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WO2018062353A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2018062353A1
WO2018062353A1 PCT/JP2017/035120 JP2017035120W WO2018062353A1 WO 2018062353 A1 WO2018062353 A1 WO 2018062353A1 JP 2017035120 W JP2017035120 W JP 2017035120W WO 2018062353 A1 WO2018062353 A1 WO 2018062353A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
aligning agent
crystal aligning
solvent
Prior art date
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PCT/JP2017/035120
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English (en)
Japanese (ja)
Inventor
淳彦 萬代
泰宏 宮本
石川　和典
柱永 李
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Nissan Chemical Corp
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Nissan Chemical Corp
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Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2018542833A priority Critical patent/JP7063270B2/ja
Priority to KR1020197012038A priority patent/KR20190060803A/ko
Priority to CN201780073610.6A priority patent/CN110023826B/zh
Priority to KR1020227036843A priority patent/KR102826032B1/ko
Publication of WO2018062353A1 publication Critical patent/WO2018062353A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a liquid crystal aligning agent that is suitable for inkjet coating and has an increased resin component ratio while maintaining a low viscosity, and a liquid crystal aligning film obtained from the liquid crystal aligning agent.
  • liquid crystal alignment film As the liquid crystal alignment film, a so-called polyimide-based liquid crystal alignment film, which is obtained by applying and baking a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution, is widely used.
  • a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution
  • spin coating, dip coating, flexographic printing, and the like are generally known as methods for forming such a liquid crystal alignment film. Actually, there are many applications by flexographic printing.
  • an inkjet method has attracted attention as a new method for applying a liquid crystal alignment film without using a printing plate.
  • the ink jet method is a method in which fine droplets are dropped on a substrate and a film is formed by wetting and spreading of the liquid. Not only the printing plate is not used, but also the printing pattern can be set freely, so that the manufacturing process of the liquid crystal display element can be simplified. In addition, there is an advantage that the waste of the coating liquid is reduced because the film formation on the dummy substrate which is necessary for flexographic printing is not necessary.
  • the inkjet method is expected to reduce the cost of liquid crystal panels and improve production efficiency.
  • the liquid crystal alignment film formed by the ink jet method is required to have small film thickness unevenness inside the coating surface and high film forming accuracy in the periphery of the coating.
  • a liquid crystal alignment film formed by an ink-jet method has a trade-off relationship between the uniformity of the film thickness in the coating surface and the film forming accuracy in the periphery of the coating.
  • a material with high in-plane uniformity has poor dimensional stability in the periphery of the coating, and the film protrudes from the set dimensions.
  • the material in which the coating peripheral part is a straight line has poor uniformity in the coated surface.
  • Patent Document 1 Patent Document 2, Patent Document 3
  • Patent Document 2 Patent Document 3
  • Patent Document 3 Patent Document 3
  • a contact hole (hereinafter also referred to as C / H) is formed on the TFT substrate in order to connect the lower layer wiring and the upper layer wiring.
  • C / H a contact hole
  • the spread of the liquid tends to be hindered during the application of the liquid crystal aligning agent due to the influence of the wiring structure and C / H.
  • unevenness in the film thickness of the alignment film such as dot-like unevenness and streaky unevenness, occurs around the C / H and other portions, and the display of the liquid crystal display element may become uneven.
  • the liquid crystal aligning agent used in the ink jet method is required to have low viscosity in order to stably discharge the aligning agent from the ink jet nozzle, and accordingly, the resin component ratio in the liquid crystal aligning agent is set to be small.
  • the resin component ratio in the liquid crystal aligning agent is set to be small.
  • the present invention can suppress poor application of the alignment film due to the influence of the wiring structure and C / H, can suppress defects in which the display of the liquid crystal display element is non-uniform, and
  • An object of the present invention is to provide a liquid crystal aligning agent in which the resin component ratio is increased while lowering the viscosity of the liquid crystal aligning agent, and a liquid crystal alignment film using the same.
  • the gist of the present invention is as described below.
  • the liquid crystal aligning agent characterized by including the solvent component containing the solvent of the following A group, the solvent of B group, and isobutyl ketone.
  • Group A At least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone and 1,3-dimethylimidazolidinone
  • Group B Butyl cellosolve, 1-butoxy -At least one solvent selected from the group consisting of 2-propanol, 2-butoxy-1-propanol and dipropylene glycol dimethyl ether;
  • a polyimide-based liquid crystal aligning agent having a high resin component ratio and a liquid crystal aligning film using the same can be provided.
  • the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyimide precursor and a polyimide which is an imidized product thereof, a polymer containing a protecting group that is eliminated by heat, a solvent of the above group A, And a solvent component containing isobutyl ketone and a group B solvent.
  • the solvent contained in the liquid crystal aligning agent of this invention contains the solvent which belongs to the said A, B, and C group.
