WO2023210532A1 - Agent d'alignement de cristaux liquides, 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 et élément d'affichage à cristaux liquides Download PDF

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WO2023210532A1
WO2023210532A1 PCT/JP2023/015956 JP2023015956W WO2023210532A1 WO 2023210532 A1 WO2023210532 A1 WO 2023210532A1 JP 2023015956 W JP2023015956 W JP 2023015956W WO 2023210532 A1 WO2023210532 A1 WO 2023210532A1
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liquid crystal
group
aligning agent
hydrogen atom
crystal aligning
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PCT/JP2023/015956
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Japanese (ja)
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瑛士郎 平賀
達也 結城
友基 玉井
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日産化学株式会社
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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
    • 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 relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
  • Liquid crystal display elements are widely used as display parts for personal computers, mobile phones, smartphones, televisions, etc.
  • a liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, and an alignment film that controls the liquid crystal orientation of liquid crystal molecules in the liquid crystal layer. , thin film transistors (TFTs), etc. that switch electrical signals supplied to pixel electrodes.
  • Driving methods for liquid crystal molecules include vertical electric field methods such as TN (Twisted Nematic) method and VA (Vertical Alignment) method, IPS (In-Plane Switching) method, and FFS (Fringe Field Switch). Transverse electric field method such as ng) method are known.
  • the horizontal electric field method in which an electrode is formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate, has a wider field area than the conventional vertical electric field method, in which voltage is applied to electrodes formed on the upper and lower substrates to drive the liquid crystal. It is known as a liquid crystal display element that has viewing angle characteristics and is capable of high-quality display.
  • Patent Document 1 describes a liquid crystal aligning agent obtained by polycondensing an aromatic diamine whose terminal amino group is alkylated and a specific alicyclic tetracarboxylic dianhydride.
  • a liquid crystal aligning agent containing a polymer is disclosed.
  • an object of the present invention to provide a liquid crystal alignment film that can reduce the generated charges in a short time while reducing the absolute value of accumulated charges, and a liquid crystal that reduces charge accumulation and flicker caused by backlight light.
  • An object of the present invention is to provide a liquid crystal aligning agent from which an alignment film can be obtained.
  • the present inventor found that the use of a specific tetracarboxylic acid component and a specific diamine component is effective in achieving the above object. Then, the inventors discovered that a liquid crystal aligning agent having the following structure is optimal for achieving the above object, and completed the present invention.
  • (X a represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
  • Y 2 is a divalent organic group having 6 to 30 carbon atoms and containing one or more aromatic groups. represents.
  • Z 2 each independently represents an alkylene group having 1 to 6 carbon atoms.
  • Each of A 2 independently represents an alkyl group having 1 to 6 carbon atoms. Any hydrogen atom may be replaced with a monovalent group.
  • halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and * indicates a bond. represents a hand.
  • liquid crystal alignment agent of the present invention By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film that can reduce the generated charge in a short time while reducing the absolute value of accumulated charge, and a liquid crystal that reduces charge accumulation and flicker caused by backlight light. An alignment film is obtained.
  • polyamic acid which is the main component of the liquid crystal aligning agent, undergoes a thermal imidization reaction. This is a reaction in which an imide ring is formed by heating, and the lower the ratio (imidization rate), the higher the polarity, which makes it easier to reduce the charge.
  • the ring-closing reaction is inhibited by the presence of A 2 in the diamine (2), so it is thought that the charge can be easily reduced even during normal firing.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention.
  • the liquid crystal aligning agent of the present invention includes at least one type selected from the group consisting of tetracarboxylic dianhydride and its derivatives represented by the above formula (1) (in the present invention, a specific aromatic tetracarboxylic acid component (p ) and a diamine component containing a diamine represented by the above formula (2) (also referred to as a specific diamine (p) in the present invention); It contains at least one polymer (P) selected from the group consisting of polyimide, which is an imidized product of the polyimide precursor.
  • the polymer (P) may be one type or two or more types.
  • the polyimide precursor is a polymer that can be imidized to obtain polyimide, such as polyamic acid or polyamic acid ester.
  • the polyamic acid (P') which is a polyimide precursor of the polymer (P) can be obtained by polymerizing, for example, a diamine component containing the above-mentioned specific diamine (p) and a tetracarboxylic dianhydride represented by the above formula (1). It can be obtained by reaction.
  • 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 acid. Derivatives of tetracarboxylic dianhydrides such as dialkyl ester dihalides can also be used.
  • X a in the above formula (1) represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative 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 an aromatic ring.
  • X a in the above formula (1) is preferably a structure selected from the following formulas (Xa-1) and (Xa-2).
