WO2021060268A1 - Agent d'alignement de cristaux liquides pour un alignement vertical, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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WO2021060268A1
WO2021060268A1 PCT/JP2020/035773 JP2020035773W WO2021060268A1 WO 2021060268 A1 WO2021060268 A1 WO 2021060268A1 JP 2020035773 W JP2020035773 W JP 2020035773W WO 2021060268 A1 WO2021060268 A1 WO 2021060268A1
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liquid crystal
group
diamine
crystal alignment
carbon atoms
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Japanese (ja)
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慎躍 大野
雄介 山本
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日産化学株式会社
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Priority to JP2021548925A priority Critical patent/JPWO2021060268A1/ja
Priority to CN202080066916.0A priority patent/CN114514303A/zh
Priority to KR1020227002339A priority patent/KR20220069916A/ko
Publication of WO2021060268A1 publication Critical patent/WO2021060268A1/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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/94—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • 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

Definitions

  • the present invention comprises a liquid crystal alignment agent for vertical alignment (VA), a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display element provided with the liquid crystal alignment film, a novel diamine suitable for them, and a heavy weight. Regarding coalescence.
  • VA vertical alignment
  • Liquid crystal display elements are widely used from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors.
  • the liquid crystal display element is generally configured by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several ⁇ m) and enclosing a liquid crystal between the electrode substrates. Then, by applying a voltage between the transparent conductive films constituting each electrode of the electrode substrate, the display on the liquid crystal display element is performed.
  • These liquid crystal display elements have a liquid crystal alignment film that is indispensable for controlling the arrangement state of liquid crystal molecules.
  • a liquid crystal display element various driving methods have been developed in which the electrode structure and the physical characteristics of the liquid crystal molecules used are different.
  • various modes such as TN (Twisted Nematic) method, STN (Super Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane Switching) method, and FFS (fringe field switching) method are known.
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • VA Very Alignment
  • IPS In-Plane Switching
  • FFS far-Plane Switching
  • the VA vertical orientation type liquid crystal display element has a wide viewing angle, a fast response speed, a large contrast, and the rubbing process can be eliminated in the production process. Therefore, there is a particular need for an increase in size. Widely used mainly for expensive TVs and monitors.
  • the above-mentioned transparent conductive film in the liquid crystal display element is usually formed of a composition (ITO) containing indium oxide as a main component and doped with several% tin oxide, and its refractive index is determined by the liquid crystal alignment film. It has a high value unlike the refractive index of. Therefore, when the light from the display light source is to be transmitted to the electrode substrate, the light is reflected at the interface between the transparent conductive film and the liquid crystal alignment film in each electrode substrate. As a result, the light transmittance of the electrode substrate cannot be sufficiently obtained, which causes a problem that the display brightness is lowered.
  • ultra-high-definition panels such as 4K and 8K have been developed, but these panels occupy a large amount of black matrix (BM), TFT, etc., and the aperture ratio of the panel decreases. It is important to improve the transmittance of the display unit.
  • BM black matrix
  • the present inventors have formed the transparent conductive film in order to increase the refractive index of the liquid crystal alignment film from the viewpoint that the above-mentioned problems can be solved by reducing the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film.
  • Various materials were examined. Specifically, in order to increase the refractive index of the liquid crystal alignment film, various types of polymers contained in the liquid crystal alignment agent forming the liquid crystal alignment film were searched for.
  • a liquid crystal alignment film formed from a liquid crystal alignment agent containing a colorable polymer has a low light transmittance and causes a decrease in display brightness, and as a result, the above object is not achieved.
  • an object of the present invention is a liquid crystal alignment agent for forming a liquid crystal alignment film for VA (vertical alignment) having a high light transmittance because it has a high refractive index but no coloring property.
  • An object of the present invention is to provide a liquid crystal alignment film obtained from an agent and a liquid crystal display element having the liquid crystal alignment film.
  • the present invention is at least one selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine (0) represented by the following formula (0) and a polyimide which is an imide of the polyimide precursor.