  • the solvent belonging to Group A is at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, and 1,3-dimethylimidazolidinone. These solvents dissolve the polymer in the liquid crystal aligning agent.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone are preferable, and N-methyl-2-pyrrolidone and ⁇ -butyrolactone are more preferable.
  • the amount of the solvent belonging to Group A is preferably 20% by mass to 90% by mass and more preferably 30% by mass to 85% by mass with respect to the total mass of the liquid crystal aligning agent. More preferably, it is 50 mass% to 85 mass% or less.
  • the solvent belonging to Group B is at least one solvent selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, 2-butoxy-1-propanol, and dipropylene glycol dimethyl ether.
  • This solvent is a solvent that contributes to improving the application uniformity of the liquid crystal aligning agent and lowering the viscosity.
  • butyl cellosolve, 1-butoxy-2-propanol and dipropylene glycol dimethyl ether are preferably contained, and 1-butoxy-2-propanol is particularly preferred.
  • 1-butoxy-2-propanol usually contains several isomers including 2-butoxy-1-propanol as isomers, and is usually used in that state.
  • the amount of the solvent belonging to the group B is preferably 1% by mass to 50% by mass and more preferably 10% by mass to 50% by mass with respect to the total mass of the liquid crystal aligning agent. More preferably, the content is 10% by mass to 30% by mass.
  • the amount of the diisobutyl ketone contained in the liquid crystal aligning agent of the present invention is preferably 1% by mass to 20% by mass and more preferably 5% by mass to 20% by mass with respect to the total mass of the liquid crystal aligning agent.
  • the polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyimide precursor that is a reaction product of a tetracarboxylic acid derivative component and a diamine component, and a polyimide that is an imidized product thereof, It is a polymer containing a protecting group that replaces a hydrogen atom by heat.
  • the diamine component used in the liquid crystal aligning agent of the present invention includes a diamine (hereinafter, also referred to as a specific diamine) that contains a protective group that is eliminated by heat in the structure.
  • the structure of the protecting group is not particularly limited as long as it is a functional group that can be removed by heating.
  • this protecting group A is preferably not desorbed at room temperature, preferably a protecting group desorbed by heat of 80 ° C. or more, more preferably 100 ° C. This is a protecting group which is eliminated by heat.
  • it is preferably a protective group that is eliminated by heat of 300 ° C. or less, more preferably 250 ° C.
  • the following protecting groups can be removed by heat, and more preferably, the protecting group can be removed by heat at 200 ° C. or less.
  • the specific diamine preferably used in the present invention contains the following structure.
  • X 1 is an oxygen atom or a sulfur atom
  • a 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9. * Represents a bond with another atom.
  • X 1 is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • a 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably 1 carbon atom. The total number of carbon atoms is 1 to 9, preferably 3 to 6. * Represents a bond with another atom.
  • Examples of the diamine having the formula (a) in the structure include diamines having the following structure.
  • “Boc” is a tert-butoxycarbonyl group.
  • the amount of the specific diamine used in the liquid crystal aligning agent of the present invention is preferably 10 mol% to 50 mol% in the total diamine component, more preferably 10 mol to 40%.
  • the diamine component used in the liquid crystal aligning agent of the present invention can contain other diamines as long as the effects of the present invention are exhibited in addition to the diamines described above.
  • the structure of other diamines is not particularly limited, and can be generalized by, for example, the following formula (2).
  • a 1 and A 2 in the above formula (2) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. . From the viewpoint of liquid crystal orientation, A 1 and A 2 are preferably a hydrogen atom or a methyl group.
  • An example of the structure of Y 1 is as follows.
  • n is an integer of 1 to 6.
  • n is an integer from 1 to 6.
  • ⁇ Vertical alignment diamine diamine having a specific side chain structure>
  • the present invention is used as a VA liquid crystal aligning agent, it is preferable to prepare a polymer using a diamine having a specific side chain structure that exhibits a vertical alignment ability.
  • the diamine having the specific side chain structure has at least one side chain structure selected from the group represented by the following formulas [S1] to [S3].
  • diamine having a specific side chain structure there is a diamine having a specific side chain structure represented by the following formula [S1].
  • X 1 and X 2 are each independently a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, — CON (CH 3 ) —, —NH—, —O—, —COO—, —OCO— or — ((CH 2 ) a1 —A 1 ) m1 — is represented.
  • the plurality of a1 are each independently an integer of 1 to 15
  • the plurality of A 1 are each independently an oxygen atom or —COO—
  • m 1 is 1 to 2.
  • X 1 and X 2 are each independently a single bond or — (CH 2 ) a — (a is an integer of 1 to 15) from the viewpoint of availability of raw materials and ease of synthesis. , —O—, —CH 2 O— or —COO— are preferred, a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or — COO- is more preferred.
  • G 1 and G 2 are each independently selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Represents a divalent cyclic group.
  • Arbitrary hydrogen atoms on the cyclic group include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
  • m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 4.
