction temperature of the siloxane moiety in the side chain polymer film of the present invention.
  • the heating temperature in this step is preferably 200 ° C. or higher.
  • the method for producing a liquid crystal alignment film of the present invention can realize the introduction of anisotropy into the side chain polymer film with high efficiency. Furthermore, the liquid crystal alignment film of the present invention with high efficiency and high reliability can be manufactured.
  • TEOS Tetraethoxysilane
  • ACPS 3-acryloxypropyltrimethoxysilane (methacrylate monomer)
  • the number average molecular weight and weight average molecular weight of the acrylic copolymer were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran was supplied at a flow rate of 1 mL (milliliter) / min. It was measured under the condition that it was eluted by flowing through (column temperature 40 ° C.).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • reaction solution was poured into 500 ml of diethyl ether to separate the polymer, and after removing AIBN, the precipitate was separated by filtration to obtain polysiloxane-polymethacrylate hybrid (P6CAS) powder (C).
  • P6CAS polysiloxane-polymethacrylate hybrid
  • NMP and BCS were added to the polysiloxane-polymethacrylate hybrid (P6CBS) (powder (B)) obtained in Synthesis Example 2 and diluted to 4% by mass to obtain a liquid crystal aligning agent (I). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Mn Mn was 35000.
  • siloxane content in hybrid polymer The siloxane content in the polysiloxane-polymethacrylate hybrid (powder (B)) was calculated from GPC. The siloxane content was calculated by comparing the peak ratio of the methacrylate monomer on the GPC chart after radical polymerization with the peak ratio of the polysiloxane-polymethacrylate hybrid. The calculated siloxane-methacrylate ratio in P6CBS was 1: 5 by weight.
  • NMP and BCS were added to the polysiloxane-polymethacrylate hybrid (P6CAS) (powder (C)) obtained in Synthesis Example 3 and diluted to 4% by mass to obtain a liquid crystal aligning agent (II). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Mn was 48000.
  • the siloxane-methacrylate ratio of P6CAS calculated from GPC was 2: 3.5 by weight.
  • Example 3 The liquid crystal alignment treatment agent (I) containing the polysiloxane-polymethacrylate hybrid (P6CBS) obtained in Example 1 was spin-coated on a quartz substrate (length 10 ⁇ width 10 ⁇ thickness 1 (mm)). After drying for 5 minutes on a hot plate at 80 ° C., a coating film with a film thickness of 50 nm was formed to obtain a substrate with a liquid crystal alignment film before the alignment treatment.
  • P6CBS polysiloxane-polymethacrylate hybrid
  • Example 4 The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used to irradiate polarized ultraviolet rays through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate.
  • the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 600 mJ.
  • this ultraviolet-irradiated substrate is heated at 150 ° C. for 5 minutes, and the coating film (polymer film) is subjected to a realignment treatment by changing the P6CBS of the coating film to a liquid crystal state.
  • a substrate was obtained.
  • the obtained substrate with a liquid crystal high film was used for measurement of an ultraviolet absorption spectrum (FIG. 5) as described later.
  • Example 5 The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used to irradiate polarized ultraviolet rays through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate.
  • the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 600 mJ.
  • substrate was heated at 150 degreeC for 5 minute (s), and the reorientation process was performed to the coating film by making P6CBS of a coating film into a liquid-crystal state.
  • the substrate subjected to the re-orientation treatment was heated to 200 ° C., and baked at that temperature for 15 minutes to cause condensation reaction of siloxane, thereby fixing the orientation. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
  • Example 6 The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used to irradiate polarized ultraviolet rays through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate.
  • the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 800 mJ.
  • this ultraviolet-irradiated substrate was heated at 150 ° C. for 5 minutes, and the P6CBS of the coating film was brought into a liquid crystal state, so that the coating film was subjected to a realignment treatment to obtain an alignment-treated substrate with a liquid crystal alignment film.
  • the obtained substrate with a liquid crystal high film was used for measurement of an ultraviolet absorption spectrum (FIG. 6) as described later.
  • Example 7 The substrate with a liquid crystal alignment film before alignment treatment obtained in Example 3 was used to irradiate polarized ultraviolet rays through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate.
  • the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 800 mJ.
  • substrate was heated at 150 degreeC for 5 minute (s), and the reorientation process was performed to the coating film by making P6CBS of a coating film into a liquid-crystal state.
  • the substrate subjected to the re-orientation treatment was heated to 200 ° C., and baked at that temperature for 15 minutes to cause condensation reaction of siloxane, thereby fixing the orientation. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
  • FIG. 5 is a UV absorption spectrum parallel and perpendicular to the polarized electric field vector of the irradiated UV of the liquid crystal alignment film obtained in Example 4.
  • FIG. 5 the ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 4 (shown as “parallel after heating” and “vertical after heating” in the figure) is shown.
  • the ultraviolet absorption spectra (shown as “parallel after polarized light irradiation” and “perpendicular after polarized light irradiation” in the figure) of the liquid crystal alignment film made (before the heat treatment of Example 4) are shown.
  • Example 4 The difference in ultraviolet absorption spectrum between the parallel direction and the perpendicular direction to the polarization electric field of the polarized ultraviolet light is larger, and the liquid crystal alignment film obtained in Example 4 is realigned by heating after irradiation with polarized ultraviolet light. You can see that it was done.
  • FIG. 6 is an ultraviolet absorption spectrum parallel and perpendicular to the polarized electric field vector of the irradiated ultraviolet rays of the liquid crystal alignment film obtained in Example 6.
  • Example 6 also shows the ultraviolet absorption spectrum of the liquid crystal alignment film obtained in Example 6 (shown as “parallel after heating” and “perpendicular after heating” in the figure). (Before the heat treatment of Example 6) UV absorption spectra of the liquid crystal alignment film (shown as “parallel after polarized light irradiation” and “perpendicular after polarized light irradiation” in the figure) are shown.
  • the polarized electric field of the irradiated polarized ultraviolet light is changed by heating after irradiation with polarized ultraviolet light.
  • the difference between the parallel UV absorption and the UV absorption in the vertical direction is only irradiated with polarized UV light (before the heat treatment in Example 4), and the direction parallel to and perpendicular to the polarization electric field of the irradiated polarized UV light. It can be seen that the liquid crystal alignment film obtained in Example 6 was realigned by heating after irradiation with polarized UV light.
  • Example 9 A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agent (I) obtained in Example 1, and a liquid crystal cell using the liquid crystal alignment film was manufactured.
  • the liquid crystal cell was a parallel aligned liquid crystal cell corresponding to the characteristics of the liquid crystal alignment film.
  • a liquid crystal display element can be constituted by sandwiching the obtained liquid crystal cell between a pair of polarizing plates.
  • a liquid crystal alignment treatment agent (I) is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then a liquid crystal alignment film as a coating film having a thickness of 50 nm. And a substrate with a liquid crystal alignment film before the alignment treatment was obtained.
  • the liquid crystal alignment films formed on the substrate were all excellent in film thickness uniformity, and the liquid crystal alignment treatment agent (I) was found to exhibit excellent coating properties.
  • the obtained substrate with a liquid crystal alignment film before the alignment treatment was used to irradiate polarized ultraviolet rays through a polarizing plate from a certain direction with respect to the liquid crystal alignment film surface on the substrate.
  • the intensity of the polarized ultraviolet light was 14 mW at a wavelength of 365 nm, and the ultraviolet irradiation amount was 600 mJ.
  • substrate was heated at 150 degreeC for 5 minute (s), and the reorientation process was performed to the coating film by making P6CBS of a coating film into a liquid-crystal state.
  • the substrate subjected to the re-orientation treatment was heated at 250 ° C. and baked at that temperature for 15 minutes to cause a condensation reaction of siloxane, thereby fixing the orientation. In this way, an alignment-treated substrate with a liquid crystal alignment film was obtained.
  • nematic liquid crystal ZLI-4792 manufactured by Merck & Co., Inc.
  • ZLI-4792 nematic liquid crystal
  • Example 10 A liquid crystal cell was produced according to the same method as in Example 9 except that the irradiation amount of polarized ultraviolet rays was 800 mJ.
  • Example 11 Using the liquid crystal cells obtained in Example 9 and Example 10, the alignment state of the liquid crystal was evaluated using a polarizing microscope. That is, a liquid crystal cell was sandwiched between a pair of polarizing plates using a polarizing microscope, and a liquid crystal display element was constructed and evaluated. In any liquid crystal cell, there was no alignment defect, and a good alignment state of the liquid crystal was observed. The evaluation results are summarized in Table 2.
  • a polymer and a liquid crystal aligning agent suitable for producing a highly efficient liquid crystal aligning film using light are provided, and the liquid crystal aligning film and the liquid crystal display element obtained from the liquid crystal aligning agent are lightweight, thin and It can be used as a display device with low power consumption.

