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WO2016186190A1 - Composition de polymères, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, substrat comprenant ledit film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides comprenant ledit film d'alignement de cristaux liquides - Google Patents

Composition de polymères, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, substrat comprenant ledit film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides comprenant ledit film d'alignement de cristaux liquides Download PDF

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Publication number
WO2016186190A1
WO2016186190A1 PCT/JP2016/064963 JP2016064963W WO2016186190A1 WO 2016186190 A1 WO2016186190 A1 WO 2016186190A1 JP 2016064963 W JP2016064963 W JP 2016064963W WO 2016186190 A1 WO2016186190 A1 WO 2016186190A1
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WIPO (PCT)
Prior art keywords
group
ring
liquid crystal
carbon atoms
polymer
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PCT/JP2016/064963
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English (en)
Japanese (ja)
Inventor
隆之 根木
達哉 名木
功一朗 別府
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Nissan Chemical Corp
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Nissan Chemical Corp
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Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2017519409A priority Critical patent/JP6858349B2/ja
Priority to CN201680042742.8A priority patent/CN107849330B/zh
Priority to KR1020177036151A priority patent/KR102540422B1/ko
Publication of WO2016186190A1 publication Critical patent/WO2016186190A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Definitions

  • the present invention relates to a polymer composition for a liquid crystal aligning agent, in particular, a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element, consisting of the composition alone, consisting essentially of the composition or the composition.
  • a liquid crystal aligning agent having liquid crystal particularly a liquid crystal aligning agent for a horizontal electric field drive type liquid crystal display element, a liquid crystal alignment film formed from the liquid crystal aligning agent, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, and the liquid crystal alignment film
  • the present invention relates to a substrate, particularly a substrate for a horizontal electric field drive type liquid crystal display element, and a liquid crystal display element having the substrate, in particular, a horizontal electric field drive type 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 component of the liquid crystal display element, and is formed on the 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.
  • a photo-alignment method is known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability.
  • the photo-alignment method eliminates the need for rubbing, does not cause the generation of dust and static electricity, and can perform the alignment treatment even on the substrate of the liquid crystal display element having the uneven surface. There is an advantage that you can.
  • the photo-alignment method As the photo-alignment method, a decomposition-type photo-alignment method, a photo-crosslinking type, a photo-isomerization-type photo-alignment method, and the like are known.
  • the decomposition type photo-alignment method is, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. This is a method of aligning the liquid crystal by the method (for example, see Patent Document 1).
  • the photo-crosslinking type or photoisomerization type photo-alignment method uses, for example, polyvinyl cinnamate, irradiates polarized ultraviolet rays, and performs a dimerization reaction (cross-linking reaction) at the double bond portion of two side chains parallel to the polarized light. This is a method of generating and aligning the liquid crystal in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1).
  • Patent Document 3 discloses a liquid crystal alignment film obtained by using a photo-alignment method by photocrosslinking, photoisomerization or photo-fleece rearrangement.
  • the photo-alignment method has a great advantage because it eliminates the rubbing process itself as compared with the rubbing method conventionally used industrially as an alignment treatment method for liquid crystal display elements. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
  • the alignment controllability of the main component used in the photo-alignment method is too sensitive to the amount of polarized light, the alignment may be incomplete in part or all of the liquid crystal alignment film, and stable liquid crystal alignment cannot be realized. Occurs.
  • the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.
  • an object of the present invention is to increase the range of light irradiation amount in which the alignment control ability is stably generated, and to efficiently obtain a high-quality liquid crystal alignment film, a polymer composition for producing a liquid crystal alignment film
  • the object is to provide a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.
  • an object of the present invention is to provide a lateral electric field drive type liquid crystal device having an improved voltage holding ratio and a polymer composition for producing a liquid crystal alignment film for the device, specifically, a lateral electric field.
  • the object is to provide a composition for producing a liquid crystal alignment film for a drive type liquid crystal display element.
  • the object of the present invention is not limited to the above object, or in addition to the above object, the liquid crystal aligning agent comprising only the composition, consisting essentially of the composition, or having the composition,
  • the object is to provide a liquid crystal alignment film produced using a liquid crystal alignment agent, a substrate having the liquid crystal alignment film, the liquid crystal alignment film and / or a liquid crystal display element having the substrate, particularly a lateral electric field drive type liquid crystal display element.
  • the object of the present invention is to provide a method for producing the liquid crystal alignment film, a method for producing a substrate having the liquid crystal alignment film, the liquid crystal liquid crystal alignment film and / or the substrate.
  • Another object of the present invention is to provide a method for manufacturing a liquid crystal display element having a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element.
  • a polymer composition comprising: The composition described above, wherein one of the at least two polymers has a crosslinkable group.
  • one of the polymers (A1) and the other polymer (A2) out of at least two kinds of polymers may be different in the amount of a structure that exhibits photoreactivity.
  • the amount of the structure expressing the photoreactivity of the polymer (A1) is preferably larger than the amount of the structure expressing the photoreactivity of the polymer (A2).
  • the crosslinkable group is represented by the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein A broken line represents a bond, R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R 50 s , they may be the same or different from each other; t is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. It may be at least one group.
  • the crosslinkable group may be included in the polymer (A1).
  • the polymer (A1) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. Is good.
  • the polymer (A2) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. Is good.
  • at least two kinds of polymers each preferably have a structure exhibiting photoreactivity and liquid crystallinity, and a structure exhibiting only liquid crystallinity.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
  • the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
  • R May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different;
  • Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • the structures that exhibit photoreactivity in the above ⁇ 1> to ⁇ 8>, particularly the structures that exhibit photoreactivity and liquid crystallinity in ⁇ 8> are represented by the following formulas (7) to (10).
  • A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO Represents —O— or —O—CO—CH ⁇ CH—;
  • Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • —NO 2 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • —CN is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • —NO 2 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • —CN is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having
  • the structures that exhibit photoreactivity in the above ⁇ 1> to ⁇ 8>, particularly the structures that exhibit photoreactivity and liquid crystallinity in ⁇ 8> are represented by the following formulas (11) to (13).
  • A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X When CH is 2 and the number of X is 2, X may be the same or different; l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3; R represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those substituents. Each of the hydrogen atoms bonded to them is independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5).
  • the structure may be any one selected from the group consisting of:
  • each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, Or represents —O—CO—CH ⁇ CH—;
  • Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • the structure that exhibits photoreactivity in the above ⁇ 1> to ⁇ 8>, particularly the structure that exhibits photoreactivity and liquid crystallinity in ⁇ 8> is represented by the following formula (16) or (17) (wherein A is a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • CH is 2 and the number of X is 2, X may be the same or different; l represents an integer of 1 to 12, and m represents an integer of 0 to 2) It is good that the structure is represented by
  • the structure exhibiting photoreactivity in the above ⁇ 1> to ⁇ 8>, particularly the structure exhibiting photoreactivity and liquid crystallinity in ⁇ 8> is represented by the following formula (18) or (19): (Wherein A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O) Represents — or —O—CO—CH ⁇ CH—; Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an
  • a structure that exhibits photoreactivity in the above ⁇ 1> to ⁇ 8>, particularly a structure that exhibits photoreactivity and liquid crystallinity in ⁇ 8> is represented by the following formula (20) (where A is A bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ CH— To express; Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • —NO 2 —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different
  • l represents an integer of 1 to 12
  • m represents an integer of 0 to 2.