  • R 1 represents alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons or alkoxyalkyl having 2 to 20 carbons. Any hydrogen that forms R 1 may be substituted with fluorine.
  • examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene, naphthalene and the like.
  • examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.
  • R 1 is the same as in the above formula [S1].
  • X p is — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, —O—, —CH 2 O—, —COO— or —OCO— is represented.
  • a 1 represents an oxygen atom or —COO— * (a bond marked with “*” binds to (CH 2 ) a2 ).
  • a 2 represents an oxygen atom or * —COO— (the bond with “*” is bonded to (CH 2 ) a2 ).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10.
  • Cy represents a 1,4-cyclohexylene group or a 1,4-phenylene group.
  • diamine having a specific side chain structure there is a diamine having a specific side chain structure represented by the following formula [S2].
  • X 3 represents a single bond, —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, —O—, —CH 2 O—, —COO— or —OCO—.
  • X 3 is preferably —CONH—, —NHCO—, —O—, —CH 2 O—, —COO— or —OCO— from the viewpoint of the liquid crystal orientation of the liquid crystal aligning agent.
  • R 2 represents alkyl having 1 to 20 carbons or alkoxyalkyl having 2 to 20 carbons. Any hydrogen that forms R 2 may be substituted with fluorine.
  • R 2 is preferably an alkyl having 3 to 20 carbon atoms or an alkoxyalkyl having 2 to 20 carbon atoms from the viewpoint of the liquid crystal alignment property of the liquid crystal aligning agent.
  • diamine having a specific side chain structure there is a diamine having a specific side chain structure represented by the following formula [S3].
  • R 3 represents a structure having a steroid skeleton.
  • the steroid skeleton here has a skeleton represented by the following formula (st) in which three six-membered rings and one five-membered ring are bonded.
  • X represents the above formula [X1] or [X2].
  • Col represents at least one selected from the group consisting of the above formulas [Col1] to [Col4], and G represents the above formula [G1] or [G2].
  • * Represents a site bonded to another group.
  • Examples of preferable combinations of X, Col and G in the above formula [S3-x] include the following. That is, a combination of [X1] and [Col1] and [G1], a combination of [X1] and [Col1] and [G2], a combination of [X1], [Col2] and [G1], and [X1] and [Col2] ] And [G2], [X1] and [Col3] and [G2], [X1] and [Col4] and [G2], [X1] and [Col3] and [G1] Combination of [X1] and [Col4] and [G1], combination of [X2] and [Col1] and [G2], combination of [X2] and [Col2] and [G2], [X2] and [Col2] and [G1], [X2], [Col3] and [G2], [X2], [Col4] and [G2], [X2], [Col1] and [G1], [X2] ], [Col4] and
  • a typical example of a steroid skeleton is cholesterol (a combination of [Col1] and [G2] in the above formula [S3-x]), but a steroid skeleton that does not contain cholesterol can also be used.
  • examples of the diamine having a steroid skeleton include cholestanyl 3,5-diaminobenzoate, and the like, but a diamine component which does not include a diamine having a cholesterol skeleton is also possible.
  • what does not contain an amide in the connection position of a diamine and a side chain can also be utilized as a diamine which has a specific side chain structure.
  • a liquid crystal alignment film or a liquid crystal display element capable of ensuring a high voltage holding ratio over a long period of time. It is possible to provide a liquid crystal aligning agent capable of obtaining
  • the diamine having a side chain structure represented by the above formulas [S1] to [S3] is represented by the following formula [1-S1]-[1-S3], respectively.
  • ⁇ Vertical alignment diamine diamine having a two-side chain characteristic side chain structure>
  • a polymer can be prepared using a two-side chain type diamine having two specific side chain structures with vertical alignment.
  • the bilateral diamine which may be contained as a diamine component is represented, for example by following formula [1].
  • X represents a single bond, —O—, —C (CH 3 ) 2 —, —NH—, —CO—, —NHCO—, —COO—, — (CH 2 ) m —, It represents a divalent organic group consisting of —SO 2 — or any combination thereof.
  • X is preferably a single bond, —O—, —NH—, —O— (CH 2 ) m —O—.
  • Examples of “any combination thereof” include —O— (CH 2 ) m —O—, —O—C (CH 3 ) 2 —, —CO— (CH 2 ) m —, —NH— (CH 2) m -, - SO 2 - (CH 2) m -, - CONH- (CH 2) m -, - CONH- (CH 2) m -NHCO -, - COO- (CH 2) m -OCO- , etc.
  • m is an integer of 1 to 8.
  • two Y's independently represent the structure of the following formula [1-1].
  • Y 1 and Y 3 are each independently a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2. O—, —COO— or —OCO— is represented.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • Y 1 or Y 3 is a single bond or — (CH 2 ) a —
  • Y 2 is a single bond.
  • Y 1 is —O—, —CH 2 O—, —COO— or —OCO—
  • / or Y 3 is —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 is a single bond or — (CH 2 ) b —.