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Abstract

L'invention fournit un procédé de fabrication de film à orientation de cristaux liquides à haut rendement mettant en œuvre une lumière, un film à orientation de cristaux liquides, et un élément d'affichage à cristaux liquides. Un polymère est obtenu par polymérisation d'un polysiloxane, et d'un monomère qui possède un groupe cristallin liquide et photosensible et un groupe polymérisable par voie radicalaire, afin de préparer un agent d'orientation de cristaux liquides. Après obtention d'un film polymère à chaîne latérale (1) à partir de cet agent d'orientation de cristaux liquides, un traitement d'orientation est effectué par irradiation à l'aide d'une lumière ultraviolette polarisée, puis une chaîne latérale (2) du film polymère à chaîne latérale (1) est réorientée par chauffage. Ensuite, le film à orientation de cristaux liquides est produit par un nouveau chauffage à haute température et fixation d'un état de réorientation. La température de chauffage pour réorientation, est inférieure ou égale à 200°C, ou similaire, et est comprise entre une température supérieure de 10°C par rapport à la limite inférieure d'une plage de température dans laquelle le film polymère à chaîne latérale (1) exprime ses propriétés cristallines liquides, et une température inférieure de 10°C par rapport à la limite supérieure de cette plage. L'élément d'affichage à cristaux liquides est fabriqué par mise en œuvre du film à orientation de cristaux liquides ainsi obtenu.
PCT/JP2013/069939 2012-07-24 2013-07-23 L'invention a pour objectif de fournir un procédé pour juger simplement l'état de différenciation, bon ou mauvais, de cellules souches pluripotentes, sans nécessiter le jugement d'un expert qualifié. l'invention a également pour objectif de fournir un procédé permettant l'application d'une détermination automatique des cellules souches pluripotentes ayant débuté une différenciation. ainsi, selon le procédé de l'invention, la bonne ou la mauvaise qualité de cellules souches pluripotentes est évaluée sur la base d'une différence de motifs de coloration des cellules souches pluripotentes. WO2014017497A1 (fr)

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CN201380049349.8A CN104937480B (zh) 2012-07-24 2013-07-23 液晶取向膜的制造方法、液晶取向膜、液晶显示元件、聚合物以及液晶取向剂

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KR20150038108A (ko) 2015-04-08
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CN104937480A (zh) 2015-09-23
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