WO2019103042A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de fabrication d'un film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de fabrication d'un film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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WO2019103042A1
WO2019103042A1 PCT/JP2018/043005 JP2018043005W WO2019103042A1 WO 2019103042 A1 WO2019103042 A1 WO 2019103042A1 JP 2018043005 W JP2018043005 W JP 2018043005W WO 2019103042 A1 WO2019103042 A1 WO 2019103042A1
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liquid crystal
group
pyrrolidone
solvent
aligning agent
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PCT/JP2018/043005
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English (en)
Japanese (ja)
Inventor
亮一 芦澤
一平 福田
直史 長谷川
美希 豊田
司 藤枝
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日産化学株式会社
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Priority to JP2019555337A priority Critical patent/JP7375544B2/ja
Priority to CN201880075387.3A priority patent/CN111386493B/zh
Priority to KR1020207016318A priority patent/KR20200079314A/ko
Publication of WO2019103042A1 publication Critical patent/WO2019103042A1/fr

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    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention is a liquid crystal aligning agent having high dimensional stability when ink jet coating is applied and which is difficult to be dried during flexographic printing, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display device having the liquid crystal aligning film. About.
  • a so-called polyimide-based liquid crystal alignment film is widely used which is obtained by applying and baking a liquid crystal alignment agent containing a polyimide precursor such as polyamic acid (polyamic acid) or a soluble polyimide solution as a main component It is done.
  • a film forming method of such a liquid crystal alignment film spin coating, dip coating, flexographic printing and the like are generally known. In flexographic printing, although it is possible to easily form an alignment film pattern and have high productivity, in order to form a uniform thin film, it is necessary to apply a liquid crystal alignment agent to the surface of the anilox roll and the doctor roll.
  • Patent Document 1 In order to prevent the drying of the alignment film material on the surface of the liquid crystal, it is necessary to supply a liquid crystal alignment agent at regular intervals (Patent Document 1). In addition, there is a problem that it is difficult to form an alignment film on a substrate having large unevenness or a substrate having a curved surface.
  • an inkjet method is proposed as a coating method of another liquid crystal aligning agent instead of the above.
  • the inkjet method is a method in which fine droplets are dropped on a substrate and a film is formed by wetting and spreading of a liquid. Since the printing pattern can be set freely, there is an advantage that it is possible to form an alignment film on a substrate with large unevenness and a substrate with a curved surface.
  • the film thickness unevenness in the coating surface is small and the film forming accuracy in the peripheral portion of the coating is high.
  • the uniformity of the film thickness in the coated surface and the film forming accuracy in the peripheral portion of the coating have a trade-off relationship.
  • a material having high in-plane uniformity has poor dimensional stability at the coating peripheral portion, and the film protrudes from the set dimension.
  • the in-plane uniformity of the coating becomes worse.
  • Patent Document 2 Patent Document 3
  • Patent Document 4 Patent Document 4
  • TFTs with multilayer wiring are becoming mainstream as liquid crystal display elements are becoming higher definition.
  • a contact hole hereinafter also referred to as C / H
  • the film thickness of the alignment film may be uneven around the C / H and other parts, such as dot-like unevenness and streak-like unevenness, and the display of the liquid crystal display may be uneven.
  • liquid crystal alignment film As the production line of the liquid crystal alignment film is enlarged, there is a problem that when the liquid crystal alignment agent is applied by flexographic printing, drying of the liquid crystal alignment agent on the surface of the anilox roll and the doctor roll is likely to occur. Furthermore, the requirement for quality improvement of a display element is more severe, and in particular, a liquid crystal alignment film having more properties than ever in liquid crystal alignment is required.
  • the present invention can suppress the coating failure of the alignment film generated due to the influence of the wiring structure or C / H, and can suppress the failure of the liquid crystal display element becoming nonuniform. It is to provide a liquid crystal alignment film and a liquid crystal display device using the same. Another object of the present invention is to provide a liquid crystal aligning agent capable of suppressing the drying of the liquid crystal aligning agent generated when flexographic printing is performed, a liquid crystal aligning film using the same, and a method of manufacturing the liquid crystal aligning film. Another object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having high liquid crystal alignment.
  • the present inventors simultaneously improve various properties by combining a polymer having a specific structure and a solvent containing a specific solvent.
  • the present invention has been completed.
  • the present invention is based on such findings and has the following gist.
  • a liquid crystal aligning agent comprising: a solvent containing at least one solvent B selected from the group consisting of diacetates, alkylene glycol monoalkyl ethers, and alkylene glycol dialkyl ethers.
  • X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -COO-,-(CH 2 ) m- , and -SO 2- And m represents an integer of 1 to 8; and a divalent organic group selected from the group consisting of Two Y's each independently represent a side chain structure selected from the group consisting of the following formulas [S1] to [S3] and a structure derived from tocopherol.
  • X 1 and X 2 are 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- (a1 each independently represents an integer of 1 to 15, and A 1 represents an oxygen atom -COO or OCO, m 1 is 1 to 2).
  • G 1 and G 2 each independently represent a divalent cyclic group selected from the group consisting of a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms, Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or It may be substituted by a fluorine atom, and m and n are independently an integer of 0 to 3, and the sum thereof is 1 to 4.
  • R 1 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxyalkyl having 2 to 20 carbons, and any hydrogen in these groups may be replaced by fluorine.
  • X 3 represents a single bond, -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or OCO-, and R 2 represents carbon
  • the alkyl is an alkyl of 1 to 20 or an alkoxyalkyl of 2 to 20 carbons, and any hydrogen in these groups may be replaced by fluorine.