  • Y 4 represents a divalent group having 17 to 51 carbon atoms having at least one divalent cyclic group or steroid skeleton selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring.
  • the optional hydrogen atom forming the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom.
  • Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring.
  • the optional hydrogen atom forming the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom.
  • Y 6 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. And at least one selected from the group consisting of a group and a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
  • n is an integer of 0-4.
  • the two-side chain diamine having a side chain structure represented by the above formulas [S1] to [S3] is represented by the following formula [2-S1]-[2-S3], respectively.
  • Y may be in the meta position or in the ortho position from the position of X, but is preferably in the ortho position. That is, the formula [1] is preferably the following formula [1 ′].
  • the position of the two amino groups may be any position on the benzene ring, but in the following formulas [1] -a1 to [1] -a3 The represented position is preferable, and the following formula [1] -a1 is more preferable.
  • X is the same as in the above formula [1].
  • the following formulas [1] -a1 to [1] -a3 are for explaining the positions of the two amino groups, and the Y notation represented in the above formula [1] is omitted.
  • the above formula [1] is selected from the following formulas [1] -a1-1 to [1] -a3-2
  • the structure represented by the following formula [1] -a1-1 is more preferable.
  • X and Y are the same as those in the formula [1].
  • examples of the formula [1-1] include the following formulas [1-1] -1 to [1-1] -22, but are not limited thereto. Among these, as examples of the above formula [1-1], the following formulas [1-1] -1 to [1-1] -4, [1-1] -8 or [1-1] -10 are preferable. .
  • * represents the bonding position with the phenyl group in the above formulas [1], [1 '] and [1] -a1 to [1] -a3.
  • the diamine component contains a two-side chain diamine having a predetermined structure
  • a liquid crystal alignment film in which the ability to align the liquid crystal vertically is hardly lowered even when exposed to excessive heating.
  • the liquid crystal alignment film is difficult to reduce the ability to align the liquid crystal vertically. That is, the liquid crystal aligning agent from which the liquid crystal aligning film excellent in the said various characteristics can be provided because a diamine component contains this 2 side chain diamine.
  • diamines having photoreactive side chains diamines having photoreactive side chains.
  • a polymer is prepared using a diamine having a photoreactive side chain for the purpose of increasing the reactivity of the polymerizable compound contained in the liquid crystal. You can also.
  • the diamine component of this embodiment may contain a diamine having a photoreactive side chain as another diamine. When the diamine component contains a diamine having a photoreactive side chain, the photoreactive side chain can be introduced into the specific polymer or other polymers.
  • diamine having a photoreactive side chain examples include, but are not limited to, those represented by the following formula [VIII] or [IX].
  • the position of the two amino groups (—NH 2 ) may be any position on the benzene ring, for example, on the benzene ring with respect to the linking group of the side chain. 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions or 3, 5 positions. From the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferred. Considering the ease of synthesis of the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • R 8 is a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) — or —N (CH 3 ) CO— is represented.
  • R 8 is preferably a single bond, —O—, —COO—, —NHCO— or —CONH—.
  • R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.
  • —CH 2 — of the alkylene group may be optionally substituted with —CF 2 — or —CH ⁇ CH—, and when any of the following groups is not adjacent to each other, these groups are substituted: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic or heterocyclic ring.
  • the divalent carbocycle or heterocycle can be specifically exemplified by the following formula (1a), but is not limited thereto.
  • R 9 can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.
  • R 10 represents a photoreactive group selected from the group consisting of the following formula (1b).
  • R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH— or —CO—.
  • Y 2 represents an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring.
  • One or a plurality of hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring herein may be substituted with a fluorine atom or an organic group.
  • —CH 2 — when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO— or a single bond.
  • Y 4 represents a cinnamoyl group.
  • Y 5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle.
  • One or a plurality of hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring herein may be substituted with a fluorine atom or an organic group.
  • Y 5 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 6 represents a photopolymerizable group such as an acryl group or a methacryl group.
  • diamine having a photoreactive side chain represented by the above formula [VIII] or [IX] include the following formula (1c), but are not limited thereto.
  • X 9 and X 10 each independently represent a single bond, —O—, —COO—, —NHCO— or —NH—.
  • Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.
  • Examples of the diamine having a photoreactive side chain include a diamine of the following formula [VII].
  • the diamine of the formula [VII] has a site having a radical generating structure in the side chain.
  • radicals are generated by decomposition by ultraviolet irradiation.
  • Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, and the hydrogen atom of those rings may be substituted with a halogen atom. Since Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays, a structure having a long conjugate length such as naphthylene or biphenylene is preferable when the wavelength is increased. On the other hand, when Ar has a structure such as naphthylene or biphenylene, the solubility may deteriorate, and in this case, the difficulty of synthesis increases. Ar is most preferably a phenyl group because sufficient characteristics can be obtained even with a phenyl group if the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm.
  • the aromatic hydrocarbon group may be provided with a substituent.