  • the structure that exhibits only liquid crystallinity has the following formulas (21) to (31): Wherein A and B have the same definition as above; Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; one of q1 and q2 is 1 and the other is 0; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more,
  • the amount of the structure expressing the photoreactivity of the polymer (A1) may exhibit a liquid crystallinity and a structure expressing the photoreactivity of the polymer (A1).
  • ⁇ mol% ⁇ is 15 or more, preferably 15 to 100, more preferably 20 to 80
  • the amount of the structure expressing the photoreactivity of the polymer (A2) is 0.95 ⁇ mol% or less when the structure expressing the photoreactivity of the polymer (A2) and the structure exhibiting liquid crystallinity are 100 mol%.
  • it is 0.1 ⁇ to 0.8 ⁇ mol%, more preferably 0.25 ⁇ to 0.5 ⁇ mol%.
  • the weight average molecular weight of the polymer (A1) is ⁇ ( ⁇ is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, More preferably, the weight average molecular weight of the polymer (A2) is 0.1 ⁇ to 0.9 ⁇ , preferably 0.2 ⁇ to 0.8 ⁇ , more preferably 0.3 ⁇ to 0.7 ⁇ . There should be.
  • ⁇ 19> In any one of the above items ⁇ 2> to ⁇ 18>, when the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%. %, More preferably 60 to 80 wt%.
  • the monomer (M1) preferably has a structure represented by any one of the above formulas (1) to (20).
  • the monomer (M2) may have a structure represented by the above formulas (21) to (31).
  • the monomer (M1) is represented by the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38. It is preferable that it is at least one selected from the group consisting of MA42, MA44 and MA46.
  • the monomer (M2) is selected from the group consisting of the following formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43, and MA45. It is good to be at least one selected.
  • the polymer (A1) is (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) Monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-3) Formulas (G-1), (G-2), (G-3) and (G-4)
  • M-1) a monomer having a structure that exhibits photoreactivity and liquid crystallinity
  • M-2) Monomer
  • M2 having a structure exhibiting only liquid crystallinity
  • M-3) Formulas (G-1), (G-2), (G-3) and (G-4)
  • a broken line represents a bond
  • R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms and a phenyl group, and when there are a plurality of R 50 s , they may be the same or different.
  • T is an integer of 1 to 7
  • J represents O, S, NH or NR 51
  • R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group.
  • the (M-3) monomer (M3) is represented by the following formula (0):
  • a and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH— Represents CO—O— or —O—CO—CH ⁇ CH—;
  • S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
  • T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different;
  • P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • the polymer (A1) is (M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group; It is good to form further.
  • the polymer (A2) is (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) a monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-4) at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. Having monomer (M4); It is good to form.
  • (M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, It may be at least one selected from the group consisting of the following formulas MA6 to MA8 and MA33.
  • the polymer (A1) has a monomer (M1) of ⁇ mol% ( ⁇ is 15 or more, preferably 15 to 100, more preferably 20 to 80) and the remainder is monomer (M2)
  • the polymer (A2) has a monomer (M1) of 0.95 ⁇ mol% or less, preferably 0.1 ⁇ to 0.8 ⁇ mol%, more preferably 0.25 ⁇ to 0.5 ⁇ mol%, and the remainder is monomer (M2 ) To be formed.
  • ⁇ 32> A liquid crystal alignment film formed from the liquid crystal aligning agent according to ⁇ 31>.
  • [I] A step of applying the polymer composition of ⁇ 1> to ⁇ 30> above onto a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
  • a method for producing a liquid crystal alignment film which obtains a liquid crystal alignment film imparted with an alignment control ability.
  • ⁇ 34> A substrate having the liquid crystal alignment film of ⁇ 32>.
  • ⁇ 35> [I] A step of applying the polymer composition according to any one of the above ⁇ 1> to ⁇ 30> onto a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II]; The manufacturing method of the board
  • ⁇ 36> A liquid crystal display device having the substrate of ⁇ 34> above.
  • ⁇ 37> a step of preparing the substrate (first substrate) of ⁇ 34>above;
  • [I ′] A step of applying the polymer composition according to any one of claims 1 to 26 on a second substrate to form a coating film;
  • [II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
  • [III ′] a step of heating the coating film obtained in [II ′];
  • a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics
  • a horizontal electric field drive type liquid crystal display element having the substrate can do.
  • a polymer composition for producing a liquid crystal alignment film that can efficiently obtain a liquid crystal alignment film having a good quality by expanding the range of the light irradiation amount in which the alignment control ability is stably generated
  • a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element can be provided.
  • a lateral electric field drive type liquid crystal element having an improved voltage holding ratio and a polymer composition for producing a liquid crystal alignment film for the element specifically, a lateral electric field drive type A composition for producing a liquid crystal alignment film for a liquid crystal display element
  • the liquid crystal aligning agent comprising the composition alone, consisting essentially of the composition only, or having the composition, the liquid crystal alignment A liquid crystal alignment film manufactured using an agent, a substrate having the liquid crystal alignment film, a liquid crystal alignment element having the liquid crystal alignment film and / or the substrate, particularly a lateral electric field drive type liquid crystal display element can be provided.
  • the method for manufacturing the liquid crystal alignment film in addition to or in addition to the above effects, the method for manufacturing the liquid crystal alignment film, the method for manufacturing the substrate having the liquid crystal alignment film, the liquid crystal liquid crystal alignment film and / or the liquid crystal having the substrate
  • a method for manufacturing a display element, particularly a lateral electric field drive type liquid crystal display element can be provided. Since the liquid crystal display element of the present invention, in particular the lateral electric field drive type liquid crystal display element, is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.
  • a liquid crystal display element having improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface, particularly a lateral electric field driven liquid crystal An element and a liquid crystal alignment film for the element can be provided.
  • the present application provides a polymer composition for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element. Moreover, this application provides the liquid crystal aligning agent which consists only of this composition, consists essentially of this composition, or has this composition, especially the liquid crystal aligning agent for lateral electric field drive type liquid crystal display elements. Furthermore, the present application relates to a liquid crystal alignment film formed from the liquid crystal alignment agent, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, a substrate having the liquid crystal alignment film, particularly a substrate for a horizontal electric field drive type liquid crystal display element, and A liquid crystal display device having the substrate, particularly a lateral electric field drive type liquid crystal display device is provided.
  • a liquid crystal alignment film formed from the liquid crystal alignment agent, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, a substrate having the liquid crystal alignment film, particularly a substrate for a horizontal electric field drive type liquid crystal display element, and A liquid crystal
  • the present application provides a polymer composition for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element.