  • j and k are integers of 0 or 1
  • R represents a hydrogen atom or a methyl group.
  • Preferred specific examples of the above formulas (Xa-1) and (Xa-2) include the following formulas (Xa-3) to (Xa-18).
  • X a is more preferably represented by the above formulas (Xa-3) to (Xa-7), and even more preferably represented by the above formulas (Xa-3) to (Xa-6).
  • the proportion of the specific aromatic tetracarboxylic acid component (p) used is preferably 10 mol% or more, more preferably 20 mol% or more, based on 1 mol of the total tetracarboxylic acid components used in the polymer (P). Preferably, 50 mol% or more is more preferable.
  • the tetracarboxylic acid component used in the production of the polymer (P) contains a tetracarboxylic acid component other than the above-mentioned specific aromatic tetracarboxylic acid component (p) (hereinafter also referred to as other tetracarboxylic acid component). You can stay there.
  • the amount of the specific aromatic tetracarboxylic acid component (p) to be used depends on the polymer (P). It is preferably 90 mol% or less, more preferably 80 mol% or less, based on 1 mol of all the tetracarboxylic acid components used.
  • Examples of the other tetracarboxylic acid components include acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and derivatives thereof.
  • the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
  • Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups is bonded to an aromatic ring. Further, it is not necessary to be composed only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
  • acyclic aliphatic or alicyclic tetracarboxylic dianhydride is selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, especially from the viewpoint of improving liquid crystal orientation.
  • a tetracarboxylic dianhydride or a derivative thereof having at least one partial structure is preferable.
  • the other tetracarboxylic acid component described above is preferably a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof.
  • X T is a structure selected from the following formulas (X1-1) to (X1-23).
  • R 1 to R 21 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. From the viewpoint of liquid crystal alignment, R 1 to R 21 are each independently preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • formula (X1-1) include the following formulas (1-1) to (1-6). From the viewpoint of improving liquid crystal orientation, (1-1) to (1-2) are particularly preferred.
  • the above X T is preferably the above formulas (X1-1) to (X1-10) or (X1-18) to (X1-23), and the above formulas (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), or (X1-23) are more preferable, and the above formulas (1-1), (1-2), (X1 -5), (X1-7), (X1-8), or (X1-9) are more preferred.
  • the specific diamine (p) of the present invention is a diamine represented by the above formula (2).
  • the above specific diamine (p) may be used alone or in combination of two or more.
  • the usage amount of the specific diamine (p) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, based on 1 mol of the diamine component used for producing the polymer (P). preferable.
  • Y 2 in the above formula (2) represents a divalent organic group having 6 to 30 carbon atoms and containing one or more aromatic groups.
  • the above-mentioned aromatic group refers to an aromatic hydrocarbon group or an aromatic heterocyclic group, and includes a monocyclic group, a condensed ring group, and a group in which monocycles or condensed rings are connected.
  • Examples of the aromatic ring structure in the aromatic group include a benzene ring, a naphthalene ring, and a biphenyl structure. Any hydrogen atom of the aromatic group may be replaced with a monovalent group.
  • the monovalent groups mentioned above include halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, fluoroalkyl groups having 1 to 10 carbon atoms, and fluoroalkyl groups having 1 to 10 carbon atoms.
  • Examples include a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.
  • Y 2 is preferably bonded to Z 2 through an atom forming an aromatic ring, and more preferably bonding to a carbon atom forming an aromatic ring. It is more preferable that the polymer (P) has the aromatic group of Y 2 in the main chain direction of the polymer (P).
  • the main chain of a polymer refers to the part of the polymer that consists of the longest chain of atoms. "The polymer (P) has the aromatic group that Y2 has in the main chain direction of the polymer (P)" means that the aromatic group that Y2 has has the aromatic group that is present in the main chain of the polymer (P). It means to constitute.
  • Y 2 preferably has a structure represented by the following formula (3).
  • R represents a hydrogen atom, methyl group, or tert-butoxycarbonyl group
  • cyclohexylene group or an alkylene group having 2 to 18 carbon atoms.
  • R 3 represents a halogen atom, or an alkyl group or alkoxy group having 1 to 5 carbon atoms, and any hydrogen atom of the alkyl group or alkoxy group may be substituted with a halogen atom, and R 3 represents any hydrocarbon group. may be substituted with an amino group protected with a tert-butoxycarbonyl group.
  • Each of the plurality of a's is an integer of 0 to 4, b is an integer of 1 to 2, and c is an integer of 0 to 1.
  • p is an integer from 1 to 6, preferably from 2 to 6.
  • q is an integer of 1 to 6, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.