  • a liquid crystal alignment agent for vertical alignment (VA) which contains a polymer (P), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a vertical alignment type liquid crystal display element having the liquid crystal alignment film. It is in.
  • L represents a single bond or -X 1- Q-X 2- group.
  • X 1 and X 2 independently represent a single bond, an oxygen atom or a sulfur atom.
  • Q is 1 carbon or 1 carbon atom or a sulfur atom. Represents 2 alkylene groups.
  • a liquid crystal alignment agent for vertical alignment (VA) that forms a liquid crystal alignment film having a high light transmittance because it has a high refractive index but no coloring property can be obtained. Since the liquid crystal alignment film on which the liquid crystal alignment agent is formed has a high refractive index, the difference between the refractive index of the transparent conductive film in the liquid crystal display element and the refractive index of the liquid crystal alignment film can be reduced, and the difference between the refractive index and the refractive index of the liquid crystal alignment film can be reduced. Since it does not have colorability, it is possible to obtain a vertically oriented (VA) type liquid crystal display element having high light transmission and high display brightness.
  • VA vertically oriented
  • the liquid crystal aligning agent of the present invention is made from a polyimide precursor obtained by using a diamine component containing a diamine (0) represented by the following formula (0) and a polyimide which is an imide of the polyimide precursor. It is characterized by containing at least one polymer (P) selected from the above group.
  • P polymer selected from the above group.
  • A, A', L, X 1 and X 2 are as defined above, respectively.
  • the monocyclic group in A and A' refers to a divalent group obtained by removing two hydrogen atoms from the monocyclic ring.
  • the monocycle include benzene; a 5-membered heterocycle such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; and a 6-membered heterocycle such as pyran, pyrone, pyridine, pyridazine, pyrimidine, and pyrazine.
  • the single ring is preferably benzene or pyridine.
  • the monocyclic group is a phenylene group.
  • the condensed ring group in A and A' refers to a divalent group obtained by removing two hydrogen atoms from the condensed ring.
  • the fused ring include condensed polycyclic aromatic hydrocarbons such as naphthalene, tetraline, inden, fluorene, anthracene, phenanthrene and pyrene; benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, aclysine, etc.
  • fused polycyclic heterocycles such as phthalazine, quinazoline and quinoxaline.
  • the fused ring is preferably naphthalene, anthracene, pyrene, indole, carbazole, coumarin, benzo-pyrone, quinoline, or isoquinoline.
  • the group in which the two monocyclic groups are bonded is preferably a biphenyl structure or a bipyridine group.
  • a and A' preferably a phenylene group, a pyridinyl group, a naphthylene group, an anthracenyl group, a quinolinyl group, a biphenyl structure or a bipyridinyl group from the viewpoint of obtaining the effects of the present invention.
  • L is a single bond, -O- (CH 2 ) n- (n is an integer of 1 or 2), or -O- (CH 2 ) n- O- (n is an integer of 1 or 2). .) Is preferable.
  • Specific examples of the diamine (0) represented by the above formula (0) include the following formulas (d-1) to (d-21).
  • a preferable specific example of the diamine (0) represented by the above formula (0) is a diamine represented by the following formula (1).
  • A, L, X 1 and X 2 are as defined above, respectively.
  • the diamine (1) represented by the above formula (1) among the above formulas (d-1) to (d-21), the formulas (d-1) to (d-7), ( Examples thereof include d-13) to (d-14), (d-17) to (d-18) and (d-21).
  • the polymer (P) contained in the liquid crystal aligning agent of the present invention is selected from the group consisting of the structures represented by the following formulas (S1) to (S3) in addition to the diamine represented by the above formula (0). It is preferable that the polymer is at least one selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine (s) having at least one kind and a polyimide which is an imide of the polyimide precursor. ..