  • the polymer composition of the present application is (A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity; and (B) an organic solvent; Containing.
  • 1 type of polymer has a crosslinkable group among at least 2 types of polymers.
  • one polymer (A1) and the other polymer (A2) have different amounts of structures that exhibit photoreactivity.
  • the amount of the structure expressing the photoreactivity of one polymer (A1) is preferably larger than the amount of the structure expressing the photoreactivity of the other polymer (A2).
  • the crosslinkable group refers to a substituent capable of crosslinking with a carboxyl group by heat.
  • VHR voltage holding ratio
  • crosslinkable group examples include, but are not limited to, an epoxy group, an oxetane group, a blocked isocyanate group, a thiirane group, and a thietane group.
  • the crosslinkable group is, for example, at least one group selected from the group consisting of the following formulas (G-1), (G-2), (G-3) and (G-4). It is good.
  • R 50 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a group selected from phenyl group, the same as or different from each other if R 50 is more T is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group.
  • the crosslinkable group may be present at the end of some side chains of the polymer. Moreover, it is good to have a crosslinking
  • At least one polymer may further have at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group.
  • both of the at least two polymers may further have at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group.
  • each polymer can have the same or different nitrogen-containing aromatic heterocyclic group.
  • the nitrogen-containing aromatic heterocycle is selected from the group consisting of the following formula [20a], formula [20b] and formula [20c] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms). It may be an aromatic cyclic hydrocarbon containing at least one selected structure, preferably 1 to 4 structures.
  • one type of polymer has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, thereby further improving the reliability such as voltage holding ratio (VHR).
  • VHR voltage holding ratio
  • Each of the at least two polymers preferably has a structure that exhibits photoreactivity and liquid crystallinity, and a structure that exhibits only liquid crystallinity.
  • liquid crystallinity only in “structure that expresses only liquid crystallinity” is a term used when considering “photoreactivity” and “liquid crystallinity”.
  • the expression “only” means that “liquid crystallinity” is expressed but “liquidity” is not expressed.
  • the “structure that exhibits photoreactivity” refers to a structure that reacts with light in a certain wavelength range, particularly light with a wavelength range of 250 nm to 400 nm.
  • the structure has a side chain of a polymer. Is good.
  • photoreactivity is not particularly limited, but means that it reacts with light to show a crosslinking reaction, an isomerization reaction, or a photo-Fries rearrangement, and preferably shows a crosslinking reaction. It is good.
  • the achieved orientation control ability can be stably maintained for a long period of time even when exposed to an external stress such as heat.
  • the “structure exhibiting liquid crystallinity” refers to a structure exhibiting liquid crystallinity in a certain temperature range, in particular, a temperature range of 100 to 300 ° C., for example, a mesogenic group or a mesogenic component in a polymer side chain. It is preferable that the structure has When a polymer having a “structure that exhibits liquid crystallinity” is used, stable liquid crystal alignment can be obtained when the polymer is used as a liquid crystal alignment film.
  • the polymer structure preferably has, for example, a main chain and a side chain bonded to the main chain, and the side chain has a “structure that exhibits photoreactivity” and a “structure that exhibits liquid crystallinity”.
  • the “structure that exhibits photoreactivity” and the “structure that exhibits liquid crystallinity” may be included in the same side chain or in different side chains.
  • the polymer is provided with a structure that exhibits photoreactivity and liquid crystallinity in a certain side chain, and a structure that exhibits only liquid crystallinity in another side chain.
  • a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, or an azobenzene group
  • the side chain has a “structure that expresses photoreactivity” that is bonded to the tip and exhibits a crosslinking reaction or isomerization reaction in response to light
  • the side chain is a “structure that exhibits liquid crystallinity”
  • the structure is a mesogenic component and has a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction, which is a “structure that exhibits photoreactivity”.
  • main chain of at least two polymers of the present invention are not particularly limited, but each independently includes hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, It may be composed of at least one selected from the group consisting of radically polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane.
  • the structure that exhibits photoreactivity may be a structure represented by any one selected from the group consisting of formulas (1) to (6).
  • A, B, D, S, Y 1 , Y 2 , R, X, Cou, q1 and q2, q3, P and Q, l1, l2, H, and I have the same definitions as described above. Have.
  • the structure that exhibits photoreactivity may be a structure represented by any one selected from the group consisting of formulas (7) to (10).
  • A, B, D, Y 1 , X, 1, m, m1, m2, n, Y 2 , and R have the same definition as described above.
  • the structure that exhibits photoreactivity may be a structure represented by any one selected from the group consisting of formulas (11) to (13).
  • A, X, l, m, m1 and R have the same definition as described above.
  • the structure that exhibits photoreactivity may be a structure represented by the formula (14) or (15).
  • A, Y 1 , l, m1, and m2 have the same definition as described above.
  • the structure that exhibits photoreactivity may be a structure represented by the formula (16) or (17).
  • A, X, l and m have the same definition as described above.
  • the structure that exhibits photoreactivity may be a structure represented by the formula (18) or (19).
  • A, B, Y 1 , q 1 , q 2, l, m 1, m 2, and R 1 have the same definition as described above.
  • the structure that exhibits photoreactivity in particular, the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by the formula (20).
  • A, Y 1 , X, 1 and m have the same definition as described above.
  • the structure exhibiting only liquid crystallinity is preferably a structure represented by any one selected from the group consisting of formulas (21) to (31).
  • A, B, Y 3 , R 3 , q 1, q 2, l, m, m 1, m 2 , m 3, R 2 , Z 1 , Z 2 have the same definition as described above.
  • ⁇ Amount of structure expressing photoreactivity of each of at least two polymers when the total of the structure expressing photoreactivity and the structure expressing only liquid crystallinity is 100 mol%, The amount of the structure expressing the photoreactivity of the polymer (A1) is ⁇ mol% ( ⁇ is 15 or more, preferably 15 to 100, more preferably 20 to 80), The amount of the structure expressing the photoreactivity of the polymer (A2) should be less than the amount of the structure expressing the photoreactivity of the polymer (A1), specifically 0.95 ⁇ mol% or less, preferably The content is 0.1 ⁇ to 0.8 ⁇ mol%, more preferably 0.25 ⁇ to 0.5 ⁇ mol%.
  • polymers having different amounts of structures that exhibit photoreactivity it is considered to have the following effects. That is, the orientation by ultraviolet irradiation is determined by the polymer (polymer (A1)) having a relatively large structure that exhibits photoreactivity.
  • a polymer (polymer (A2)) having a relatively small structure that exhibits photoreactivity but a relatively large structure that exhibits liquid crystallinity (polymer (A2)) is aligned according to the alignment defined by the polymer (A1).
  • each polymer can share the function of each and exhibit the function effectively.
  • Weight average molecular weight of each of at least two polymers is ⁇ ( ⁇ is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, more preferably 60,000 to 150,000). And The other weight average molecular weight is 0.1 ⁇ to 0.9 ⁇ , preferably 0.2 ⁇ to 0.8 ⁇ , more preferably 0.3 ⁇ to 0.7 ⁇ . In the present specification, unless otherwise specified, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) method.