  • p', q', and r' are integers from 0 to 6. Furthermore, 0 ⁇ p'+q' ⁇ 10 is satisfied, and 2 ⁇ p'+q+r' ⁇ 16 is satisfied.
  • Z 2 is each independently an alkylene group having 1 to 6 carbon atoms. From the viewpoint of improving liquid crystal orientation, methylene groups or ethylene groups are preferred. A 2 is an alkyl group having 1 to 6 carbon atoms. From the viewpoint of improving liquid crystal orientation, A 2 is preferably a methyl group or an ethyl group.
  • diamine represented by the above formula (2) include diamines represented by any of the following formulas (d2-1) to (d2-3).
  • the diamine component used in the production of the above polymer (P) may contain diamines other than the specific diamine (p) (hereinafter also referred to as other diamines).
  • the amount of specific diamine (p) to be used with respect to the diamine component is based on 1 mole of the diamine component used in the production of the polymer (P). , is preferably 90 mol% or less, more preferably 80 mol% or less.
  • Examples of other diamines are listed below, but are not limited to these.
  • the other diamines mentioned above may be used alone or in combination of two or more.
  • p-phenylenediamine m-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diamino biphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
  • Diamines having a photo-alignable group such as 4,4'-diaminoazobenzene or diaminotolane; Diamines having an amide bond such as 4,4'-diaminobenzanilide; 1,3-bis(4-aminophenyl)urea , 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea and other diamines having a urea bond; 2,6-diaminopyridine, 3,4-diaminopyridine, 2 , 4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl- 3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole,
  • diamines having siloxane bonds such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; metaxylylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexa Methylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), formulas (Y-1) to (Y-167) described in WO2018/117239 diamine etc. in which two amino groups are bonded to a group represented by any one of ).
  • m and n are each independently an integer of 0 to 3, satisfying 1 ⁇ m+n ⁇ 4.
  • j is an integer of 0 or 1.
  • X 1 is -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, Represents -CH 2 O-, -CH 2 -OCO-, -COO-, or -OCO-.
  • R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and Represents a monovalent group such as an alkoxyalkyl group having 2 to 10 carbon atoms.
  • X 2 represents -O-, -CH 2 O-, -CH 2 -OCO-, -COO-, or -OCO-.
  • Boc represents a tert-butoxycarbonyl group.
  • Examples of the nitrogen atom-containing heterocycle that the diamine having the nitrogen atom-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, and isoquinoline. , naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine. Among these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferred.
  • the above-mentioned other diamines include the first diamine, a diamine having an amide bond, a diamine having a urea bond, a diamine having a group "-N(D)-", and a specific nitrogen atom-containing diamine.
  • the diamine may be selected from the group consisting of a diamine having a structure and a diamine having a carboxy group.
  • the liquid crystal aligning agent of the present invention is a liquid composition in which the polymer (P) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.
  • the liquid crystal aligning agent of the present invention may contain other polymers than the polymer (P).
  • other polymers include polyimide precursors obtained by using, in addition to the above polymer (P), a tetracarboxylic acid component that does not contain the above specific aromatic tetracarboxylic acid component (p); At least one polymer selected from the group consisting of polyimide, which is an imidized product of a polyimide precursor, a polyimide precursor obtained using a diamine component that does not have the above-mentioned specific diamine (p), and an imidized product of the polyimide precursor.
  • a certain polyimide also referred to as polymer (B) in the present invention
  • poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Cerac Manufacturing Co., Ltd.), and poly(isobutylene-maleic anhydride) copolymers include A specific example of the anhydride copolymer is Isoban-600 (manufactured by Kuraray Co., Ltd.).
  • a specific example of the poly(vinyl ether-maleic anhydride) copolymer includes Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation).
  • polymer (B) is more preferable from the viewpoint of reducing afterimages derived from residual DC.
  • the other polymers mentioned above may be used alone or in combination of two or more.
  • the content ratio of 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 the total 100 parts by mass of the polymers contained in the liquid crystal aligning agent. preferable.
  • the tetracarboxylic acid component used in the production of the polymer (B) include the same compounds as those exemplified for the polymer (P), including preferred specific examples.
  • the tetracarboxylic acid component used for producing the polymer (B) is more preferably a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. It is more preferable to include a compound or a derivative thereof (hereinafter also referred to as a specific tetracarboxylic acid component (B)).
  • the amount of the specific tetracarboxylic acid component (B) used is preferably 10 mol% or more, and 20 mol% or more, based on 1 mol of the total tetracarboxylic acid component used for producing the polymer (B). is more preferable, and even more preferably 50 mol% or more.
  • Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above. Among these, at least one diamine selected from the group consisting of the first diamine, a diamine having a urea bond, a diamine having an amide bond, and a diamine having a group "-N(D)-" (in the present invention, these is also referred to as a specific diamine (b)).
  • the diamine component one type of diamine may be used alone, or two or more types may be used in combination.
  • the amount used is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total diamine components used for producing the polymer (B).
  • the amount of the specific diamine (b) used is preferably 90 mol% or less, and 80 mol% or less, based on 1 mol of the total diamine components used for producing the polymer (B). The following are more preferred.
  • Polyamic acid is produced by reacting a diamine component and a tetracarboxylic acid component in an organic solvent.
  • the ratio of the tetracarboxylic acid component and diamine component used in the polyamic acid production reaction is such that the acid anhydride group in the tetracarboxylic acid component is 0.5 to 2 equivalents per 1 equivalent of amino group in the diamine component.
  • the ratio is preferably 0.8 to 1.2 equivalents, and more preferably 0.8 to 1.2 equivalents.
  • the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent the larger the molecular weight of the polyamic acid produced becomes.
  • the reaction temperature in the production of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. Further, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. Polyamic acid can be produced at any concentration, but the concentration of polyamic acid is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. It is also possible to carry out the reaction at a high concentration in the initial stage and then add a solvent.
  • organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl
  • examples include sulfoxide and 1,3-dimethyl-2-imidazolidinone.
  • the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Solvents such as glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.
  • Polyamic acid esters can be produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a method of reacting a tetracarboxylic acid diester with a diamine, and [III] a method of reacting a tetracarboxylic acid diester with a diamine. It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.
  • Polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the above polyamic acid or polyamic acid ester.
  • the imidization ratio as used herein refers to the ratio of imide groups to the total amount of imide groups and carboxy groups (or derivatives thereof) derived from tetracarboxylic dianhydride or its derivatives.
  • the imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the use and purpose.
  • Examples of methods for imidizing the polyimide precursor include thermal imidization, in which the polyimide precursor solution is directly heated, and catalytic imidization, in which a catalyst is added to the polyimide precursor solution.
  • the temperature when thermally imidizing the polyimide precursor in a solution is preferably 100 to 400°C, more preferably 120 to 250°C, and it is preferable to carry out thermal imidization while removing water generated by the imidization reaction from the system. is preferred.
  • Catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, and stirring the mixture preferably at -20 to 250°C, more preferably at 0 to 180°C. Can be done.
  • the amount of the basic catalyst is preferably 0.5 to 30 times the amount of the amic acid group, more preferably 2 to 20 times the amount, and the amount of the acid anhydride is preferably 1 to 50 times the amount of the amic acid group. Preferably it is 3 to 30 times the mole.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc.
  • pyridine is preferred because it has an appropriate basicity to allow the reaction to proceed.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride.
  • acetic anhydride is preferably used because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like.
  • the polymer precipitated in a solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating.
  • the amount of impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more types of solvents selected from these, since the efficiency of purification will further increase.
  • an appropriate end-capping agent is used together with a tetracarboxylic acid component containing tetracarboxylic dianhydride or a derivative thereof and a diamine component containing a diamine to form an end-capped type.
  • Polymers may be produced.
  • the terminal-capped polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.
  • Examples of the terminals of the polyimide precursor and polyimide in the present invention include amino groups, carboxy groups, acid anhydride groups, and groups derived from the terminal capping agent described below.
  • the amino group, carboxy group, and acid anhydride group can be obtained by a conventional condensation reaction or by capping the terminal using the terminal capping agent shown below.
  • terminal capping agent examples include acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride.
  • Examples include isocyanates having unsaturated bonds.
  • the proportion of the terminal capping agent used is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, based on a total of 100 parts by mole of the diamine component used.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. It is. Further, the molecular weight distribution (Mw/Mn) expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. By having a molecular weight within this range, good liquid crystal alignment of the liquid crystal display element can be ensured.
  • the organic solvent contained in the liquid crystal aligning agent according to the present invention is not particularly limited as long as it can uniformly dissolve the polymer (P) and other polymers added as necessary.
  • P polymer
  • N-ethyl-2-pyrrolidone dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethyl Propanamide, 3-butoxy-N,N-dimethylpropanamide, 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-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N- Examples include cyclol
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or ⁇ -butyrolactone are preferred.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvents and a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the coating film when applying the liquid crystal aligning agent. Preference is given to using a solvent. Specific examples of poor solvents are shown below, but are not limited thereto.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the type and content of the poor solvent are appropriately selected depending on the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.
  • the poor solvent examples include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethyl butyl acetate, 2 - Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl
  • diisobutyl carbinol propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
  • Preferred solvent combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether.