  • substituent here are preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 1 and R 2 may form a ring.
  • T 1 and T 2 are each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH. 2 O -, - N (CH 3) -, - CON (CH 3) - or an -N (CH 3) CO- linking group.
  • S represents a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted with a fluorine atom.
  • the alkylene group —CH 2 — or —CF 2 — in this case may be optionally substituted with —CH ⁇ CH—, and when any of the following groups is not adjacent to each other, May be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, divalent carbocycle, divalent heterocycle;
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents —CH 2 —, —NR—, —O—, or —S—.
  • Q is preferably an electron-donating organic group, and is preferably an alkyl group, a hydroxyl group, an alkoxy group, an amino group, or the like as described in the example of Ar.
  • Q is an amino derivative
  • a defect such as the formation of a salt between the carboxylic acid group and the amino group generated during polymerization of the polyamic acid, which is a polyimide precursor, may result in a hydroxyl group or an alkoxy group. Is more preferable.
  • the position of the two amino groups (—NH 2 ) may be any of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, but is reactive with acid dianhydride. In this respect, m-phenylenediamine or p-phenylenediamine is preferable.
  • n is an integer of 2 to 8.
  • diamines having a photoreactive side chain represented by the above formula [VII], [VIII] or [IX] can be used singly or in combination of two or more.
  • a single type or a mixture of two or more types may be used. It may be used, or in the case of using a mixture of two or more, the proportion thereof may be appropriately adjusted.
  • the tetracarboxylic acid derivative component for producing the polymer having the structural unit of the above formula (1), which is contained in the liquid crystal aligning agent of the present invention includes not only tetracarboxylic dianhydride but also its tetracarboxylic acid.
  • Derivatives such as tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalide compound can also be used.
  • tetracarboxylic dianhydride or a derivative thereof it is more preferable to use at least one selected from a tetracarboxylic dianhydride represented by the following formula (3) and a derivative thereof.
  • X 1 is a tetravalent organic group having an alicyclic structure, and the structure is not particularly limited. Specific examples include the following formulas (X1-1) to (X1-44).
  • R 3 to R 23 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon An alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, which may be the same or different.
  • R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • Specific examples of the structure of the formula (X1-1) include structures represented by the following formulas (X1-1-1) to (X1-1-6). (X1-1-1) is particularly preferable from the viewpoints of liquid crystal alignment and photoreaction sensitivity.
  • the polyimide precursor and the tetracarboxylic dianhydride which is a raw material of the polyimide described in the present invention and derivatives thereof are represented by the above formula (3) with respect to 1 mol of all tetracarboxylic dianhydrides and derivatives thereof. It is preferable to contain 60 to 100 mol% of tetracarboxylic dianhydride and derivatives thereof. Since a liquid crystal alignment film having good liquid crystal alignment properties can be obtained, it is more preferably 80 mol% to 100 mol%, and still more preferably 90 mol% to 100 mol%.
  • the polyamic acid ester which is one of the polyimide precursors used in the present invention can be synthesized by the following method (1), (2) or (3).
  • the polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
  • the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
  • the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of polymer solubility. These may be used alone or in combination of two or more. Good.
  • the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine.
  • tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
  • a base pyridine, triethylamine, 4-dimethylaminopyridine, etc. are used.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
  • the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • the polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.
  • tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can synthesize
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the addition amount of the base is preferably 2 to 4 times mol with respect to the diamine component from the viewpoint of easy removal and high molecular weight.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
  • the synthesis method (1) or (2) is particularly preferable.
  • the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method.
  • tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours.
  • an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours.
  • the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more. It may be used.
  • the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight body is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyimide used in the present invention can be produced by imidizing the polyamic acid ester or polyamic acid.
  • chemical imidization in which a basic catalyst is added to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
  • Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
  • the temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
  • Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
  • the liquid crystal aligning agent of the present invention is preferable.
  • the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the liquid crystal aligning agent used in the present invention has a form of a solution in which a polymer having a specific structure is dissolved in an organic solvent.
  • the molecular weight of the polyimide precursor and polyimide described in the present invention is preferably 2,000 to 500,000 in weight average molecular weight, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100. , 000.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, but it is 1 weight from the viewpoint of forming a uniform and defect-free coating film. % From the viewpoint of storage stability of the solution, and preferably 10% by weight or less.
  • the polyimide precursor described in the present invention can be used as a solvent other than the solvents belonging to the groups A, B and C (hereinafter also referred to as other solvents).
  • a solvent also referred to as a good solvent
  • a solvent also referred to as a poor solvent
  • improves the coating properties and surface smoothness of the liquid crystal alignment film when a liquid crystal aligning agent is applied may be contained. .
  • the good solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide (IPMA or 4-hydroxy-4 -Methyl-2-pentanone and the like.