  • the polymer (A1) having a relatively large amount of structure that exhibits photoreactivity has a weight average molecular weight of ⁇ ( ⁇ is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 20 10,000, more preferably 60,000 to 150,000)
  • the polymer (A2) having a relatively small amount of structure that exhibits photoreactivity has a weight average molecular weight of 0.1 ⁇ to 0.9 ⁇ , preferably 0.2 ⁇ to 0.8 ⁇ , more preferably 0.3 ⁇ to It should be 0.7 ⁇ .
  • the polymer having a large weight average molecular weight is relatively lower layer of the liquid crystal alignment film (relative to the substrate).
  • a polymer having a small weight average molecular weight tends to be formed in a relatively upper layer (layer relatively far from the substrate) of the liquid crystal alignment film.
  • the polymer (A2) having a relatively small structure that exhibits photoreactivity and a small weight average molecular weight is formed in a relatively upper layer (a layer far from the substrate) of the liquid crystal alignment film.
  • the polymer (A1) in the lower layer (layer relatively close to the substrate) is oriented according to the polarized ultraviolet rays.
  • the polymer (A2) of the upper layer (layer relatively far from the substrate) is oriented along the orientation of the polymer (A1).
  • the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%, more preferably 60 to 80 wt%. ) Should be the remainder.
  • the polymer (A1) and the polymer (A2) have two or more of the above three characteristics, ie, “amount of structure that develops photoreactivity”, “weight average molecular weight”, and “weight ratio”. It is preferred to have properties, preferably all three properties.
  • the production method of the at least two polymers of the present invention is not particularly limited as long as it has the above-described configuration.
  • at least two polymers of the present invention include (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) a monomer having a structure that exhibits only liquid crystallinity.
  • the polymer (A1) is (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) a monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-3) a monomer having a crosslinkable group, specifically, the above formulas (G-1), (G-2), Monomer (M3) having at least one group selected from the group consisting of (G-3) and (G-4), more specifically the following formula (0) (in formula (0), A, B, S, T, X, P, Q, 11, 12, and G have the same definition as above, and a monomer having a structure represented by: It is good to form.
  • the polymer (A1) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group
  • the polymer (A1) (M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group; It is good to form further.
  • the polymer (A2) is (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) a monomer (M2) having a structure that exhibits only liquid crystallinity; It is good to form.
  • the polymer (A2) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group
  • the polymer (A2) is: (M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group; It is good to form further.
  • the polymer (A2) when the polymer (A2) has a crosslinkable group, the polymer (A2) may further be formed to further include the above-described (M-3) monomer (M3).
  • the polymer (A1) and the polymer (A2) may have other monomers in addition to the above-mentioned monomers and may be formed by copolymerization within a range not impairing the photoreactive property and / or liquid crystallinity. Good.
  • at least two kinds of polymers of the present invention are formed having the monomer (M1) and the monomer (M2), but the total of the monomer (M1) and the monomer (M2) is 100 mol%.
  • the monomer (M1) is ⁇ mol% ( ⁇ is 15 or more, preferably 15 to 100, more preferably 20 to 80) and the balance is the monomer (M2). ) To be formed.
  • the monomer (M1) is 0.95 ⁇ mol% or less, preferably 0.1 ⁇ to 0.8 ⁇ mol%, more preferably 0.25 ⁇ to 0.5 ⁇ mol%, and the remainder is monomer. It may be formed so as to be (M2).
  • the monomer (M1) and the monomer (M2) used in the polymer (A1) and the polymer (A2) are common to each other.
  • Monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity and its production method At least two polymers of the present invention have the monomer (M1) having a structure that exhibits the above-described photoreactivity and liquid crystallinity; and (M-2) the monomer (M2) having a structure that exhibits only liquid crystallinity. It is good to obtain by forming and specifically copolymerizing.
  • the monomer (M1) having a structure that develops photoreactivity and liquid crystallinity may form a polymer having a structure that develops photoreactivity and liquid crystallinity at the side chain site of the polymer when the polymer is formed. It is a monomer that can be used.
  • the structure that exhibits photoreactivity at the side chain site the following structures and derivatives thereof are preferable.
  • the monomer (M1) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane
  • the monomer (M1) is polymerized in the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38 to MA42, MA44 and MA46, and their compounds.
  • the polymerizable group of the compound having methacrylate as a functional group is replaced with a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It may be at least one selected from the group consisting of compounds.
  • the monomer (M1) may have (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH. Note that MA1 to MA46 can be synthesized as follows.
  • MA1 can be synthesized by a synthesis method described in a patent document (WO2011-084546).
  • MA2 can be synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).
  • MA3 can be synthesized by a synthesis method described in non-patent literature (Macromolecules 2002, 35, 706-713).
  • MA4 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
  • MA5 can be synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 2010-18807).
  • MA6 to MA9 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
  • As MA10 commercially available M6BC (manufactured by Midori Chemical Co., Ltd.) can be used.
  • MA11 to 13 can be synthesized by the synthesis method described in the patent document
  • MA14 to 18 are commercially available, and M4CA, M4BA, M2CA, M3CA, and M5CA (all of which are manufactured by Midori Chemical Co., Ltd.) can be used.
  • MA19 to 23 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
  • MA24 can be synthesized by a synthesis method described in non-patent literature (Polymer Journal, Vol. 29, No. 4, pp 303-308 (1997)).
  • MA25 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
  • MA26 and MA27 are the synthesis methods described in non-patent literature (Macromolecules (2012), 45 (21), 8547-8554) and non-patent literature (Liquid Crystals (1995), 19 (4), 433-40), respectively. Can be synthesized.
  • MA28 to 33 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
  • MA34 to 39 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
  • MA40 and 41 can be synthesized by a synthesis method described in a patent document (Japanese Patent Publication No. 2009-511431).
  • MA42 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
  • MA43 can be synthesized by a synthesis method described in a patent document (WO2012-115129).
  • MA44 can be synthesized by a synthesis method described in a patent document (WO2013-1333078).
  • MA45 can be synthesized by the synthesis method described in the patent document (WO2008-072652).
  • MA46 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
  • the monomer (M2) having a structure that exhibits only liquid crystallinity is a monomer that allows a polymer derived from the monomer to exhibit liquid crystallinity and to form a mesogenic group at a side chain site.
  • a mesogenic group having a side chain even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good.
  • the mesogenic group possessed by the side chain the following structure is preferable.
  • the monomer (M2) having a structure exhibiting only liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, A structure having a structure composed of at least one polymerizable group selected from the group consisting of radically polymerizable groups such as norbornene and siloxane and at least one of the above formulas (21) to (31). Is preferred.
  • the monomer (M2) is composed of the above-described formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45, and compounds having a methacrylate as a polymerizable group in these compounds. At least one selected from the group consisting of compounds in which the group is replaced by a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane It is good to be.