  • X 1 and X 2 are independently single-bonded,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CON. (CH 3 )-, -NH-, -O-, -COO-, -OCO- or-((CH 2 ) a1- A 1 ) m1- (a 1 is an integer from 1 to 15, and A 1 is oxygen.
  • atom or -COO- the stands, if .m 1 m 1 is an integer of 1 or 2 is 2, a plurality of a1 and a 1 represent each independently have the definitions).
  • G 1 and G 2 each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms.
  • Any hydrogen atom on the cyclic group may be 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. Alternatively, it may be substituted with a fluorine atom.
  • m and n are independently integers of 0 to 3, and the total of m and n is 1 to 6, preferably 1 to 4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy alkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 1 is substituted with a fluorine atom. You may.
  • Examples of the divalent cyclic group in G 1 and G 2 include a cyclopropylene group, a cyclohexylene group and a phenylene group.
  • Any hydrogen atom on these cyclic groups can be 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.
  • X 3 is a single bond, -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxy alkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 2 may be substituted with a fluorine atom. Further, R 2 is preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms from the viewpoint of enhancing the liquid crystal orientation.
  • X 4 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -OCH 2-, -COO- or -OCO-.
  • R 3 represents a structure having a steroid skeleton. Further, R 3 preferably has a structure containing a cholestanyl group, a cholesteryl group or a lanostenyl group.
  • Preferred specific examples of the formula [S1] include the following formulas [S1-x1] to [S1-x7].
  • R 1 is 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.
  • 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- * (however, the bond with "*” binds to (CH 2 ) a2 ), and A 2 is an oxygen atom * -COO- (however, "*").
  • a given binding hands (CH 2) binds to a2)
  • a 3 is 0 or 1
  • a 1 are each independently an integer of 1 ⁇ 10, Cy 1 , 4-Cyclohexylene group or 1,4-phenylene group.
  • X 3 is any of -O-, -CH 2 O-, -COO- or -OCO-
  • R 2 is an alkyl group having 3 to 20 carbon atoms or an alkyl group.
  • R 2 is an alkyl group having 3 to 20 carbon atoms, any hydrogen atoms that form the R 2 is substituted with a fluorine atom May be good.
  • a preferable specific example of the above formula [S3] is the following formula [S3-x].
  • X is the formula [X1], the formula [X2] or [X3]
  • Col is the formula [Col1], the formula [Col2] or the formula [Col3]
  • G Is a formula [G1], a formula [G2], a formula [G3], or a formula [G4].
  • Me represents a methyl group.
  • Preferred diamines (s) having the structures represented by the above formulas (S1) to (S3) include diamines represented by the following formulas (d1) or (d2).
  • Y represents the side chain structure represented by the above formulas [S1] to [S3], and the two Ys in the formula (d2) may be the same or different. You may be.
  • X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-,-(CH 2 ) m- , -SO 2- , -O- (CH 2 ) m.
  • m is an integer from 1 to 8.
  • Preferred specific examples of the diamine of the above formula (d1) include the following formulas (d1-1) to (d1-18). (N is an integer from 1 to 20.)
  • Examples of the diamine represented by the above formula (d2) include structures selected from the group consisting of the following formulas (d2-1) to (d2-6).
  • X p1 to X p8 are independently synonymous with X p in the above formulas [S1-x1] to [S1-x6], and X s1 to X s4 are independent and ⁇ O.
  • -, - CH 2 O -, - OCH 2 -, - COO- or -OCO- indicates, the X a ⁇ X f, -O - , - NH -, - O- (CH 2) m -O-, -C (CH 3 ) 2- , -CO-, -COO-, -CONH-,-(CH 2 ) m- , -SO 2- , -OC (CH 3 ) 2- , -CO- (CH) 2) m -, - NH- ( CH 2) m -, - NH- (CH 2) m -NH -, - SO 2 - (CH 2) m -, - SO 2 - (CH 2)
  • the polymer (P) contained in the liquid crystal aligning agent of the present invention contains a diamine component containing the diamine (0), preferably a diamine component containing a diamine (s) in addition to the diamine (0). It is a polyimide precursor obtained by using it, or a polyimide which is an imidized product of the polyimide precursor.