  • the liquid crystal aligning agent of the present invention contains the above-mentioned polymer (P), and if necessary, the above-mentioned other polymers and the above-mentioned organic solvent.
  • the total content of the polymers contained in the liquid crystal aligning agent of the present invention can be changed as appropriate depending on the thickness of the coating film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, the total content is 1 mass. % or more, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable.
  • a particularly preferred total polymer content is 2 to 8% by weight.
  • the content of the polymer (P) used in the present invention is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and 20 to 100% by mass based on the total amount of polymers contained in the liquid crystal aligning agent. % is particularly preferred.
  • the liquid crystal aligning agent of the present invention may contain other components (hereinafter also referred to as additive components) in addition to the polymer (P), the other polymers, and the organic solvent. Examples of such additive components include crosslinkable compounds having at least one substituent selected from oxiranyl groups, oxetanyl groups, blocked isocyanate groups, oxazoline groups, cyclocarbonate groups, hydroxy groups, and alkoxy groups, and polymerizable inorganic compounds.
  • At least one crosslinkable compound selected from the group consisting of crosslinkable compounds having a saturated group, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, Examples include compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film.
  • crosslinkable compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicote 828 (manufactured by Mitsubishi Chemical Corporation), etc.
  • Bisphenol A type epoxy resins Bisphenol F type epoxy resins such as Epicote 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), etc.
  • Biphenyl skeleton-containing epoxy resins phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), Triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.), alicyclic epoxy resin such as Celloxide 2021P (manufactured by Daicel Corporation), N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1, A compound containing a tertiary nitrogen atom represented by 3-bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, Compounds having
  • Examples of compounds for adjusting the dielectric constant and electrical resistance include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine.
  • the content of the monoamine having a nitrogen atom-containing aromatic heterocycle is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Part by mass.
  • Preferred specific examples of the functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrimethoxysilane.
  • the solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferably It is 1 to 10% by mass.
  • the particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when using a spin coating method, it is particularly preferable that the solid content concentration is 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable that the solid content concentration is 3 to 9% by mass, and thereby the solution viscosity is 12 to 50 mPa ⁇ s.
  • the solid content concentration be 1 to 5% by mass and the solution viscosity be 3 to 15 mPa ⁇ s.
  • the temperature when preparing the polymer composition is preferably 10 to 50°C, more preferably 20 to 30°C.
  • a liquid crystal aligning film can be manufactured by using the above-mentioned liquid crystal aligning agent.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film described above.
  • the operation mode of the liquid crystal display element according to the present invention is not particularly limited, and may be, for example, TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, It can be applied to various operation modes such as FFS method and optically compensated bend type (OCB type).
  • the liquid crystal alignment film of the present invention is particularly suitable for horizontal alignment type liquid crystal display elements such as IPS mode or FFS mode.
  • the liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), and a method including steps (1) to (3), (4). ) and (5), or by a method including steps (1) to (3), (4) and (6).
  • Step (1) is a step of applying the liquid crystal aligning agent of the present invention onto a substrate.
  • a specific example of step (1) is as follows.
  • the liquid crystal aligning agent of the present invention is applied onto one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or the like.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and in addition to glass substrates and silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used.
  • an opaque material such as a silicon wafer can be used as long as only one substrate is used, and in this case, a material that reflects light such as aluminum can also be used for the electrodes.
  • a substrate is provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate is not provided with an electrode. and use.
  • Examples of methods for applying the liquid crystal aligning agent to the substrate to form a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, coating and film forming methods using an inkjet method can be suitably used.
  • Step (2) is a step of baking the liquid crystal alignment agent applied onto the substrate to form a film.
  • a specific example of step (2) is as follows. After applying the liquid crystal aligning agent onto the substrate in step (1), the solvent is evaporated by heating means such as a hot plate, a thermal circulation oven, or an IR (infrared ray) oven, or the polyamic acid or polyamic acid ester is heated. It is also possible to perform thermal imidization.
  • the drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and time, and may be performed multiple times.
  • the temperature at which the solvent of the liquid crystal aligning agent is reduced can be, for example, 40 to 180°C.
  • the firing time is not particularly limited, but examples include 1 to 10 minutes or 1 to 5 minutes.
  • a step of firing at a temperature range of 150 to 300° C. or 150 to 250° C. may be added after the above steps.
  • the firing time is not particularly limited, but examples include a firing time of 5 to 40 minutes or 5 to 30 minutes.
  • the thickness of the film-like material after firing is preferably 5 to 300 nm, more preferably 10 to 200 nm, since reliability of the liquid crystal display element may decrease if it is too thin.