  • the monomer (M2) may have (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.
  • the polymer (A1) or, if desired, the polymer (A2) is an (M-3) monomer having a crosslinkable group, specifically, the following formulas (G-1), (G-2), ( A monomer (M3) having at least one group selected from the group consisting of G-3) and (G-4), more specifically a monomer having a structure represented by the following formula (0): It is good to be formed.
  • monomers having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether.
  • the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.
  • the monomer having aziridine include those in which the epoxy structure of the monomer having the epoxy group is replaced with aziridine or 1-methylaziridine.
  • Examples of the monomer having an oxetane group include (meth) acrylic acid ester having an oxetane group.
  • monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyl-oxetane, 3- (acryloyloxymethyl) -3- Methyl-oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- ( Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (acryloyl
  • the monomer having a thietane group for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with a thietane group is preferable.
  • the monomer having an azetidine group for example, a monomer in which an oxetane group of a monomer having an oxetane group is replaced with an azetidine group is preferable.
  • a monomer having an epoxy group and a monomer having an oxetane group are preferable from the viewpoint of availability and the like, and a monomer having an epoxy group is more preferable.
  • glycidyl (meth) acrylate is preferable from the viewpoint of availability.
  • the polymer (A1) or the polymer (A2) optionally has (M-4) at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group.
  • the nitrogen-containing aromatic heterocycle is selected from the group consisting of the following formula [20a], formula [20b] and formula [20c] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms). It may be an aromatic cyclic hydrocarbon containing at least one selected structure, preferably 1 to 4 structures.
  • the polymer composition of the present invention has an ionicity.
  • the cross-linking reaction of the group represented by the above formula (0), or a more durable liquid crystal alignment film Obtainable In order to reduce the elution of impurities and promote the cross-linking reaction of the cross-linkable group, more specifically, the cross-linking reaction of the group represented by the above formula (0), or a more durable liquid crystal alignment film Obtainable.
  • the monomer (M4) is replaced with the monomer (M1) and the monomer (M2), and optionally with the monomer (M3). What is necessary is just to copolymerize.
  • the monomer (M4) is selected from the group consisting of hydrocarbons, (meth) acrylates, itaconates, fumarate, maleates, ⁇ -methylene- ⁇ -butyrolactone, radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane.
  • It preferably has a polymerizable group composed of at least one kind and a structure having a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group.
  • NH in the amide group and urethane group may or may not be substituted.
  • substituent in the case where it may be substituted include an alkyl group, an amino-protecting group, and a benzyl group.
  • the monomer having a nitrogen-containing aromatic heterocyclic group examples include 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate and 2- (3-pyridylcarbonyloxy). And ethyl (meth) acrylate, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.
  • the monomer having an amide group or a urethane group examples include 2- (4-methylpiperidin-1-ylcarbonylamino) ethyl (meth) acrylate and 4- (6-methacryloyloxyhexyloxy) benzoic acid.
  • Examples thereof include N- (tertiary butyloxycarbonyl) piperidin-4-yl ester, 4- (6-methacryloyloxyhexyloxy) benzoic acid, 2- (tertiary butyloxycarbonylamino) ethyl ester, and the like.
  • a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group is represented by the following formulas MA6 to MA8 and MA33, and Polymerizability wherein the polymerizable group of the compound having a methacrylate as a polymerizable group in the compound is selected from the group consisting of acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane It may be at least one selected from the group consisting of compounds in which the group is replaced.
  • the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the method for producing at least two kinds of polymers of the present invention is not particularly limited, and a general-purpose method handled industrially can be used.
  • the monomer (M1) having a structure that exhibits the above-described photoreactivity and liquid crystallinity
  • the monomer (M2) having a structure that exhibits only liquid crystallinity
  • a monomer having a crosslinkable group (M3) if desired.
  • radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
  • RAFT reversible addition-cleavage chain transfer
  • a radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher.
  • radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
  • the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
  • a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group is copolymerized and used in the reaction to obtain each of at least two polymers of the present invention.
  • the organic solvent is not particularly limited as long as the produced polymer is soluble. Specific examples are given below.
  • organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the produced
  • the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. 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. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass 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 molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
  • the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
  • the reaction solution may be poured into a poor solvent to precipitate these polymers.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water.
  • the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
  • the resin component includes at least two kinds of polymers having the structure that expresses (A) the photoreactivity and the structure that exhibits the liquid crystallinity described above, and one of the polymers has a crosslinkable group. It is a resin component to be included. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.
  • the resin component described above may be at least two types of polymers having the above-described (A) structure that exhibits photoreactivity and the structure that exhibits liquid crystallinity.
  • other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired.
  • the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
  • examples of such other polymers include poly (meth) acrylates, polyamic acids, polyimides, and the like, and examples include polymers that are not polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity. .
  • the organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. 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 ethyl ketone
  • the polymer composition used in the present invention may contain components other than the above components (A) and (B).
  • the polymer composition of the present invention when used for a liquid crystal alignment film for a liquid crystal display element, particularly for a horizontal electric field drive type liquid crystal display element, it may contain components other than the components (A) and (B).
  • the polymer composition when applied to a substrate, particularly a substrate for a liquid crystal display element, more particularly a substrate for a lateral electric field drive type liquid crystal display element, the film thickness uniformity and the surface smoothness are improved.
  • substrate it is not limited to this.
  • the polymer composition used in the present invention may have (C) a specific amine compound as a component other than the components (A) and (B).
  • the specific amine compound as the component (C) specifically has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is an aliphatic hydrocarbon group or It can be an amine compound bonded to a non-aromatic cyclic hydrocarbon group.
  • a liquid crystal alignment film having higher durability can be obtained.
  • the specific amine compound is not particularly limited as long as it exhibits the following effects i) and / or ii) when the polymer composition used in the present invention forms a liquid crystal alignment film. i) Adsorbs ionic impurities in the liquid crystal at the liquid crystal alignment film interface and / or ii) exhibits improved voltage holding ratio.
  • the amount of the specific amine compound is not particularly limited as long as the above effect is obtained, but is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention. It is good that it is a mass part.
  • aliphatic hydrocarbon group examples include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond.
  • the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • divalent non-aromatic cyclic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring
  • it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and even more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.
  • the nitrogen-containing aromatic heterocyclic ring contained in the amine compound has the following formula [20a], formula [20b] and formula [20c] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms) And an aromatic cyclic hydrocarbon containing at least 1, preferably 1 to 4 structures selected from the group consisting of:
  • the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
  • More preferred amine compounds are those represented by the following formula A- [1] (wherein Y 11 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y 12 is a nitrogen-containing group.
  • the amine compound is preferably an aromatic heterocyclic ring.
  • Y 12 is not particularly limited as long as Y 12 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
  • Preferred Y 11 in formula A- [1] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. It is good to be.
  • Examples of the non-aromatic cyclic hydrocarbon group include the above-described structures.
  • Y 11 is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y 11 is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 11 is —O—, —NH—, —CO—O—.