  • X 4 represents —CONH—, —NHCO—, —O—, —COO— or OCO—, and R 3 represents a structure having a steroid skeleton.
  • R 1a represents a monovalent hydrocarbon group having 2 to 8 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group.
  • R 2a and R 2b independently represent an alkyl group having 1 to 6 carbon atoms.
  • R 3a represents a methyl group or an ethyl group.
  • R 5a represents an alkyl group having 1 to 6 carbon atoms.
  • R 5b and R 5c independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds of the hydrocarbon group. Show. n is 1 or 2;
  • r 1a and r 1b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 2 to 6.
  • the coating failure of the alignment film caused by the influence of the wiring structure and C / H can be suppressed, the failure that the display of the liquid crystal display element becomes uneven can be suppressed, and the flexo printing is performed. Drying of the liquid crystal aligning agent is also suppressed at the same time. A liquid crystal alignment film having higher liquid crystal alignment can be obtained.
  • the liquid crystal aligning agent of the present invention comprises at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor having the structure of the above formula [1] and a polyimide which is an imidized product thereof. contains.
  • the specific polymer preferably has the structure of the formula [1] in the main chain of the polymer from the viewpoint of easiness of synthesis.
  • the main chain of the polymer refers to a portion consisting of a chain of the longest atoms in the polymer.
  • the presence of the structure of the above-mentioned formula [1] in a portion other than the main chain is not excluded.
  • X in the formula [1] in 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 a combination thereof, and m represents an integer of 1 to 8.
  • Y in the formula [1] has a side chain structure selected from the following formulas [S1] to [S3] or a structure having a tocopherol skeleton.
  • X 1 and X 2 are as defined above.
  • a single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -O- or -CH 2 O- Or COO- is preferred. More preferably, it is a single bond,-(CH 2 ) a- (a is an integer of 1 to 10), -O-, -CH 2 O- or COO-.
  • G 1 and G 2 are as defined above.
  • Examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene and naphthalene. Further, examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.
  • R 1 is an alkyl group having 1 to 20 carbon atoms
  • X p is — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON ( CH 3 ) —, —NH—, —O—, —CH 2 O—, —CH 2 OCO—, —COO—, or —OCO—.
  • a 1 is an oxygen atom or -COO- * (wherein the bond attached with "*" is bonded to (CH 2 ) a 2 ),
  • a 2 is an oxygen atom or * -COO- ("*" The bond is (CH 2 ) a2 ).
  • a 1 and a 3 are independently an integer of 0 or 1
  • a 2 is an integer of 1 to 10
  • Cy is a 1,4-cyclohexylene group or a 1,4-phenylene group.
  • X 3 is a group as defined above. Among them, -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or OCO- is preferable from the viewpoint of liquid crystal alignment.
  • R 2 is as defined above. Among them, alkyl having 3 to 20 carbons or alkoxyalkyl having 2 to 20 carbons is preferable from the viewpoint of liquid crystal alignment.
  • X 4 is a group as defined above.
  • -O-, -COO- or -OCO- is preferable from the viewpoint of liquid crystal alignment.
  • a structure having a steroid skeleton a structure in which a hydroxy group is removed from a compound such as ⁇ -sitosterol or ergosterol, a structure in which a hydroxy group is removed from a steroid compound described in [0024] of JP-A-4-281427, [0030] ]
  • the structures described in [0018] to [0022] of -146421 can be mentioned.
  • Examples of the structure having a tocopherol skeleton in the formula [1] include structures derived from compounds such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and ⁇ -tocopherol.
  • the structure shown by following formula [T] can be mentioned, for example.
  • "*" shows a coupling
  • the specific polymer contained in the liquid crystal aligning agent of the present invention is a group consisting of a polyimide precursor having a divalent group represented by the above formula [1] and a polyimide which is an imidized product of the polyimide precursor. As long as it is at least 1 or more types of polymers chosen from, it may be synthesize
  • the specific polymer is a tetracarboxylic acid having the structure of the formula [1] or a derivative thereof (hereinafter, also referred to as a specific tetracarboxylic acid compound), or a tetracarboxylic acid containing the specific tetracarboxylic acid compound
  • a polyimide precursor obtained by reacting a component and a diamine component; a polyimide of the polyimide precursor; a tetracarboxylic acid component, and a diamine having a structure of the formula [1] hereinafter referred to as "specific diamine"
  • a polyimide precursor obtained by reacting a diamine component containing a specific diamine and one or more selected from the group consisting of the polyimide of the polyimide precursor.
  • the tetracarboxylic acid component used to synthesize the specific polymer contains either or both of the specific tetracarboxylic acid compound or the other tetracarboxylic acid compound.
  • the specific tetracarboxylic acid compound is a tetracarboxylic acid compound having a structure of the above formula [1], and examples thereof include a compound represented by the formula [T] or a derivative thereof.
  • A represents a trivalent group, and two A may be the same or different.
  • Examples of A include a trivalent organic group having at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, a benzene ring structure and the following formula (A-1).
  • P represents a divalent organic group having the structure of the above formula [1].
  • Examples of the derivative of the tetracarboxylic acid compound include tetracarboxylic acid dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide.
  • tetracarboxylic acid compounds include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3, 3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenone Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,1 3,3,3-Hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxy
  • tetracarboxylic dianhydride having a structure represented by the formula [4] and its tetracarboxylic acid derivative are preferable.
  • Z represents a structure selected from the group consisting of the following [4a] to [4k].
  • Z 1 to Z 4 independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.
  • Preferred specific examples of Z 1 to Z 4 include the following formulas [4a-1] and [4a-2]. (* 1 and * 2 are as defined above.)