  • Step (3) is a step of subjecting the film obtained in step (2) to an orientation treatment, depending on the case. That is, in a horizontal alignment type liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a vertical alignment type liquid crystal display element such as a VA system or a PSA system, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo alignment treatment method.
  • the surface of the film-like material is irradiated with radiation polarized in a certain direction, and optionally, heat treatment is preferably performed at a temperature of 150 to 250°C to improve liquid crystal alignment (liquid crystal alignment).
  • heat treatment is preferably performed at a temperature of 150 to 250°C to improve liquid crystal alignment (liquid crystal alignment).
  • One example is the method of imparting the ability (also called Noh).
  • the radiation ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among these, ultraviolet light having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm.
  • Examples of the above-mentioned rubbing treatment include a treatment in which the coating film is rubbed in a certain direction with a roll wrapped around a cloth made of fibers such as nylon, rayon, and cotton.
  • the radiation when the radiation is polarized light, it may be linearly polarized light or partially polarized light. Further, when the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these may be performed. When irradiating non-polarized radiation, the direction of irradiation is preferably oblique.
  • Step (4) Step of producing a liquid crystal cell> Two substrates each having a liquid crystal alignment film formed thereon as described above are prepared, and a liquid crystal is placed between the two substrates which are placed facing each other. Specifically, the following two methods can be mentioned. In the first method, first, two substrates are placed facing each other with a gap (cell gap) in between so that the respective liquid crystal alignment films face each other. Next, the peripheral parts of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealant to contact the film surface, and then the injection hole is sealed. Stop.
  • the second method is a technique called ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light-curable sealant is applied to a predetermined location on one of the two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is further applied to several predetermined locations on the surface of the liquid crystal alignment film. drip.
  • the other substrate is bonded together so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface.
  • the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
  • the two substrates are arranged facing each other so that the rubbing directions of each coating film are at a predetermined angle, for example, perpendicular or antiparallel to each other.
  • the sealant for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.
  • the liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one type of liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used.
  • a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive type liquid crystal
  • a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative type liquid crystal.
  • the liquid crystal composition may include a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (for example, a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, It may contain a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, and a compound having two or more rigid sites (mesogen skeletons) that exhibit liquid crystallinity within the molecule (for example, two rigid biphenyl structure, or a bimesogenic compound in which a terphenyl structure is connected with an alkylene group).
  • a fluorine atom for example, a trifluoromethyl group
  • a cyano group for example, an alkyl group, an alkoxy group,
  • the liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
  • the above-mentioned liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal alignment.
  • additives include photopolymerizable monomers such as compounds having polymerizable groups; optically active compounds (e.g. S-811 manufactured by Merck & Co., Ltd.); antioxidants; ultraviolet absorbers; pigments; Examples include antifoaming agents; polymerization initiators; and polymerization inhibitors.
  • Examples of the positive liquid crystal include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck & Co., Ltd.
  • Examples of the negative type liquid crystal include MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck & Co., Ltd.
  • a liquid crystal containing a compound having a polymerizable group MLC-3023 manufactured by Merck & Co., Ltd. can be mentioned.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and has a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates.
  • a step of arranging objects and polymerizing a polymerizable compound by at least one of active energy ray irradiation and heating while applying a voltage between electrodes hereinafter, this step is also referred to as step (5)). It is also preferably used for liquid crystal display elements (PSA type liquid crystal display elements).
  • 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 that is polymerized by at least one of active energy rays and heat is provided between the pair of substrates.
  • a liquid crystal display element (SC-PVA type liquid crystal display element) manufactured through a step of arranging a liquid crystal alignment film containing the liquid crystal alignment film and applying a voltage between the electrodes (hereinafter, this step is also referred to as step (6)).
  • this step (6) Preferably used.
  • a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell, if necessary.
  • the polarizing plate bonded to the outer surface of the liquid crystal cell is a polarizing plate in which a polarizing film called "H film” made by stretching and aligning polyvinyl alcohol and absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • a polarizing plate consisting of:
  • An IPS substrate which is a comb-teeth electrode substrate used in the IPS method, includes a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-teeth pattern, and a base material that covers the linear electrodes. It has a liquid crystal alignment film formed as shown in FIG.
  • the FFS substrate which is a comb-teeth electrode substrate used in the FFS method, consists of a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, and an insulating film formed on the insulating film. , has a plurality of linear electrodes arranged in a comb-teeth shape, and a liquid crystal alignment film formed on an insulating film so as to cover the linear electrodes.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention, and is an example of an IPS type liquid crystal display element.