  • —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • divalent cyclic hydrocarbon group examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Ring, cyclon
  • divalent heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring.
  • Y 12 in the formula A- [1] is a nitrogen-containing aromatic heterocyclic ring, and as described above, at least one selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c]
  • An aromatic cyclic hydrocarbon containing the structure Specific examples thereof include the structure described above.
  • pyrrole ring imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring and a phthalazine ring are preferable.
  • Y 11 is a formula [20a], a formula included in Y 12 It is preferable that it is combined with a substituent not adjacent to [20b] and formula [20c].
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 12 in formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, sulfur You may contain hetero atoms, such as an atom and a nitrogen atom.
  • a preferred combination of Y 11 and Y 12 in the formula A- [1] is a group in which Y 11 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
  • Y 12 is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, A benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 12 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. May be contained.
  • Y 13 is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms
  • Y 14 Is a single bond, or —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms
  • the total of carbon atoms of Y 13 and Y 14 Is an amine compound represented by:
  • Y 15 is a nitrogen-containing aromatic heterocyclic ring.
  • Y 13 in the formula A- [2] is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cycloo
  • a linear or branched alkylene group having 1 to 10 carbon atoms cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring.
  • Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 13 is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C ( CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • the cyclic hydrocarbon group and the heterocyclic ring mentioned here have the same meaning as defined for Y 11 in the formula A- [1].
  • Y 14 in the formula A- [2] is a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms.
  • the divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y 14 are given below.
  • Y 15 in the formula A- [2] is a nitrogen-containing aromatic heterocyclic ring and has the same definition as Y 12 in the formula A- [1]. Specific examples may include the same structure as Y 12 described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.
  • Y 14 is a formula [20a] or formula included in Y 15. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c]. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 15 in the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom or a sulfur atom. And may contain a hetero atom such as a nitrogen atom.
  • Y 13 is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y 14 is a single bond, having 1 carbon atom To 10 linear or branched alkylene groups, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —, —CO—, —
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane A ring, a cycloheptane ring, a norbornene ring, or an adamantane ring
  • Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CH (OH) —, —NH—CH 2 —, —S— CH 2 —, —O—CH 2 —, —O—C 2 H 4
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, or A cyclohexane ring
  • Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—.
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • a particularly preferred combination of Y 13 , Y 14 and Y 15 in the formula A- [2] is that Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y 14 is , Single bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CH (OH) —, benzene ring, naphthalene ring, fluorene ring, or anthracene Y 15 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Specific examples of the specific amine compound of the component (C) of the present invention include compounds M1 to M156.
  • More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156.
  • M6 to M8 M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.
  • the polymer composition used for this invention may have the following (D) components as components other than the said (A) and (B) component. That is, the component (D) is a compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted (hereinafter also referred to as compound D).
  • the compound D is not particularly limited as long as the compound D has one or more alkoxysilyl groups and one or more urea structures substituted at both the 1-position and the 3-position. From the viewpoint of properties and the like, a compound represented by the following formula (d) is one of preferred examples.
  • X 102 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, and R 102 is a hydrogen atom Or represents an alkyl group, and when n is 2 or more, R 102 becomes alkylene together with other R 102 , or when n is 1 to 6, it also binds to X 102 to form a ring together with X 102
  • L may represent an alkylene having 2 to 20 carbon atoms, and R 103 and R 104 may each independently represent an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or (It is an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.
  • R 103 and R 104 in the formula (d) are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, but availability of raw materials and reactivity From the viewpoint, methyl or ethyl is preferable.
  • L in the formula (d) examples include alkylene having 2 to 20 carbon atoms, but trimethylene is preferable from the viewpoint of obtaining the raw material.
  • One embodiment of the compound of component (D) is a compound in which X 102 is a divalent organic group, R 102 is a hydrogen atom, and L is trimethylene.
  • Such a compound represented by the formula (2-1) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.
  • X in the compound represented by the formula (2-1) is preferably a structure selected from the following structural formulas.
  • One embodiment of the compound of component (D) is a compound in which X 102 is a divalent organic group, R 102 together forms an alkylene, and L is trimethylene.
  • Such a compound represented by the formula (2-2) can be obtained by reacting 2.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing two NH.
  • X in the compound represented by the formula (2-2) is preferably a structure selected from the following structural formulas.
  • the description includes a nitrogen atom in the ring.
  • X 102 is a divalent organic group, one of R 102 is a hydrogen atom, and the other is also bonded to X 102 to form a ring, A compound in which L is trimethylene.
  • Such a compound represented by the formula (2-3) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.
  • X in the compound represented by the formula (2-3) is preferably a structure selected from the following structural formulas.
  • the description includes a nitrogen atom in the ring.
  • One embodiment of the compound of component (D) is a compound in which X 102 is a trivalent organic group, R 102 is a hydrogen atom, and L is trimethylene.
  • Such a compound represented by the formula (2-4) can be obtained by reacting a triamine compound with 3.05 equivalent of trialkoxysilylpropyl isocyanate.
  • X in the compound represented by the formula (2-4) is preferably a structure selected from the following structural formulas.
  • One embodiment of the compound of component (D) is a compound in which X 102 is a monovalent organic group, R 102 is a hydrogen atom, and L is trimethylene.
  • Such a compound represented by the formula (2-5) can be obtained by reacting a monoamine compound with 1.05 equivalent of trialkoxysilylpropyl isocyanate.
  • X in the compound represented by the formula (2-5) is preferably a structure selected from the following structural formulas.
  • One embodiment of the compound of component (D) is a compound in which X 102 is a monovalent organic group, R 102 is bonded to X 102 to form a ring, and L is trimethylene.
  • Such a compound represented by the formula (2-6) can be obtained by reacting 1.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing one NH.
  • X in the compound represented by the formula (2-6) is preferably a structure selected from the following structural formulas.
  • the description includes a nitrogen atom in the ring.
  • the amount of the isocyanate compound used may be 0.98 equivalent times to 1.2 equivalent times with respect to one NH or NH 2 group. More preferably, it is 1.0 equivalent times to 1.05 equivalent times.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sul
  • Sulfur aprotic polar solvent pyridine, pyridines picoline and the like. These solvents may be used alone or as a mixture of two or more thereof. Preferred are toluene, acetonitrile, ethyl acetate and tetrahydrofuran, and more preferred are acetonitrile and tetrahydrofuran.
  • the amount of the solvent used is not particularly limited, but the reaction may be carried out without using a solvent.
  • the solvent is used in an amount of 0.1 to 100 times the amount of the isocyanate compound. It may be used.
  • the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
  • the reaction temperature is not particularly limited but is, for example, ⁇ 90 to 150 ° C., preferably ⁇ 30 to 100 ° C., and more preferably 0 ° C. to 80 ° C.
  • the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
  • a catalyst may be added to shorten the reaction time.
  • examples thereof include dibutyltin dilaurate, dioctyltin bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dibutyltin diacetate, etc.
  • Inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid
  • titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate
  • bismuth compounds such as bismuth tris (2-ethylhexanoate); quaternary An ammonium salt etc. are mentioned.
  • These catalysts may be used alone or in combination of two or more. These catalysts are preferably liquid or soluble in the reaction solvent.
  • the catalyst When a catalyst is added, the catalyst may be used in an amount of 0.005 wt% to 100 wt%, preferably 0.05 wt% to 10 wt%, based on the total amount (mass) of the compound having an isocyanate group. Preferably, it is 0.1 wt% to 5 wt%. If an organotin compound, a titanium compound, or a bismuth compound is used as the catalyst, the amount is preferably 0.005 wt% to 0.1 wt%.
  • This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
  • Specific examples of the preferred component (D) include compounds represented by any one of S1 to S4.
  • the amount of the component (D) component is preferably 0.1 to 20% by mass and more preferably 1 to 10% by mass with respect to the polymer of the (A) component.
  • the polymer composition used for this invention can mention the following as components other than the said (A) and (B) component, it is not limited to these.
  • the following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
  • solvents may be used alone or in combination.
  • it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.
  • Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
  • 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 polymer composition
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
  • phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
  • An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.
  • Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
  • 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 polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
  • photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
  • Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
  • a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
  • a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.
  • the present application has a polymer composition as described above, or consists essentially of the polymer composition as described above, or a liquid crystal aligning agent composed of only the polymer composition as described above, particularly for a liquid crystal display element, more particularly laterally.
  • a liquid crystal aligning agent for an electric field driven liquid crystal display element is provided.
  • liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent, especially the liquid crystal aligning film for liquid crystal display elements, and more especially for a horizontal electric field drive type liquid crystal display element.
  • present application relates to a liquid crystal alignment film formed from the liquid crystal alignment agent described above, particularly a substrate having a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, particularly a liquid crystal display element.
  • a substrate for a horizontal electric field drive type liquid crystal display element is provided.
  • the liquid crystal alignment film described above is [I] The process of apply
  • a liquid crystal alignment film imparted with an alignment control ability, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, or a substrate having the liquid crystal alignment film can be obtained.
  • ⁇ Board Although it does not specifically limit about a board
  • the substrate has a conductive film for driving a horizontal electric field when used in a horizontal electric field drive type liquid crystal display element.
  • the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
  • examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
  • a method for forming a conductive film on a substrate a conventionally known method can be used.
  • Step [I] a coating film is formed by applying the polymer composition of the present invention, which exhibits liquid crystallinity in a predetermined temperature range, onto a substrate having a conductive film for driving a lateral electric field.
  • the method for applying the polymer composition described above or the liquid crystal aligning agent described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
  • the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
  • the heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven is used.
  • the solvent can be evaporated at 50 to 150 ° C. to obtain a coating film.
  • the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the polymer of the component (A) of the present invention.
  • the liquid crystal phase expression temperature of the polymer of component (A) is a temperature at which at least two polymers of component (A) exhibit a liquid crystal phase as a whole.
  • the thickness of the coating film is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
  • step [II] the coating film obtained in step [I] is irradiated 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 nm to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
  • ultraviolet light having a wavelength in the range of 290 nm 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 polarized ultraviolet rays depends on the coating film used.
  • the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
  • the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
  • Step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
  • An orientation control ability can be imparted to the coating film by heating.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
  • the heating temperature is preferably within the temperature range of the temperature at which the polymer of the component (A) of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature).
  • the liquid crystallinity expression temperature on the coating film surface is expected to be lower than the liquid crystallinity expression temperature when the polymer of the component (A) of the present invention is observed in bulk.
  • the heating temperature is more preferably within the temperature range of the liquid crystallinity expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C.
  • the temperature is in a range where the upper limit is 10 ° C. lower than the upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
  • the liquid crystalline expression temperature is equal to or higher than the glass transition temperature (Tg) at which the polymer or coating film surface of the component (A) of the present invention undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase ( A temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition in the isotropic phase.
  • Tg glass transition temperature
  • Tiso isotropic phase transition temperature
  • the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
  • the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
  • liquid crystal display element> and ⁇ Method for manufacturing liquid crystal display element>
  • the present application provides a liquid crystal display element having a substrate having a liquid crystal alignment film obtained as described above, particularly a lateral electric field drive type liquid crystal display element.
  • a second substrate is prepared, whereby a lateral electric field drive type liquid crystal display element can be obtained.
  • the second substrate uses a substrate having no lateral electric field driving conductive film instead of the substrate having the lateral electric field driving conductive film, the second electric field driving conductive film as in the first substrate is used.
  • a substrate having In addition, the second substrate preferably has a liquid crystal alignment film as in the first substrate.
  • the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
  • the obtained liquid crystal alignment film-attached substrate (second substrate) is arranged to face each other with the liquid crystal alignment film facing each other through the liquid crystal, and a liquid crystal cell is manufactured by a known method.
  • This is a step of manufacturing a drive type liquid crystal display element.
  • the steps [I ′] to [III ′] can be performed in the same manner as the steps [I] to [III] except for the difference in the presence or absence of the conductive film for driving the lateral electric field in the step [I]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
  • the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
  • the other substrate is bonded and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • Etc. can be illustrated.
  • the diameter of the spacer is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
  • the polymer composition or the liquid crystal aligning agent of the present invention As described above, the polymer composition or the liquid crystal aligning agent of the present invention, the liquid crystal alignment film formed using the composition or the liquid crystal aligning agent, the substrate having the alignment film, and the liquid crystal alignment film or substrate are provided.
  • the liquid crystal display element formed in this manner in particular the lateral electric field drive type liquid crystal display element, has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • M1 as a monomer having a photoreactive group used in Examples M2 as a monomer having a liquid crystal group, HBAGE as a monomer having a crosslinking group, and A1 as a monomer having an amide group are shown below.
  • M1 and M2 were synthesized as follows. That is, M1 was synthesized by the synthesis method described in the patent document (WO2011-084546). M2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). A polymer formed using M1 as a monomer has photoreactivity and liquid crystallinity, and a polymer formed using M2 as a monomer has only liquid crystallinity. The monomer A1 to be copolymerized was synthesized by the synthesis method described in Synthesis Example 1 below. As HBAGE (hydroxybutyl acrylate glycidyl ether), a commercially available product was used.
  • HBAGE hydroxybutyl
  • Example 1 Add the methacrylate polymer powder P1 (0.105 g) obtained in Polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.245 g) obtained in Polymer Synthesis Example P2 to NMP (5.65 g) at room temperature. Stir for 1 hour to dissolve. To this solution, PB (4.0 g) was added and stirred to obtain a polymer solution T1. This polymer solution T1 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.
  • the polymer types used and their wt%, and for Example 1, two types of polymers were used.
  • Amount of photoreactive group, monomer species from which “photoreactive group” and “liquid crystalline group” in each polymer are derived, “amount of photoreactive group” in the monomer, and liquid crystal aligning agent derived therefrom is summarized in Table 2 below.