  • the polyimide precursor is a polymer capable of obtaining a polyimide by imidization of a polyamic acid, a polyamic acid ester, or the like.
  • the polyamic acid (P), which is a polyimide precursor of the polymer (P), is a diamine component containing the diamine (0), preferably a diamine component containing a diamine (s) in addition to the diamine (0). It can be obtained by a polymerization reaction with a tetracarboxylic acid component.
  • the amount of the diamine (0) used is preferably 1 to 100 mol%, more preferably 1 to 99 mol%, still more preferably 5 to 95 mol%, based on the diamine component to be reacted with the tetracarboxylic acid component. ..
  • the amount of diamine (s) used is preferably 1 to 99 mol% with respect to the diamine component to be reacted with the tetracarboxylic acid component, and 1 to 95 mol%. More preferably mol%.
  • the diamine component used in the production of the polyamic acid (P) may contain diamines other than diamine (0) and diamine (s) (hereinafter, these are also referred to as other diamines). Examples of other diamines are given below, but the present invention is not limited thereto.
  • Diamines with carboxy groups such as p-phenylenediamine, m-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 3,3' -Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,2-bis (4-aminophenyl) ethane, 1 , 3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1,2-bis (4-aminophenoxy) ethane, 1,
  • Phenoxy) ethyl diamine having a photopolymerizable group such as 2,4-diamino-N, N-diallylaniline at the end, diamine having a radical initiation function such as the following formulas (R1) to (R5), 2,6- Diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, the following formulas (z-1) to (z-18), etc.
  • Groups such as -1) to (5-11) "-N (D)-" (D represents a protecting group that is desorbed by heating and replaced with a hydrogen atom, and is preferably a tert-butoxycarbonyl group. ), Diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2), diamines described in International Publication No. 2016/125870, and the like.
  • D1 indicates an integer of 2 to 10.
  • N represents an integer from 2 to 10.
  • Boc represents a tert-butoxycarbonyl group.
  • the diamine represented by (Ox-2) is preferable.
  • the amount of the other diamines used is preferably 1 to 99 mol%, more preferably 5 to 9 mol%, based on the total diamine components used. It is 95 mol%.
  • the amount of the diamines (s) used is preferably 98 mol% or less with respect to the diamine component to be reacted with the tetracarboxylic acid component. More preferably, it is 94 mol% or less.
  • the amount of the other diamine used is preferably 5 to 40 mol%, more preferably 10 to 40 mol%, based on the total diamine component used in the production of the polyamic acid (P).
  • the tetracarboxylic acid component to be reacted with the diamine component is not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic dianoxide.
  • tetracarboxylic dianhydride such as acid dialkyl ester dihalide can also be used.
  • the tetracarboxylic dianhydride or its derivative examples include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and derivatives thereof.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the aromatic ring.
  • the aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
  • the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.
  • the tetracarboxylic dianhydride or a derivative thereof is preferably represented by the following formula (T).
  • X represents a structure selected from the group consisting of the following (x-1) to (x-13).
  • R 1 to R 4 independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a phenyl group.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
  • j and k are independently 0 or 1, respectively, and A 1 and A 2 are independently single bonds, ether (-O-), carbonyl (-CO-), ester (-COO-), respectively. ), phenylene, sulfonyl group (-SO 2 - represents) or amide groups (-CONH-), 2 pieces of a 2 may be the same or may be different.
  • * 1 is a bond that binds to one acid anhydride group
  • * 2 is a bond that binds to the other acid anhydride group.
  • X is the above formulas (x-1) to (x-7), (x-11) to (x).
  • the one selected from -13) can be mentioned.
  • the proportion of the tetracarboxylic dianhydride or its derivative represented by the above formula (T) is preferably 1 mol% or more, more preferably 5 mol% or more, based on 1 mol of the total tetracarboxylic acid component used. Preferably, 10 mol% or more is more preferable.