  • the poor solvent include, for example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl -1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3- Methylcyclohex Nord, 1,2-ethanediol, 1,
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms
  • the liquid crystal aligning agent of the present invention includes at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. Or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
  • the crosslinkable compound having an oxetane group is a compound having at least two oxetane groups represented by the following formula [4A].
  • crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
  • the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol
  • Examples of the melamine derivative or benzoguanamine derivative include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
  • MX-750 which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
  • MW-30 manufactured by Sanwa Chemical Co., Ltd.
  • Methoxymethylated ethoxymethyl Benzomethylamine methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (Mitsui Cyanamid) For example).
  • glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
  • crosslinkable compounds of the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27) can be mentioned. It is done.
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl
  • E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring; 2 represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
  • the crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, or may combine 2 or more types.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
  • the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymer component. More preferred is 1 to 50 parts by mass.
  • the liquid crystal aligning agent of the present invention can use a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied.
  • the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
  • the amount of the surfactant used 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 all the polymer components contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent is disclosed in International Publication No. WO2011 / 132751 (published 2011.10.27) on pages 69 to 73 as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device.
  • Nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] can also be added.
  • the amine compound may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine compound after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
  • the solvent is not particularly limited as long as the specific polymer (A) is dissolved.
  • the liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal aligning film, and a compound that promotes charge removal.
  • a polymer other than the polymer described in the present invention, a silane coupling agent for the purpose of improving the adhesion between the alignment film and the substrate, and further when firing the coating film An imidization accelerator for the purpose of efficiently progressing imidization by heating of the polyimide precursor may be added to.
  • the liquid crystal alignment film is a film obtained by applying the above liquid crystal aligning agent to a substrate, drying and baking.
  • the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with a glass substrate or a silicon nitride substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is used from the viewpoint of simplification of the process.
  • an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like is common.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.
  • the solvent can be evaporated by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention.
  • a condition of baking at 50 to 120 ° C. for 1 to 10 minutes and then baking at 150 to 300 ° C. for 5 to 120 minutes is mentioned in order to sufficiently remove the contained solvent.
  • the thickness of the liquid crystal alignment film after baking is too thin, the reliability of the liquid crystal display element may be lowered, and thus it is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
  • the liquid crystal alignment treatment agent of the present invention is applied to a substrate, baked, and then subjected to an alignment treatment by a rubbing treatment, a rubbing treatment or a photo-alignment treatment performed by a conventional apparatus or method, or in a vertical alignment application. Without alignment treatment, it can be used as a liquid crystal alignment film.
  • liquid crystal display element having a passive matrix structure
  • the liquid crystal display element may be an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display.
  • switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display.
  • a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
  • These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a SiO 2 —TiO 2 film formed by a sol-gel method.
  • a liquid crystal alignment film is formed on each substrate, the other substrate is overlapped with one substrate so that the liquid crystal alignment film faces each other, and the periphery is bonded with a sealant.
  • a spacer is usually mixed in the sealant, and it is preferable to spray a spacer for controlling the substrate gap on the in-plane portion where no sealant is provided.
  • a part of the sealant is provided with an opening that can be filled with liquid crystal from the outside.
  • a liquid crystal material is injected into the space surrounded by the two substrates and the sealing agent through the opening provided in the sealing agent, and then the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • the liquid crystal material either a positive liquid crystal material or a negative liquid crystal material may be used, but a negative liquid crystal material is preferable.
  • a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer.
  • a line / slit electrode pattern of, for example, 1 ⁇ m to 10 ⁇ m is formed on one substrate, and a slit pattern or projection pattern is not formed on the counter substrate.
  • the liquid crystal display element having this structure can simplify the manufacturing process and obtain high transmittance.
  • an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate provided with no electrode A liquid crystal aligning agent is apply
  • the metal film for example, a film made of a metal such as chromium can be used.
  • the liquid crystal material constituting the liquid crystal layer of the vertical alignment type liquid crystal display element is not particularly limited, and liquid crystal materials used in the conventional vertical alignment method, for example, MLC-6608, MLC-6609, MLC-3022 manufactured by Merck & Co., Inc. Negative type liquid crystal such as can be used.
  • MLC-3023 which is a liquid crystal containing a polymerizable compound can be used.
  • a liquid crystal containing a polymerizable compound represented by the following formula can be used.
  • liquid crystal material constituting the liquid crystal layer of the horizontal alignment type liquid crystal display element such as IPS or FFS is not particularly limited, and liquid crystal materials conventionally used in the horizontal alignment type, such as MLC-2003 and MLC manufactured by Merck Negative-positive liquid crystals such as ⁇ 2041 and negative-type liquid crystals such as MLC-6608 can also be used.
  • a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
  • a liquid crystal cell can also be produced by a method in which the other substrate is bonded to each other so as to be inside, and sealing is performed.
  • the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • a liquid crystal cell is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
  • a method of applying an electric voltage to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between the electrodes installed on the substrate and irradiating ultraviolet rays while maintaining the electric field can be mentioned.