  • Z 5 and Z 6 are independently a hydrogen atom or a methyl group.
  • formula [4a], formula [4c] to formula [4 g] or formula [4] 4k] is preferred.
  • Formula [4a] or Formula [4e] to Formula [4g] are more preferable, and [4a], Formula [4e] or Formula [4f] is particularly preferable.
  • Preferred examples thereof include tetracarboxylic acid dianhydrides of structures shown by [4a-1], formulas [4a-2], formulas [4e] and formulas [4f] or their tetracarboxylic acid derivatives.
  • the tetracarboxylic acid compound represented by the formula [4] in the polymer of the present invention is preferably 1 mol% or more in 100 mol% of all tetracarboxylic acid compounds from the viewpoint of enhancing the solubility of the polymer. Among them, 5 mol% or more is preferable, and 10 mol% or more is more preferable.
  • the tetracarboxylic acid compound is selected depending on the solubility of the polymer of the present invention in the solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal alignment property in the liquid crystal aligning film, the voltage holding ratio, and the accumulated charge. One kind or two or more kinds can be mixed and used.
  • the diamine component used to synthesize a specific polymer contains a specific diamine.
  • a specific diamine is a diamine which has a structure of said Formula [1], for example, the compound represented by following formula [2] is mentioned.
  • the specific diamine used for the liquid crystal aligning agent of this invention is represented by following formula [2].
  • Each of X and Y in the formula [2] has the same meaning as in the above-mentioned formula [1].
  • X is preferably a single bond, -O-, -NH- or -O- (CH 2 ) m -O- from the viewpoint of easy synthesis of the specific diamine.
  • m is an integer of 1 to 8;
  • Y may be a meta position or an ortho position from the position of X, but is preferably an ortho position from the viewpoint of high reactivity of a specific diamine.
  • Formula [2] is the following Formula [2 '].
  • the above formula [2] is preferably a structure of any of the following formulas from the viewpoint of high reactivity of the specific diamine, and a structure represented by the formula [2] -a1-1 is more preferred.
  • the preferable form of Y in said Formula [1] can be applied.
  • a structure selected from the formulas [S1-x3] to [S1-x4], [S1-x6] and the formula [S3-x] is preferable, and the following formula is preferred as a preferred example
  • the structures of [W-1] to [W-6] can be mentioned.
  • X p1 to X p8 are independently-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-, -NH -, -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
  • X s1 to X s4 independently represent -O-, -COO- or -OCO-.
  • X a to X f independently represent a single bond, -O-, -NH-, or -O- (CH 2 ) m -O-.
  • R 1a to R 1h independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
  • m is an integer of 1 to 8;
  • Specific diamines are 1 according to the ink jet coatability of the liquid crystal alignment agent, the liquid crystal alignment when used as a liquid crystal alignment film, voltage holding characteristics, characteristics such as accumulated charge, and the response speed of liquid crystal when used as a liquid crystal display element.
  • the species or two or more species can be mixed and used.
  • the specific diamine is preferably used in an amount of 1 to 100% by mole, more preferably 2 to 100% by mole, and particularly preferably 5 to 90% by mole, of the diamine component used for the synthesis of the specific polymer.
  • a diamine for synthesizing a polyamic acid or a polyamic acid ester only a specific diamine may be used, or other diamine may be used in combination with the specific diamine.
  • the other diamine for example, a diamine having a pretilt angle developing property other than the above (2), a diamine having a function of generating polymerization or radical upon irradiation with light, WO [WO 46/2015] [0169 ], Diamine having a carboxyl group or a hydroxyl group as described in [0171] to [0172], diamine having a nitrogen-containing heterocycle as described in [0173] to [0188], JP-A-2016-218149 Diamine having the nitrogen-containing structure described in [0050], 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) And organosiloxane-containing diamines such as -1,1,1,
  • a diamine having a function of generating polymerization or generating a radical by light irradiation is preferable from the viewpoint of enhancing the response speed.
  • Preferred specific examples of other diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-difluoro-4 4,4'-Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, 4,4'- Diaminobenzophenone, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4 -Aminophenyl) butane, 1,4-bis (4-aminophenoxy)
  • Examples of the diamine having a pretilt angle developing property other than the above formula (2) include diamines represented by the structural formulas of the following formulas [V-1] to [V-7].
  • X v1 to X v4 are independently-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-,- NH -, - O -, - CH 2 O -, - CH 2 OCO -, - COO-, or -OCO- shows a.
  • X v5 represents -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
  • X V6 to X V7 independently represent -O-, -COO- or -OCO-.
  • diamine having a function of polymerizing by light irradiation examples include diamines in which the structures represented by the following formulas [p1] to [p7] are directly or linked to an aromatic ring such as a benzene ring via a linking group.
  • R 8 is a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N (CH 3 ) -, - CON (CH 3 ) -, or -N (CH 3) shows a CO-.
  • a single bond, -O-, -COO-, -NHCO-, or -CONH- is preferable from the easiness of synthesis.
  • R 9 represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, a divalent group selected from an aromatic ring having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and cyclohexane Ring or other divalent alicyclic group having 3 to 8 carbon atoms, such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, purine, tetrahydrofuran, thiophene, etc.
  • k is an integer of 0 to 4;
  • R 10 represents a structure selected from the group consisting of the above formulas [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2] and [p4] are preferable.
  • Y 1 and Y 3 independently represent -CH 2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO -Indicates.
  • Y 2 and Y 5 are independently synonymous with R 9 in the above [Pa].
  • Y 4 represents a cinnamoyl group.
  • Y 6 represents a structure selected from the group consisting of the above formulas [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2], or [p4] is preferable.