  • the tetracarboxylic dianhydride and its derivative used for producing the polyamic acid (P) may contain a tetracarboxylic dianhydride other than the above formula (T) or a derivative thereof.
  • the polyamic acid (P) is produced by reacting the diamine component and the tetracarboxylic acid component in a solvent (polycondensation).
  • the solvent is not particularly limited as long as the produced polymer dissolves. Specific examples of the above solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl. -2-Imidazolidinone can be mentioned.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] can be used.
  • the indicated solvents can be used.
  • 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.
  • solvents may be used alone or in combination. Further, even if the solvent does not dissolve the polymer, it may be mixed with the above solvent and used as long as the produced polymer does not precipitate.
  • the reaction can be carried out at an arbitrary concentration, but the concentration of the diamine component and the tetracarboxylic acid component with respect to the solvent is preferably 1 to 50 mass by mass. %, More preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration and then the solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is 0.8 to 1.2. Is preferable. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the specific polymer produced.
  • the polyamic acid ester which is a polyimide precursor is, for example, [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [II] a method of reacting a tetracarboxylic acid diester with a diamine. III] It can be obtained by a known method such as a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
  • the polyimide contained in the liquid crystal alignment agent of the present invention is a polyimide obtained by ring-closing the above-mentioned polyimide precursor.
  • the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method of imidizing the polyimide precursor to obtain polyimide include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
  • the temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the outside of the system.
  • the catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times that of the amic acid group. It is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, and tributylamine trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
  • the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution may be added to a solvent for precipitation.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
  • the polymer which has been put into a solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure.
  • the solvent at this time include alcohols, ketones hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these because the purification efficiency is further improved.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. 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. Within such a molecular weight range, good orientation of the liquid crystal display element can be ensured.
  • the liquid crystal alignment agent of the present invention is a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in a suitable solvent.
  • the liquid crystal alignment agent of the present invention for the purpose of improving, for example, electrical properties, vertical orientation, and solution properties, in addition to the polymer (P), other polymers (hereinafter, other polymers) are also used. ) May be contained.
  • the other polymer at least one selected from the group consisting of the structures represented by the above formulas (S1) to (S3) in addition to the above polymer (P) from the viewpoint of enhancing the vertical orientation. It may contain at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a seed-bearing diamine and a polyimide which is an imide of the polyimide precursor.
  • the content ratio of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polymers contained in the liquid crystal alignment agent. preferable.
  • polymers are not particularly limited, and are main skeletons such as polyimide precursors, polyimides, polysiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates.
  • polyimide precursors polyimides, polyamides, polyorganosiloxanes, poly (meth) acrylates and polyesters
  • polyimide precursors, polyimides and polysiloxanes is more preferable.
  • other polymers may be used in combination of 2 or more types.
  • the liquid crystal alignment agent of the present invention may contain other components other than the above, if necessary.
  • the component include a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group, and a polymerizable unsaturated group.
  • crosslinkable compound examples include compounds represented by the following formulas (CL-1) to (CL-11).
  • Examples of the compound for adjusting the dielectric constant and the electric resistance of the liquid crystal alignment film include monoamines having a nitrogen-containing aromatic heterocycle such as 3-picorylamine.
  • organic solvent used in the liquid crystal alignment agent of the present invention examples include N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, and N- (n-propyl).
  • the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 1 to 10% by mass. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by mass.
  • the liquid crystal alignment film for vertical alignment using the liquid crystal alignment agent of the present invention can be produced by sequentially performing the steps of applying, drying and firing the above liquid crystal alignment agent on a substrate.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate, and in addition to the 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 a liquid crystal is formed. Further, in the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can also be used as the electrode in this case.
  • Examples of the method for applying the liquid crystal alignment agent include screen printing, offset printing, flexographic printing inkjet method, dip method, roll coater method, slit coater method, spinner method, and spray method. From the viewpoint of enhancing, a method of applying by flexographic printing or an inkjet method is preferable.