  • a liquid crystal 3 is sandwiched between a comb-teeth electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-teeth electrode substrate 2 includes a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-teeth shape, and a plurality of linear electrodes 2b formed on the base material 2a so as to cover the linear electrodes 2b.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2c is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4c is also the liquid crystal alignment film of the present invention.
  • this horizontal electric field liquid crystal display element 1 when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as shown by lines of electric force L.
  • FIG. 2 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention, and is an example of an FFS type liquid crystal display element.
  • a liquid crystal 3 is sandwiched between a comb-teeth electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-teeth electrode substrate 2 is formed on a base material 2d, a surface electrode 2e formed on the base material 2d, an insulating film 2f formed on the surface electrode 2e, and an insulating film 2f, and has a comb-like shape.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2h is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film of the present invention can be applied to various uses other than the liquid crystal alignment film for the above-mentioned uses, such as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna. It can also be used as a liquid crystal alignment film for a transmission scattering type liquid crystal light control element. Furthermore, applications other than liquid crystal alignment films, such as protective films (e.g., protective films for color filters), spacer films, interlayer insulation films, antireflection films, wiring coating films, antistatic films, motor insulation films (flexible It can also be used as a gate insulating film for displays.
  • protective films e.g., protective films for color filters
  • spacer films interlayer insulation films
  • antireflection films e.g., antireflection films
  • wiring coating films e.g., antistatic films
  • motor insulation films flexible It can also be used as a gate
  • the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.
  • (diamine) DA-1 to DA-3 Compounds represented by the following formulas (DA-1) to (DA-3), respectively.
  • the compounds represented by the above formula (DA-1) are the specific diamines (p)
  • the compounds represented by the above formulas (DA-2) to (DA-3) are compounds included in the range of other diamines.
  • DA-1 was synthesized according to the synthesis method described in WO2015/030071.
  • GPC device GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50°C, eluent: N,N-dimethylformamide (added)
  • lithium bromide monohydrate LiBr H 2 O
  • phosphoric acid/anhydrous crystal o-phosphoric acid
  • tetrahydrofuran (THF) 10 mL/L
  • flow rate 1.0 mL/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide (molecular weight: approx. 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approx. 12, 000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
  • DA-2 (1.50 g, 10.00 mmol) and NMP (11.3 g) were added to a 50 mL four-necked flask equipped with a stirrer and dissolved by stirring at room temperature. Then, by adding CA-1 (2.93 g, 9.95 mmol) and NMP (20.0 g) and stirring at 50°C for 24 hours, a polyamic acid solution (PAA2) with a solid content concentration of 12% by mass (viscosity :302 mPa ⁇ s) was obtained. This polyamic acid had Mn of 5,600 and Mw of 11,900.
  • DA-3 (2.04 g, 15.0 mmol) and NMP (15.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and dissolved by stirring at room temperature. Then, by adding CA-1 (4.06 g, 13.8 mmol) and NMP (29.8 g) and stirring at room temperature for 3 hours, a polyamic acid solution (PAA3) with a solid content concentration of 12% by mass (viscosity: 356 mPa ⁇ s) was obtained. This polyamic acid had Mn of 5,200 and Mw of 13,800.
  • Example 1 The polyamic acid solution (PAA1) obtained in Synthesis Example 1 was diluted with NMP, GBL, and BCS, and stirred at room temperature for 2 hours to determine the mass ratio of polymer solid content to each solvent (polymer solid content: NMP: A liquid crystal aligning agent (AL-1) with GBL:BCS) of 4:46:30:20 was obtained. No abnormalities such as turbidity or precipitation were observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.
  • Liquid crystal alignment agents AL-R1 and AL-R2 were prepared in the same manner as in Example 1 except that PAA2 and PAA3 were used instead of PAA1, respectively. Table 1 shows the composition of each liquid crystal aligning agent obtained in Examples and Comparative Examples. In Table 1, the numerical value in parentheses of the composition ratio represents the ratio (parts by mass) of each component to 100 parts by mass of the components of the liquid crystal aligning agent.
  • a liquid crystal cell having a configuration of a fringe field switching (FFS) mode liquid crystal display element was manufactured.
  • a substrate with electrodes was prepared.
  • the substrate used was a glass substrate measuring 30 mm x 35 mm and having a thickness of 0.7 mm.
  • An ITO electrode with a solid pattern constituting a counter electrode is formed as a first layer on the substrate, and a CVD (chemical vapor deposition) electrode is formed as a second layer on top of the first layer counter electrode.
  • a SiN (silicon nitride) film was formed using a method.
  • As the second layer SiN film a film having a thickness of 300 nm and functioning as an interlayer insulating film was used.
  • a comb-shaped pixel electrode formed by patterning an ITO film as a third layer is arranged on the second layer of SiN film, and two pixels, a first pixel and a second pixel, are formed.