  • m is 0 or 1;
  • the diamine having a function of polymerizing by light irradiation is determined according to the liquid crystal alignment property when formed into a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, and the response speed of the liquid crystal when formed into a liquid crystal display element. , 1 type, or 2 or more types can be mixed and used. It is preferable to use 10 to 70% by mole, more preferably 10 to 60% by mole, and particularly preferably 10 to 50% by mole of the diamine component used for the synthesis of the specific polymer, as the diamine having a function of polymerizing by light irradiation. is there.
  • diamines having a function of generating radicals by light irradiation include diamines having a moiety having a radical generating structure which is decomposed by ultraviolet irradiation to generate radicals in the side chain, for example, diamines represented by the following formula (R) It can be mentioned.
  • Ar, R 1 , R 2 , T 1 , T 2 , S and Q in the above formula (R) have the following definitions. That is, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, to which an organic group may be substituted, and a hydrogen atom may be substituted by a halogen atom.
  • R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group.
  • T 1 are independently a single bond or -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH -, - CH 2 O -, - N (CH 3) - And -CON (CH 3 )-or -N (CH 3 ) CO-.
  • S is the same as R 9 in the above [Pa].
  • Q is a structure selected from the group consisting of the following formulas [q-1] to [q-4] (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 3 represents -CH 2- , -NR -, -O-, or -S- is shown. (In the formula, * indicates a bonding position.)
  • Ar having carbonyl bonded thereto is preferably a structure having a long conjugation length such as naphthylene or biphenylene from the viewpoint of efficiently absorbing the ultraviolet light.
  • Ar may have a substituent, and such a substituent is preferably an electron donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group or an amino group. If the wavelength of ultraviolet light is in the range of 250 to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so a phenyl group is most preferable.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group, and in the case of an alkyl group or an alkoxy group, a ring is formed by R 1 or R 2 You may form.
  • Q is more preferably a hydroxyl group or an alkoxyl group.
  • the diaminobenzene in the formula (R) may be any of o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, but m-phenylenediamine or p in view of high reactivity with the tetracarboxylic acid component. Phenylenediamine is preferred.
  • n is an integer of 2 to 8.
  • the diamine component used for the synthesis of the specific polymer it is preferable to use 5 to 70 mol% of the diamine component used for the synthesis of the specific polymer, and more preferably 10 to 60 mol% from the viewpoint of maintaining liquid crystal alignment, as the diamine having the function of generating radicals upon light irradiation. And particularly preferably 10 to 50 mol%.
  • the specific polymer is obtained by reacting a diamine and a tetracarboxylic acid compound as described above.
  • a method of obtaining a polyamic acid a method of polycondensation of tetracarboxylic acid dianhydride and diamine to obtain a polyamic acid or a method of polycondensation of a tetracarboxylic acid dihalide compound and a diamine compound to obtain a polyamic acid can be mentioned. .
  • the specific polymer can be obtained by reacting with a molecular weight modifier as needed.
  • the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamines such as aniline, cyclohexylamine and n-butylamine, and monoisocyanates such as phenyl isocyanate and naphthyl isocyanate. be able to.
  • the use ratio of the molecular weight modifier is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic acid compound and diamine used.
  • a method of polycondensing a diamine with a tetracarboxylic acid dialkyl ester compound in which a carboxylic acid group is dialkylesterified a method of polycondensing a diamine with a tetracarboxylic acid dialkyl ester compound in which a carboxylic acid group is dialkylesterified, a tetracarboxylic acid dialkyl ester dihalide in which a carboxylic acid group is dialkylesterified and dihalified.
  • Examples thereof include a method of polycondensation of a compound and a primary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester.
  • the method of making said polyimide precursor ring-closing and making it a polyimide is mentioned.
  • the reaction of the diamine with the tetracarboxylic acid compound is preferably carried out in a solvent.
  • the solvent is not particularly limited as long as it can dissolve the produced polymer. Specific examples of the solvent are listed below, but are not limited to these examples.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-2-imidazolidinone
  • solvent solubility of the polymer is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D-1] to [D-3] Solvents can be used.
  • D 1 represents an alkylene group having 1 to 3 carbon atoms
  • D 2 represents an alkylene group having 1 to 3 carbon atoms
  • D 3 represents an alkylene group having 1 to 4 carbon atoms
  • solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polymer, it may be mixed and used for the said solvent in the range which the produced
  • the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer of high molecular weight, and the concentration is too high And the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction may be performed at high concentration, and then solvent may be added.
  • the ratio of the total number of moles of diamine to the total number of moles of the tetracarboxylic acid compound is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the specific polymer to be produced increases as the molar ratio approaches 1.0.
  • the polyimide is a polyimide obtained by ring-closing the polyimide precursor, and in this polyimide, the ring-closing rate (also referred to as imidation rate) of the amic acid group does not necessarily have to be 100%, depending on the application and purpose. It can be adjusted arbitrarily.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which the catalyst is added to the solution of the polyimide precursor.
  • the temperature for thermally imidizing the polyimide precursor in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.
  • Catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 ° C to 250 ° C, preferably 0 to 180 ° C. .
  • the amount of basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of acid anhydride is 1 to 50 moles, preferably 3 to 30 moles of the amic acid group. It is a double.
  • the basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
  • acetic anhydride trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is particularly preferable to use acetic anhydride because purification after completion of the reaction becomes easy.
  • the imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.
  • the reaction solution may be introduced into a solvent and precipitated.
  • a solvent used for precipitation methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like can be mentioned.
  • the polymer precipitated by charging in a solvent may be recovered by filtration and then dried at normal temperature or under heating under normal pressure or reduced pressure.