  • the liquid crystal alignment agent After applying the liquid crystal alignment agent on the substrate, it is dried at 40 to 150 ° C. by a heating means such as a hot plate or a heat circulation type oven IR (infrared) type oven, depending on the solvent used for the liquid crystal alignment agent. Then, the liquid crystal alignment film can be obtained by firing at a temperature of preferably 150 to 300 ° C., more preferably 180 to 250 ° C.
  • a heating means such as a hot plate or a heat circulation type oven IR (infrared) type oven, depending on the solvent used for the liquid crystal alignment agent.
  • the thickness of the liquid crystal alignment film after firing is preferably 5 to 300 nm, more preferably. Is 10 to 100 nm.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film.
  • the coating film formed as described above can be used as it is as a liquid crystal alignment film, but if necessary, a rubbing treatment or a PSA treatment described later may be performed.
  • the liquid crystal aligning agent of the present invention has a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display element manufactured through a step of arranging an object and polymerizing a polymerizable compound by at least one of irradiation and heating of active energy rays while applying a voltage between electrodes.
  • the voltage to be applied can be, for example, a direct current or an alternating current of 5 to 50 V.
  • the active energy ray ultraviolet rays are suitable.
  • the ultraviolet rays include ultraviolet rays having a wavelength of 300 to 400 nm, preferably ultraviolet rays having a wavelength of 310 to 360 nm.
  • the irradiation amount of light is preferably 0.1 to 20 J / cm 2 , and more preferably 1 to 20 J / cm 2 .
  • the above liquid crystal alignment agent is applied onto a pair of substrates having a conductive film to form a coating film, and a coating film is formed through a layer of liquid crystal molecules.
  • the liquid crystal cells are arranged so as to face each other so that the coating films are opposed to each other, and the liquid crystal cells are irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates.
  • the above liquid crystal display element controls the pre-tilt of liquid crystal molecules by the PSA (Polymer Sustained Alignment) method.
  • PSA Polymer Sustained Alignment
  • a small amount of a photopolymerizable compound for example, a photopolymerizable monomer is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then an ultraviolet ray is applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer.
  • the pretilt of the liquid crystal molecules is controlled by the polymer produced by irradiating the liquid crystal molecules.
  • the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Further, since the PSA method does not require a rubbing process, it is suitable for forming a vertically oriented liquid crystal layer in which it is difficult to control the pre-tilt by the rubbing process.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent of the present invention by the above-mentioned method, and then producing a liquid crystal cell by a known method.
  • a method for producing a liquid crystal cell a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is sprayed on the liquid crystal alignment film of one substrate, the liquid crystal alignment film surface is on the inside, and the other is produced.
  • Examples thereof include a method in which the substrates of the above are bonded and the liquid crystal is injected under reduced pressure to seal the liquid crystal, and a method in which the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is sprayed and then the substrates are bonded and sealed.
  • the liquid crystal may be mixed with a polymerizable compound that polymerizes by ultraviolet irradiation or heat.
  • the polymerizable compound is a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule, for example, a polymerizable compound represented by the following formulas (M-1) to (M-3). Compounds can be mentioned.
  • the content of the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the orientation of the liquid crystal cannot be controlled. If the amount is more than 10 parts by mass, the number of unreacted polymerizable compounds increases and the liquid crystal display element. The seizure characteristics of the polymer are reduced. After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating the liquid crystal cell with heat or ultraviolet rays while applying an AC / DC voltage to the liquid crystal cell. Thereby, the orientation of the 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 contains a polymerizable group that polymerizes between the pair of substrates by at least one of active energy rays and heat. It may also be used in a liquid crystal display element manufactured through a step of arranging an alignment film and applying a voltage between electrodes, that is, in SC-PVA mode.
  • ultraviolet rays are suitable as the active energy rays.
  • the ultraviolet rays the ultraviolet rays used in the PSA method can be applied including a preferable embodiment. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heating may be performed at the same time.