  • the “photoreactive group amount in each polymer” and “total photoreactive group amount” in Table 2 can be determined, for example, as follows.
  • the monomer from which the “photoreactive group” in the polymer species P1 is derived is M1.
  • M2 has only a “liquid crystalline group”.
  • the amount of photoreactive groups in each polymer is a mol% value of “photoreactive groups” when the total of “liquid crystalline groups” and “photoreactive groups” is 100 mol%.
  • the “photoreactive group amount” of the polymer species P1 is 100 ⁇ ⁇ 0.1 / (0.1 + 0.9) ⁇ , which is 10 mol%.
  • the “photoreactive group amount” in the polymer species P2 is 20 mol%.
  • the “total photoreactive group amount” is determined from the weight ratio of the polymer species P1 and P2 and the “photoreactive group amount” in the polymer species P1 and P2, and is 0.1 mol% ⁇ 0.3 (P1 0.17 mol% is obtained from (the seed is derived from 30 wt%) + 0.2 mol% ⁇ 0.7 (the P2 seed is derived from 70 wt%).
  • the liquid crystal aligning agent (T1) obtained in Example 1 was filtered through a 0.45 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C. for 90 seconds, and a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the surface of the coating film was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 to 80 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.
  • liquid crystal alignment film Two substrates with such a liquid crystal alignment film are prepared, a 6 ⁇ m spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other.
  • the periphery was sealed, and an empty cell with a cell gap of 4 ⁇ m was produced.
  • Liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
  • Liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
  • liquid crystal cells were prepared using the liquid crystal alignment agents CT1, CT2 and CT3 obtained in Controls 1 to 3.
  • VHR voltage holding ratio
  • Example 1 two polymers having different photoreactive group amounts are used, and a polymer having a relatively large photoreactive group amount has an epoxy group (derived from HBAGE).
  • an epoxy group derived from HBAGE.
  • the film shows a good orientation and a good VHR in a wide range of UV irradiation doses.
  • Example 1 and Control 1 are compared, they have almost the same amount of total photoreactive groups (Example 1: 0.17; Control 1: 0.20), and both are epoxy.
  • a polymer having a group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group is used, whereby VHR shows almost the same value.
  • Example 1 in both, in Example 1, two types (P1 and P2) are used as the polymer type, while in Control 1, only one type (P2) is used as the polymer type.
  • P1 and P2 two types
  • P2 only one type
  • UV irradiation dose 50 mJ / cm 2 and while excellent orientation in 80 mJ / cm 2 is confirmed
  • Example 1 shows better orientation in a wide range of UV irradiation dose and VHR also has a desired value as compared with Control 1.
  • Example 1 Comparing Example 1 with Control 2, both have approximately the same amount of total photoreactive groups (Example 1: 0.17; Control 2: 0.20), thereby allowing them to have a wide range of UV irradiation. It shows good orientation in the amount.
  • Example 1 two types (P1 and P2) are used as polymer species, and a polymer having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group is used in the two types of polymers.
  • P3 only one type (P3) is used as the polymer type. Due to this difference, VHR shows a desired value in Example 1, whereas VHR is lower than the desired value in Control 2, and Example 1 has a wider range of UV irradiation than Control 2.
  • Example 1 and Control 3 both have the same total photoreactive group amount (Example 1: 0.17; Control 3: 0.17), but two polymer types (P1 and P2). ) And a polymer having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group in the two types of polymers, while in Control 3, only one type (P4) is used as the polymer type, The P4 is different in that it does not have an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group.
  • Example 1 shows good orientation in a wide range of UV irradiation doses and VHR also shows a desired value, whereas in Control 3, VHR is lower than the desired value and the UV irradiation amount is also related. It can be seen that the desired characteristics cannot be achieved at any dose.

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Abstract

La présente invention concerne une composition de polymères pour la fabrication d'un film d'alignement de cristaux liquides dans laquelle la fonctionnalité de contrôle d'alignement est stable, la plage de la quantité de lumière irradiée qui est générée peut être agrandie, et le taux de rétention de tension est amélioré. Plus précisément, la présente invention concerne une composition permettant la fabrication d'un film d'alignement de cristaux liquides destiné à un élément d'affichage à cristaux liquides à commutation dans le plan. La composition de polymères comprend (A) au moins deux polymères ayant une structure qui présente une photoréactivité et une structure qui présente une cristallinité liquide, et (B) un solvant organique, et l'un des deux polymères ou plus comprend un groupe de réticulation.
PCT/JP2016/064963 2015-05-20 2016-05-20 Composition de polymères, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, substrat comprenant ledit film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides comprenant ledit film d'alignement de cristaux liquides Ceased WO2016186190A1 (fr)

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CN201680042742.8A CN107849330B (zh) 2015-05-20 2016-05-20 聚合物组合物、液晶取向剂、液晶取向膜、具有该液晶取向膜的基板及具有该液晶取向膜的液晶表示元件
KR1020177036151A KR102540422B1 (ko) 2015-05-20 2016-05-20 중합체 조성물, 액정 배향제, 액정 배향막, 그 액정 배향막을 갖는 기판 및 그 액정 배향막을 갖는 액정 표시 소자

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WO2017170681A1 (fr) * 2016-03-30 2017-10-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2018155675A1 (fr) * 2017-02-27 2018-08-30 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage de cristaux liquides
JPWO2017199986A1 (ja) * 2016-05-18 2019-03-14 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
WO2023095925A1 (fr) * 2021-11-29 2023-06-01 日産化学株式会社 Composition polymère et matériau retardateur monocouche
JP7605027B2 (ja) 2021-06-01 2024-12-24 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、並びに重合体及びその製造方法

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WO2017170681A1 (fr) * 2016-03-30 2017-10-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP6992746B2 (ja) 2016-05-18 2022-01-13 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
JPWO2017199986A1 (ja) * 2016-05-18 2019-03-14 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR20190124743A (ko) * 2017-02-27 2019-11-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
CN110546560A (zh) * 2017-02-27 2019-12-06 日产化学株式会社 液晶取向剂、液晶取向膜及液晶表示元件
JPWO2018155675A1 (ja) * 2017-02-27 2019-12-19 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
WO2018155675A1 (fr) * 2017-02-27 2018-08-30 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage de cristaux liquides
JP7106059B2 (ja) 2017-02-27 2022-07-26 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
CN110546560B (zh) * 2017-02-27 2022-08-19 日产化学株式会社 液晶取向剂、液晶取向膜及液晶表示元件
TWI805572B (zh) * 2017-02-27 2023-06-21 日商日產化學工業股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
KR102573453B1 (ko) 2017-02-27 2023-08-31 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP7605027B2 (ja) 2021-06-01 2024-12-24 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、並びに重合体及びその製造方法
WO2023095925A1 (fr) * 2021-11-29 2023-06-01 日産化学株式会社 Composition polymère et matériau retardateur monocouche

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KR20180008677A (ko) 2018-01-24
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