  • the precipitated and recovered polymer is redissolved in a solvent and the operation for reprecipitating and recovering is repeated twice to 10 times, impurities in the polymer can be reduced.
  • the solvent for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more solvents selected from these, since the efficiency of purification is further improved.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimide is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. It is.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
  • the liquid crystal aligning agent of the present invention is constituted by dissolving, in a solvent, at least one polymer selected from the group consisting of a polyimide precursor as described above and a polyimide and optionally added components used as needed.
  • the solvent used for the liquid crystal aligning agent of the present invention is, as described above, at least one solvent A selected from the group consisting of the above formulas (d-1) to (d-5), the above formula (e), a boiling point
  • at least one solvent B selected from the group consisting of alkylene glycol monoalkyl ether acetate, alkylene glycol diacetate, alkylene glycol monoalkyl ether, and alkylene glycol dialkyl ether.
  • the boiling point means the boiling point at 1 atm.
  • the solvent A By containing the solvent A, the drying of the liquid crystal aligning agent is suppressed, so that the concentration change at the time of applying the liquid crystal aligning agent is suppressed, and a liquid crystal aligning agent having excellent coatability can be obtained.
  • the solubility of the polymer in the solvent is also high, and it is possible to suppress the phenomenon that the precipitation of the polymer occurs at the time of firing and the film thickness becomes uneven.
  • the solvent B the difference in boiling point from the solvent A becomes small, and the liquid crystal aligning agent can be spread by wetting when baking the coated substrate of the liquid crystal aligning agent, and therefore, for a substrate having a complicated step structure. Even in the case, it becomes possible to apply uniformly, and it is possible to obtain a liquid crystal alignment film excellent in uniformity of film thickness.
  • examples of the monovalent hydrocarbon group having 2 to 8 carbon atoms as R 1a include a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include a chain having 2 to 8 carbon atoms. Examples thereof include an alkyl group and a cycloalkyl group having 3 to 8 carbon atoms. Further, examples of the monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group include, for example, an alkoxyalkyl group having 2 to 8 carbon atoms.
  • cycloalkyl group having 3 to 8 carbon atoms examples include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
  • alkoxyalkyl group having 2 to 8 carbon atoms examples include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group and an ethoxyethyl group. These groups may be linear or branched.
  • examples of the alkyl group having 1 to 6 carbon atoms as R 2a , R 2b , R 5a , r 1a and r 1b include methyl and ethyl And a propyl group, a butyl group, a pentyl group, a hexyl group and the like, which may be linear or branched.
  • R 3a represents a methyl group or an ethyl group.
  • examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R 5b and R 5c include a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include 1 to 6 carbon atoms And a linear alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, and the like.
  • the monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group includes, for example, an alkoxyalkyl group having 1 to 6 carbon atoms.
  • linear alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like can be mentioned; And cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • formula (d-1) include N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2- Pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (n-hexyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- (n And -octyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone and the like.
  • formula (d-2) examples include 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-diethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone And 1,3-diisopropyl-2-imidazolidinone.
  • DMI 1,3-dimethyl-2-imidazolidinone
  • DMI is preferred from the viewpoint of the solubility of the specific polymer.
  • formula (d-5) examples include 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, iso Propoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like.
  • 3-butoxy-N, N-dimethylpropanamide and 3-methoxy-N, N-dimethylpropanamide are preferable from the viewpoint of the solubility of the specific polymer and the like.
  • the content ratio of the solvent A in the solvent is preferably 5 to 99% by mass, and more preferably 10 to 99% by mass, with respect to the entire solvent contained in the liquid crystal aligning agent.
  • Specific examples of the formula (e) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate, 2-methyl-1,3-propylene carbonate, and 2,2-dimethyl-1,3-propylene carbonate Etc.
  • propylene carbonate, ethylene carbonate and butylene carbonate are preferable from the viewpoint of the solubility of the specific polymer and the like.
  • Specific examples of the alkylene glycol monoalkyl ether acetate having a boiling point of 200 to 300 ° C. include diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate and the like.
  • alkylene glycol diacetate having a boiling point of 200 to 300 ° C. examples include 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2-propylene glycol dibutyrate and the like.
  • ethylene glycol monohexyl ether examples include ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, propylene glycol phenyl ether, diethylene glycol monoethyl ether, diethylene glycol Monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monopropyl ether, tripropylene glycol methyl ether, tripropylene glycol-n-butyl ether and the like can be mentioned.
  • alkylene glycol dialkyl ether having a boiling point of 200 to 300 ° C. examples include diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and the like.
  • solvents B from the viewpoint of solubility of a specific polymer, propylene carbonate, ethylene carbonate and butylene carbonate, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol At least one selected from the group consisting of monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monopropyl ether and tripropylene glycol methyl ether is preferred.