  • a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent or a polymer containing a polymerizable group A method using an ingredient can be mentioned.
  • the polymer containing a polymerizable group include a polymer obtained by using a diamine having a function of polymerizing by the above-mentioned light irradiation.
  • the molecular weight of the polyimide precursor and the polyimide can be determined by using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805) (manufactured by Shodex). It was measured as follows. Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr ⁇ H 2 O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L.
  • GPC room temperature gel permeation chromatography
  • THF tetrahydrofuran
  • Flow velocity 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
  • reaction solution was added to water (750 g) to precipitate crystals, and the crystals were collected by filtration.
  • Isopropyl alcohol (216 g) was added to the obtained crystals, and the mixture was heated and stirred at 65 ° C., and toluene (300 g) was added while cooling to room temperature for crystallization. This was filtered, the cake was washed with toluene and hexane, and the crystals were dried to obtain compound [9] (yield: 28.0 g, 106 mmol, yield 78%).
  • reaction solution was poured into water (2268 g) to precipitate crystals.
  • the mixture was filtered using a Büchner funnel to obtain sticky black-purple crystals (93 g).
  • N, N-dimethylformamide was added to the obtained crude product, dissolved by heating at 80 ° C., crystallized with methanol while cooling to room temperature, filtered and dried to obtain compound [11] (yield: 28). 0.0 g, 51.4 mmol, yield 67%).
  • reaction solution was cooled to 0 ° C., and a solution of Compound 2 (105.60 g, 42.2 mmol, 1.0 eq.) In THF (200 g) was added dropwise. After the dropping was completed, the temperature of the reaction solution was returned to room temperature, and the mixture was stirred at room temperature for 3 hours. Then, toluene (1 L) was added to dilute the reaction solution, the reaction solution was cooled to 0 ° C. again, and a 10% acetic acid solution (500 g) was gradually added dropwise.
  • the aqueous layer is removed by a liquid separation operation, the organic layer is washed with saturated brine (1 L), saturated aqueous sodium hydrogen carbonate solution (1 L), and saturated brine (1 L), and the organic layer is washed with anhydrous magnesium sulfate. Was dried. Then, it was filtered and distilled by an evaporator to obtain 172 g of a crude crystal of compound 3. The obtained crude crystals were used as they were in the next reaction.
  • the obtained crude product was recrystallized from an acetonitrile / ethanol (2: 1) solution, filtered, and then the filtered crystals were washed with ethanol to obtain crude crystals of Compound 8.
  • the crude crystals were purified by column chromatography (SiO 2 , CHCl 3 ) to obtain crystals of compound 8 (yield 7.1 g, yield 49%).
  • the solid content ratio in Table 2 above represents the content ratio of the polymer solid content with respect to 100 parts by mass of the liquid crystal aligning agent, and the solvent composition ratio represents the content ratio (parts by mass) in each organic solvent.
  • Example 14 The liquid crystal alignment agent (R1) obtained in Example 1 and the liquid crystal alignment agent (R4) obtained in Example 4 are mixed so that their mass ratios are 3: 7, and the mixture is stirred at room temperature for 3 hours. , Example 14 liquid crystal alignment agent (B5) was prepared. Further, in Examples 15 to 21, by carrying out in the same manner as in Example 14 except that the combination of the liquid crystal alignment agents used was changed to those shown in Table 3 below, Examples 15 to 21 shown in Table 3 below, respectively. Liquid crystal alignment agents (B6 to B8, R10 to R13) were prepared.
  • Examples 22 to 35 A liquid crystal alignment film and a liquid crystal cell were prepared as described below, and the characteristics of each of the prepared liquid crystal cells were evaluated. The results are shown in Table 4 below. In the following examples, Examples 22 to 25 and 28 to 31 are examples of the present invention, and Examples 26, 27 and 32 to 35 are comparative examples.