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p or DC 2.5 to 15 V, preferably 10 to 30 Vp-p or DC 5 to 15 V.
  • ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
  • the light source of the irradiation light is as described above.
  • the irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is increased.
  • the polymerizable compound when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer.
  • the response speed of the obtained liquid crystal display element can be increased.
  • a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.
  • liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film excellent in the uniformity of the film thickness within the coating surface and the linearity and dimensional stability of the peripheral portion of the coating.
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • BCS butyl cellosolve
  • PB 1-butoxy-2-propanol
  • DPM dipropylene glycol monomethyl ether
  • DIBK diisobutyl ketone
  • DC-1 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • DC-2 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • DC-3 bicyclo [ 3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
  • DC-4 pyromellitic anhydride
  • DC-5 3,3,4,4-biphenyltetracarboxylic dianhydride
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Boc represents a t-butoxy group
  • the measuring method of each characteristic is as follows.
  • the viscosity of the polyamic acid ester, the polyamic acid solution and the polyimide solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL (milliliter) and cone rotor TE-1 (1 ° 34 ′ R24) at a temperature of 25 ° C.
  • the molecular weights of the polyamic acid ester and the polyamic acid were measured by a GPC (room temperature gel permeation chromatography) device, and converted into a polyethylene glycol (polyethylene oxide) conversion value as a number average molecular weight (hereinafter, also referred to as Mn) and a weight average molecular weight (hereinafter, Mw) was calculated.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml / L) Flow rate: 1.0 ml / min
  • Standard sample for preparing a calibration curve TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation and polyethylene glycol (peak top molecular weight manufactured by Polymer Laboratory) (Mp) of about 12,000, 4,000, and 1,000).
  • Mw weight average molecular weight
  • Mp peak top molecular weight manufactured by Polymer Laboratory
  • Example 1 In a 40 ml sample tube containing a stir bar, 4.00 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 4.80 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were weighed. Weighed 23.20 g of NMP, 6.80 g of PB and 1.20 g of DIBK and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A1.
  • Liquid crystal aligning agent A1 adjusted above was apply
  • the coating conditions were a discharge pitch of 40 ⁇ m, a coating speed of 100 mm / sec, an injection voltage of 13.0 V, and a coating area of 36 ⁇ 80 mm.
  • the film thickness of the coating film was applied under the conditions of 100 nm when baked in an IR oven at 230 ° C. for 30 minutes after being temporarily dried on an 80 ° C. hot plate for 2 minutes.
  • Lv4 is a material that can be visually confirmed to have a noticeable unevenness on the entire surface
  • Lv3 is a material that can be visually confirmed to be partially uneven
  • Lv2 is a material that cannot be seen visually
  • Lv1 is an image that has no unevenness even on an optical microscope.
  • Silicone-based water repellent film OA-160R1 (manufactured by Nissan Chemical Industries, Ltd.) was dropped on a 10 ⁇ 10 cm glass substrate and spin-coated on the glass substrate at a rotational speed of 2000 rpm. Thereafter, this glass substrate was baked in an IR oven at 200 ° C. for 30 minutes to obtain a hydrophobic glass substrate.
  • liquid crystal aligning agent A1 adjusted above, it apply
  • the coating conditions were a discharge pitch of 500 ⁇ m, a coating speed of 100 mm / sec, an injection voltage of 13.0 V, and a coating area of 36 ⁇ 80 mm.
  • coating liquid crystal aligning agent A1 on the said conditions after performing temporary drying for 2 minutes on an 80 degreeC hotplate, it baked by IR oven on the conditions for 230 degreeC for 30 minutes.
  • Examples 2 to 9 and Comparative Examples 1 to 9 The polyamic acid solutions obtained in Synthesis Examples 1 to 3, 5, and 7 to 9 and the polyimide solutions obtained in Synthesis Examples 4 and 6 have the predetermined blend ratio, solid content concentration, and solvent ratio shown in Table 1 below.
  • the liquid crystal aligning agents A2 to A6 and the liquid crystal aligning agents B1 to B5, C1, D1, E1, F1, G1, H1, and I1 were obtained.
  • the composition ratio of the polyamic acid solution, the polyimide solution and the solvent is shown in Table 1 together with Example 1.
  • the solid content composition and the weight ratio represent the mixing ratio (mass%) of each polymer.
  • the composition and weight ratio of the solution represent the ratio (mass%) of each organic solvent to the whole polymer solution.
  • Table 2 summarizes the evaluation results and the like in Examples 1 to 9 and Comparative Examples 1 to 9.