  • the solvent contained in the liquid crystal aligning agent of the present invention preferably contains one combination selected from the following MS1 to MS14 from the viewpoint of achieving both the solubility of the specific polymer and the wettability of the liquid crystal aligning agent;
  • MS1 N-ethyl-2-pyrrolidone and propylene carbonate
  • MS2 N-cyclohexyl-2-pyrrolidone and propylene carbonate
  • MS3 N- (n-hexyl) -2-pyrrolidone and propylene carbonate
  • MS4 ⁇ -valerolactone And propylene carbonate
  • MS5 N-ethyl-2-pyrrolidone and diethylene glycol monoethyl ether acetate
  • MS6 N-ethyl-2-pyrrolidone and diethylene glycol monobutyl ether acetate
  • MS 7 N-ethyl-2-pyrrolidone and dipropylene glycol monomethyl ether acetate
  • MS 8 N-ethyl 2-pyrrolidone and ethylene glycol monohexyl ether
  • MS 9 N-ethyl-2-pyrrolidone and diethylene glycol monoethyl ether
  • MS 10 N-ethyl-2-pyrrolidone and diethylene glycol monopropyl ether
  • MS11 N-ethyl 2-pyrrolidone and diethylene glycol monobutyl ether
  • MS12 N-ethyl 2-pyrrolidone and diethylene glycol monohexyl ether
  • MS13 N-ethyl-2 -Pyrrolidone and dipropylene glycol monopropyl ether ⁇
  • MS 14 N-ethyl-2-pyrrolidone and tripropylene glycol methyl ether
  • the content ratio of the solvent B in the solvent is preferably 1 to 95% by mass, and more preferably 1 to 90% by mass, with respect to the entire solvent contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention preferably further contains N-methyl-2-pyrrolidone as a solvent from the viewpoint of enhancing the solubility of the specific polymer and securing the printability.
  • the content ratio is preferably 10 to 90% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 90% by mass with respect to the total amount of the solvent.
  • the liquid crystal aligning agent of the present invention may be used in combination with other solvents as the solvent.
  • other solvents for example, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, methyl methoxypropionate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol-n -Propyl ether, ethylene glycol-i-propyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, low as described in [0203] of WO2011 / 132751 Mention may be made of solvents having a surface tension.
  • the solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is selected in consideration of viscosity, volatility, etc.
  • the range of the solid content concentration which is particularly preferable depends on the method used when applying the liquid crystal aligning agent to the substrate.
  • 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.
  • the crosslinkable compound preferably has two or more of these substituents and polymerizable unsaturated bonds.
  • crosslinkable compound which has an epoxy group or an isocyanate group the compound as described in [0087] of WO2015 / 008846 etc. are mentioned, for example.
  • Specific examples of the crosslinkable compound having a cyclocarbonate group include the crosslinkable compounds represented by Formula [5-1] to Formula [5-42] described on pages 76 to 82 of WO2012 / 014898. Be
  • crosslinkable compound having at least one type of substituent selected from the group consisting of a hydroxyl group and an alkoxyl group compounds described in [0090] to [0092] of WO 2015/008846, described in [0054] of WO 2015/072554 And compounds described in WO 2014/156314 [0126], and the like. More preferable specific examples are the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed in [181] to [185] of WO2011 / 132751, and described in [0054] of WO2015 / 072554 And compounds described in WO 2014/156314 [0126].
  • crosslinkable compound which has a polymerizable unsaturated bond the compound as described in [0186] of WO2011 / 132751 is mentioned, for example.
  • the compound represented by the formula [5] described in [0188] of WO2011 / 132751 can also be used.
  • the above compounds are examples of crosslinkable compounds and are not limited thereto.
  • the crosslinkable compound used for the liquid crystal aligning agent of the present invention may be one type or a combination of two 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 the polymer components.
  • 0.1 to 100 parts by mass is preferable with respect to 100 parts by mass of all the polymer components. More preferably, it is 1 to 50 parts by mass.
  • the liquid crystal aligning agent of this invention can use the compound which improves the uniformity of film thickness of a liquid crystal aligning film at the time of apply
  • a fluorine-type surfactant As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonion type surfactant etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (above, made by Tochem Products), Megafuck F171, F173, R-30 (above, made by Dainippon Ink Co., Ltd.), Florards FC430, FC431 (above, Sumitomo 3M Ltd.), Asahi Guard AG 710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.
  • the proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal
  • liquid crystal aligning agent of the present invention as a compound that promotes charge transfer in the liquid crystal alignment film to promote charge loss of the device, pages 69 to 73 of WO2011 / 132751 (released on Oct. 17, 2011). It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] listed below.
  • the amine compound may be added directly to the liquid crystal aligning agent, but is preferably added after being made into a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, using a suitable solvent.
  • the solvent is not particularly limited as long as it dissolves the specific polymer described above.
  • the liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvents, crosslinkable compounds, compounds for improving film thickness uniformity and surface smoothness of a resin film or liquid crystal alignment film, and compounds for promoting charge loss,
  • a dielectric or a conductive substance may be added for the purpose of changing the electrical properties such as the dielectric constant and the conductivity of the alignment film.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation and the like. Moreover, in the case of the vertical alignment application etc., it can be used as a liquid crystal aligning film, without an orientation process.
  • the substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed.
  • an opaque substrate such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used as an electrode.
  • the liquid crystal aligning agent may be applied by screen printing, offset printing, flexographic printing or ink jet method, dip method, roll coater method, slit coater method, spinner method or spray method, etc. From the viewpoint of increasing the viscosity, a method of coating by flexographic printing or an inkjet method is preferred.
  • the solvent can be evaporated at a temperature of -250 ° C. to form a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be lowered. Is 10 to 100 nm.
  • the coating film formed as described above can be used as it is as a liquid crystal alignment film, but rubbing treatment or PSA described later may be used as needed. You may process.
  • the display mode of the liquid crystal display element manufactured is a vertical electric field method other than the VA type or a lateral electric field method
  • the formed coating film surface is subjected to rubbing treatment or polarized ultraviolet irradiation and the like. Processing is performed for orientation processing.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and includes a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy ray and heat between the pair of substrates. It is preferably used also for a liquid crystal display device manufactured through a step of arranging a substance, polymerizing a polymerizable compound by at least one of irradiation of active energy rays and heating while applying a voltage between electrodes.