  • a liquid crystal alignment film was prepared as follows. Each liquid crystal alignment agent is spin-coated on a quartz substrate or a silicon wafer, dried on a hot plate at 70 ° C. for 90 seconds, and then baked in a hot air circulation oven (MB1-1G3030X, manufactured by Denko) at 230 ° C. for 20 minutes. , A liquid crystal alignment film having a film thickness of 100 nm was formed.
  • a measurement cell was prepared using two quartz substrates. A liquid crystal alignment film was formed on one of the two sheets, and a quartz substrate on which the liquid crystal alignment film was not formed was attached with the side surface on which the liquid crystal alignment film was formed inside. In the meantime, a refracting liquid (contact liquid, manufactured by Shimadzu Device Manufacturing Co., Ltd.) was inserted using a dropper to prepare a measurement cell. The refracting liquid was used from 11 types in 0.01 increments of 1.60 to 1.70 according to the respective refractive index.
  • a liquid crystal cell was prepared as follows. Each liquid crystal alignment agent was spin-coated on the ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m, and dried on a hot plate at 70 ° C. for 90 seconds. , 230 ° C., hot air circulation type oven (MB1-1G3030X, manufactured by Denko) for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
  • hot air circulation type oven M1-1G3030X, manufactured by Denko
  • liquid crystal aligning agent is spin-coated on the ITO surface on which the electrode pattern is not formed, dried on a hot plate at 70 ° C. for 90 seconds, and then placed in a hot air circulation oven (MB1-1G3030X, manufactured by Denko) at 230 ° C. It was baked for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
  • a 4 ⁇ m bead spacer was sprayed on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent type thermosetting type epoxy resin) was printed on the bead spacers.
  • a sealant solvent type thermosetting type epoxy resin
  • the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell.
  • a liquid crystal MLC-3023 (trade name manufactured by Merck & Co., Inc.) containing a polymerizable compound was injected into the empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
  • UV ultraviolet irradiation degree meter
  • evaluation of liquid crystal cell The method for evaluating the characteristics of each liquid crystal cell produced as described above is as follows. (Evaluation of vertical orientation) The liquid crystal cell was sandwiched between cross Nicol polarizing plates, and the liquid crystal cell was rotated in a state where the backlight was irradiated from the rear part, and it was visually observed whether the liquid crystal was vertically oriented by the change of brightness. The evaluation criteria are as follows. ⁇ : The liquid crystal is vertically oriented. X: The liquid crystal is not vertically oriented.

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Abstract

L'invention concerne : un agent d'alignement de cristaux liquides qui est destiné à former un film d'alignement de cristaux liquides pour un alignement vertical (VA) et qui a un indice de réfraction élevé et une transmittance élevée de la lumière en raison de n'avoir pas de coloration ; un film d'alignement de cristaux liquides obtenu à partir dudit agent d'alignement de cristaux liquides ; et un élément d'affichage à cristaux liquides ayant ledit film d'alignement de cristaux liquides.　Cet agent d'alignement de cristaux liquides pour un alignement vertical est caractérisé en ce qu'il contient au moins un polymère (P) choisi dans le groupe constitué par les polyimides et les précurseurs de polyimide obtenus en utilisant un composant diamine comprenant une diamine (0) représentée par la formule (0). (A et A' représentent chacun indépendamment un groupe à cycle unique, un groupe à cycle fusionné, ou un groupe obtenu par liaison de deux desdits groupes à cycle unique, et au moins l'un parmi A et A' représente un groupe à cycle fusionné. L représente une liaison simple ou -X1-Q-X2-. X1 et X2 représentent chacun indépendamment une liaison simple, un atome d'oxygène ou un atome de soufre. Q représente un groupe alkylène ayant 1 ou 2 atomes de carbone.)
PCT/JP2020/035773 2019-09-24 2020-09-23 Agent d'alignement de cristaux liquides pour un alignement vertical, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2021060268A1 (fr)

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JP2011257736A (ja) * 2010-05-10 2011-12-22 Jsr Corp 液晶配向剤
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