  • Tetracarboxylic dianhydride DC-3 (12.51 g, 50.0 mmol), diamine DA-7 (13.66 g, 40.0 mmol), diamine DA-11 (6.61 g, 20.0 mmol), diamine DA- 13 (17.39 g, 40.0 mmol) was dissolved in NMP (179.3 g), reacted at 60 ° C. for 5 hours, and then tetracarboxylic dianhydride DC-2 (9.61 g, 49.0 mmol). And NMP (59.8 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
  • NMP (27.0 g) was added to the obtained polyimide powder (J) (3.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 3.0g, NMP (2.0g), and BCS (50.0g) were added to this solution, and the liquid crystal aligning agent (J1) was obtained by stirring at room temperature for 5 hours.
  • NMP (27.0 g) was added to the obtained polyimide powder (K) (3.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 3.0g, NMP (2.0g), and BCS (50.0g) were added to this solution, and the liquid crystal aligning agent (K1) was obtained by stirring at room temperature for 5 hours.
  • NEP (27.0 g) was added to the obtained polyimide powder (L) (3.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • NEP (20.0g) and BCS (50.0g) were added to this solution, and the liquid crystal aligning agent (L1) was obtained by stirring at room temperature for 5 hours.
  • NMP (27.0 g) was added to the obtained polyimide powder (M) (3.0 g) and dissolved by stirring at 70 ° C. for 20 hours.
  • NEP (20.0g) and BCS (50.0g) were added to this solution, and the liquid crystal aligning agent (M1) was obtained by stirring at room temperature for 5 hours.
  • Tetracarboxylic dianhydride DC-3 (5.00 g, 20.0 mmol), diamine DA-9 (6.09 g, 40.0 mmol), diamine DA-10 (7.27 g, 30.0 mmol), diamine DA- 12 (11.42 g, 30.0 mmol) was dissolved in NMP (137.1 g), reacted at 60 ° C. for 5 hours, and then tetracarboxylic dianhydride DC-4 (4.36 g, 20.0 mmol). Then, tetracarboxylic dianhydride DC-2 (11.57 g, 59.0 mmol) and NMP (45.7 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
  • NMP (27.0 g) was added to the obtained polyimide powder (N) (3.0 g) and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 3.0g, NMP (2.0g), and BCS (50.0g) were added to this solution, and the liquid crystal aligning agent (N1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agents J1, K1, L1, M1 and N1 were obtained.
  • Example 10 About liquid crystal aligning agent J2 and N3 obtained by the synthesis example 16 and the synthesis example 20, it stirred at room temperature for 3 hours so that the weight ratio of the resin composition contained in each might be set to 3: 7, and liquid crystal aligning agent (JN1) was prepared.
  • Examples 11 and 12 Comparative Examples 10 to 14> Each liquid crystal aligning agent was mix
  • the liquid crystal aligning agent in Table 5 was evaluated in the same manner as in Example 1. The evaluation results were as shown in Table 6.
  • Example 10 and Comparative Example 10 Example 11 and Comparative Example 12, and Example 12 and Comparative Example 14 are compared, diisobutylketone is introduced, so that the polymer contains a protecting group that is eliminated by heat. It was confirmed that the coatability can be improved even when the film is exposed.

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Abstract

La présente invention a trait : à un agent d'alignement de cristaux liquides qui peut supprimer des défauts de revêtement se produisant dans un film d'alignement en raison des effets d'une structure de câblage ou du rapport C/H, et supprimer un défaut rendant l'affichage d'un dispositif d'affichage à cristaux liquides non uniforme, et qui a une viscosité réduite et une plus grande proportion de constituants de résine ; et à un film d'alignement de cristaux liquides utilisant l'agent d'alignement de cristaux liquides. La présente invention se rapporte à un agent d'alignement de cristaux liquides caractérisé en ce qu'il contient : au moins un polymère choisi dans le groupe constitué par un précurseur de polyimide et du polyimide, qui est un produit imidisé de celui-ci, et contenant un groupe protecteur qui est éliminé par la chaleur ; et un constituant de solvant contenant un solvant issu du groupe A ci-dessous, un solvant issu du groupe B ci-dessous, et de la cétone d'isobutyle. Le solvant issu du groupe A est au moins un solvant choisi dans le groupe constitué par de la N-méthyl-2-pyrrolidone, de la N-éthyl-2-pyrrolidone, de la γ-butyrolactone et de la 1,3-diméthylimidazolidinone, et le solvant issu du groupe B est au moins un solvant choisi dans le groupe constitué par de l'éther monobutylique de l'éthylèneglycol, du 1-butoxypropan-2-ol, du 2-butoxypropan-1-ol, et de l'éther diméthylique de dipropylèneglycol.
PCT/JP2017/035120 2016-09-29 2017-09-28 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides Ceased WO2018062353A1 (fr)

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CN113412449B (zh) * 2019-02-08 2025-02-18 日产化学株式会社 液晶取向剂、液晶取向膜以及使用了该液晶取向膜的液晶显示元件
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KR20220147158A (ko) 2022-11-02
TWI773689B (zh) 2022-08-11
JP7063270B2 (ja) 2022-05-09
CN110023826B (zh) 2022-10-25
CN110023826A (zh) 2019-07-16

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