  • the applied voltage can be, for example, direct current or alternating current of 5 to 50 V.
  • an active energy ray an ultraviolet-ray is suitable.
  • the ultraviolet light is ultraviolet light including light of a wavelength of 300 to 400 nm, preferably ultraviolet light including light of a wavelength of 310 to 360 nm.
  • the irradiation dose of light is preferably 0.1 to 20 J / cm 2 , more preferably 1 to 20 J / cm 2 .
  • the liquid crystal display element described above controls the pretilt of liquid crystal molecules by the PSA method.
  • a small amount of a photopolymerizable compound for example, a photopolymerizable monomer
  • ultraviolet light is applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer.
  • the pretilt of liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after removing the voltage, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer.
  • the PSA method does not require rubbing treatment, it is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by rubbing treatment.
  • the liquid crystal display element of the present invention is a liquid crystal display element produced by a known method after producing a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above.
  • a liquid crystal cell is prepared by preparing a pair of substrates on which a liquid crystal alignment film is formed, dispersing spacers on the liquid crystal alignment film on one of the substrates so that the liquid crystal alignment film surface is on the inside, For example, there is a method in which a substrate of the above is attached and sealed by injecting a liquid crystal under reduced pressure, or a method in which a substrate is attached and sealed after liquid crystal is dropped on the liquid crystal alignment film surface to which spacers are dispersed.
  • the liquid crystal may be mixed with a polymerizable compound which is polymerized by ultraviolet irradiation or heat as described above.
  • a polymerizable compound which is polymerized by ultraviolet irradiation or heat as described above.
  • the polymerizable compound compounds having one or more polymerizable unsaturated groups such as acrylate group and methacrylate group in the molecule, for example, polymerizable compounds represented by the following formulas (M-1) to (M-3) It can be mentioned.
  • the amount of the polymerizable compound used is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the amount of the polymerizable compound is less than 0.01 parts by mass, the alignment control of the liquid crystal can not be performed without polymerization of the polymerizable compound, and when the amount is more than 10 parts by mass, the amount of unreacted polymerizable compounds increases The burn-in characteristics of the After producing the liquid crystal cell, while applying an alternating current or direct current voltage to the liquid crystal cell, heat or ultraviolet light is irradiated to polymerize the polymerizable compound. Thereby, the alignment of liquid crystal molecules can be controlled.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group which polymerizes between the pair of substrates by at least one of active energy ray and heat.
  • a liquid crystal alignment film including the above may be disposed, and a liquid crystal display element manufactured through a process of applying a voltage between the electrodes, that is, the SC-PVA mode may also be used.
  • ultraviolet rays are preferable as the active energy ray.
  • the ultraviolet light the ultraviolet light used in the above-mentioned PSA method can be applied including the preferred embodiment.
  • the heating temperature is 40 to 120 ° C., preferably 60 to 80 ° C. Also, ultraviolet light and heating may be performed simultaneously.
  • a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, a polymer containing a polymerizable group The method of using an ingredient is mentioned.
  • the polymer containing a polymerizable group include polymers obtained by using a diamine having a function of polymerizing by the light irradiation.
  • W-A1 compound represented by the formula [W-A1]
  • W-A2 compound represented by the formula [W-A2]
  • W-A3 compound represented by the formula [W-A3]
  • A1 a compound represented by the formula [A1]
  • NEP N-ethyl-2-pyrrolidone
  • GVL ⁇ -valerolactone
  • GBL ⁇ -butyrolactone
  • NMP N-methyl-2-pyrrolidone
  • CHP N-cyclohexyl-2-pyrrolidone
  • NHP N- (n-hexyl) -2-pyrrolidone
  • 3BMP 3-butoxy-N, N-dimethylpropanamide
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEMBA diethylene glycol monobutyl ether
  • Acetate DPMEA Dipropylene glycol monomethyl ether acetate
  • EMH Ethylene glycol monohexyl ether
  • DEME diethylene glycol monoethyl ether
  • DEMP diethylene glycol monopropyl ether
  • DEMB diethylene glycol monobutyl ether
  • DEMH diethylene glycol monohexyl ether
  • DPMP dipropylene glycol monopropyl ether
  • TPME tripropylene glycol methyl ether
  • the molecular weight of the polyimide precursor and the polyimide is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.) It measured like.
  • GPC room temperature gel permeation chromatography
  • the imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm It calculated
  • Imidation ratio (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from the NH group of the amic acid
  • y is a peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%)
  • Viscosity measurement The viscosity of the polyimide polymer was measured at a sample volume of 1.1 mL, cone rotor TE-1 (1 ° 34 ', R24) at a temperature of 25 ° C. using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) did.
  • W-A1 to W-A3 are novel compounds which have not been published in literatures and so forth, and were synthesized as follows.
  • the products described in the following Synthesis Examples 1 to 3 were identified by 1 H-NMR analysis under the following conditions.
  • GVL was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, then acetic anhydride (4.32 g) and pyridine (1.34 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. It was allowed to react for 3 hours. The reaction solution was poured into methanol (382 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (PI-3). The imidation ratio of this polyimide was 74.7%, Mn was 13,340, and Mw was 41,948.
  • a polyimide powder (PI-R2) was obtained in the same manner as in the polymer comparative synthesis example 1 except that the type and composition of the diamine used were changed as described in Table 1 below.
  • the imidation ratio of this polyimide was 65%, Mn was 10,500, and Mw was 20,900.
  • S-1 mass liquid crystal aligning agent
  • a substrate to which a liquid crystal aligning agent is applied As a substrate to which a liquid crystal aligning agent is applied, a substrate just after ultraviolet cleaning of a stepped substrate (made of glass) having a height of 0.5 ⁇ m, a line width of 50 ⁇ m, and an inter-line space of 120 ⁇ m was used.
  • the liquid crystal aligning agent (after filtration) prepared above was applied onto the above glass substrate using HIS-200 (manufactured by Hitachi Plant Technologies, Ltd.).
  • the coating conditions at this time were a coating area of 70 mm ⁇ 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40 mm / sec.
  • the film After standing for 60 seconds after application, the film was heated at 70 ° C. to form a coating having an average film thickness of 100 nm. With respect to the obtained coating film, evaluation of the coating film property and evaluation of the linearity of the liquid crystal alignment film end were performed.
  • the coating property is evaluated by observing with naked eye under irradiation of interference fringe measurement lamp (sodium lamp), and it is excellent when both unevenness and reed is not seen, and at least one of unevenness and reed is seen. The case where both good, unevenness and reed were seen was evaluated as a defect.
  • the evaluation of the linearity of the end of the liquid crystal alignment film was performed by observing the coating on the right end with respect to the printing direction with an optical microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation). Specifically, the magnification was observed with an optical microscope at a magnification of 25 and evaluated according to the following evaluation criteria. Excellent: homogeneous line shape was obtained on all four sides. Good: Line width disturbance was observed on one to three sides. Poor: Line width disturbance was generally observed.
  • the liquid crystal aligning agent prepared above was subjected to a coatability test by performing flexographic printing on a cleaned Cr plate using an alignment film printer ("Ong Stromer” manufactured by Nipponsha Printing Co., Ltd.). About 1.0 mL of the liquid crystal aligning agent was dropped onto the anilox roll, and after performing idle operation 20 times, the printing press was stopped for 10 minutes under the atmosphere to dry the printing plate. Thereafter, printing was performed on one Cr substrate, and the substrate after printing was heated to 70 ° C. to observe the film state. The observation was performed by visual observation and an optical microscope (“ECLIPSE ME600” manufactured by Nikon Corporation) at 50 ⁇ . Excellent when no film thickness unevenness at the pinhole and edge is observed, good when one of film thickness unevenness at the pinhole and edge is observed, both film thickness unevenness at the pinhole and edge occur. Was rated as poor.
  • the liquid crystal aligning agent prepared above was subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m.
  • the above-mentioned inkjet coating is performed on the ITO surface of a 40 mm ⁇ 30 mm ITO electrode-attached glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) in which the obtained solution is washed with pure water and IPA (isopropyl alcohol)
  • a film is formed by flexographic printing, and heat treatment is performed at 70 ° C. for 90 seconds on a hot plate at 230 ° C.
  • the periphery was coated with a sealing agent (XN-1500T manufactured by Mitsui Chemicals, Inc.).
  • a sealing agent XN-1500T manufactured by Mitsui Chemicals, Inc.
  • the sealing material was cured to form an empty cell.
  • a negative liquid crystal MLC-3023 (trade name of Merck & Co., Inc.) was injected into this empty cell by a pressure reduction injection method to prepare a liquid crystal cell.
  • the numerical value of the polymer indicates the blending ratio (mass ratio) of each polymer to the total amount of the polymer used for the preparation of the liquid crystal aligning agent.
  • the numerical value of the solvent composition indicates the blending ratio (mass ratio) of each compound to the total amount of the solvent used for the preparation of the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention can suppress coating defects of the alignment film caused by the influence of the wiring structure and C / H, and can suppress the drying of the liquid crystal aligning agent even when flexographic printing is performed. It is.
  • the liquid crystal display device having the liquid crystal alignment film obtained in this manner can display an image of high quality, and can be suitably used for a large screen and high definition liquid crystal television etc., and a TN element, STN element, TFT liquid crystal It is useful for a liquid crystal display device of a vertical alignment type such as a device.

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui permet d'éliminer les défauts de revêtement de film d'alignement dus à l'influence de la structure de câblage ou des trous de contact et qui permet également d'éliminer les défauts entraînant une irrégularité de l'affichage d'un élément d'affichage à cristaux liquides. L'invention concerne en outre un film d'alignement de cristaux liquides et un élément d'affichage à cristaux liquides. Ledit agent d'alignement de cristaux liquides est caractérisé en ce qu'il contient : au moins un polymère choisi dans le groupe constitué par un acide polyamique ou un ester d'acide polyamique ayant la structure de formule [1] et un polyimide qui est un composé imide de ceux-ci ; et un solvant contenant au moins un solvant A choisi dans le groupe constitué par les formules (d-1) à (d-5) et au moins un solvant B choisi dans le groupe constitué par la formule (e) et le monoalkyléther-acétate de l'alkylèneglycol, le diacétate de l'alkylèneglycol, le monoalkyléther de l'alkylèneglycol et le dialkyléther de l'alkylèneglycol ayant un point d'ébullition compris entre 200 et 300 °C, les symboles dans les formules étant tels que définis dans la description.
PCT/JP2018/043005 2017-11-21 2018-11-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de fabrication d'un film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2019103042A1 (fr)

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JP2019555337A JP7375544B2 (ja) 2017-11-21 2018-11-21 液晶配向剤、液晶配向膜、液晶配向膜の製造方法、及び液晶表示素子
CN201880075387.3A CN111386493B (zh) 2017-11-21 2018-11-21 液晶取向剂、液晶取向膜、液晶取向膜的制造方法和液晶表示元件
KR1020207016318A KR20200079314A (ko) 2017-11-21 2018-11-21 액정 배향제, 액정 배향막, 액정 배향막의 제조 방법, 및 액정 표시 소자

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