  • the size of each pixel was 10 mm in length and about 5 mm in width.
  • the first-layer counter electrode and the third-layer pixel electrode were electrically insulated by the action of the second-layer SiN film.
  • the third layer pixel electrode has a comb-shaped shape in which a plurality of electrode elements each having a width of 3 ⁇ m and whose central portion is bent at an internal angle of 160° are arranged in parallel with an interval of 6 ⁇ m.
  • Each pixel had a first region and a second region separated by a line connecting the bent portions of the plurality of electrode elements. Comparing the first region and the second region of each pixel, it was found that the formation directions of the electrode elements of the pixel electrodes constituting the first region and the second region were different. That is, when the line connecting the bent portions of the plurality of electrode elements is used as a reference, the electrode elements of the pixel electrode are formed at an angle of 80° clockwise in the first region of the pixel, and in the second region of the pixel. In this case, the electrode elements of the pixel electrode were formed at an angle of 80° counterclockwise.
  • the directions of rotational movement (in-plane switching) within the substrate plane of the liquid crystal induced by voltage application between the pixel electrode and the counter electrode are mutually different. It was configured to run in the opposite direction.
  • the liquid crystal aligning agent obtained above was filtered through a filter with a pore size of 1.0 ⁇ m, and then applied to the surface of the electrode-equipped substrate (first glass substrate) prepared above by a spin coating method.
  • baking was performed for 20 minutes in a hot air circulation oven at 230° C. to obtain a polyimide film with a thickness of 60 nm.
  • This polyimide film was rubbed and oriented with a rayon cloth (HY-5318 manufactured by Hyperflex) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 30 mm/sec, pushing length: 0.4 mm, rubbing direction: third
  • the direction was 180° C. with respect to the direction connecting the bent portions of the plurality of electrode elements of the pixel electrode of the second layer.
  • it was washed by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then dried in an oven at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
  • a glass substrate having a columnar spacer with a height of 4 ⁇ m and an ITO electrode formed on the back surface was also treated in the same manner as above to obtain a substrate with a liquid crystal alignment film subjected to alignment treatment.
  • Ta a sealant (XN-1500T manufactured by Mitsui Chemicals) is printed on one substrate leaving a liquid crystal injection port on the other substrate. They were bonded together so that the alignment film surfaces faced each other and the rubbing directions were antiparallel. Thereafter, heat treatment was performed at 150° C. for 60 minutes to harden the sealant, and empty cells with a cell gap of 4 ⁇ m were produced.
  • Negative liquid crystal MLC-7026-100 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120° C. for 1 hour and left at 23° C. overnight before being used for evaluation.
  • the liquid crystal cell was driven by applying an AC voltage with a frequency of 30 Hz, and the AC drive was performed so that the transmittance inside the cell became 100% every 3 minutes.
  • the curve was measured and the offset voltage that minimized flicker was calculated. Thereafter, the amount of change in the minimum offset voltage value was measured every 3 minutes, and the maximum voltage value when changing within 30 minutes from immediately after lighting was calculated. At that time, if the amount of change in the maximum offset voltage exceeded 20 mV, it was defined as "defective" and evaluated. Further, when the amount of change in the maximum offset voltage did not exceed 20 mV, it was defined as "good” and evaluated.
  • the flicker amplitude is determined by converting the transmitted light of the LED backlight that has passed through two polarizing plates and the liquid crystal cell between them into a data acquisition/data logger switch unit 34410A (KEYSIGHT Co., Ltd.) connected via a photodiode and an IV conversion amplifier. (Manufactured).
  • z is the value of the brightness read by the data collection/data logger switch unit 34410A when driven with an AC voltage with a frequency of 30 Hz, which gives a relative transmittance of 23%.
  • the evaluation of photoresponsiveness is "good” if the amount of change in flicker level remains less than 3% within 30 minutes from the time when the LED backlight is turned on and the application of AC voltage is started. When the above was reached, it was defined as “poor” and evaluated. The results are shown in Table 2. Note that the evaluation of photoresponsiveness according to the method described above was performed under room temperature conditions.
  • Example 1 and Comparative Examples 1-2 Characteristic evaluation results regarding liquid crystal display elements obtained using the liquid crystal aligning agents (AL-1) and (AL-R1) to (AL-R2) obtained in Example 1 and Comparative Examples 1 and 2 above are shown below. It is shown in Table 2.
  • the liquid crystal display device using the liquid crystal aligning film of Example 1 obtained from the liquid crystal display agent had good both of the relaxation rate of accumulated charges and the photoresponsiveness.

Abstract

L'invention concerne un agent d'alignement de cristaux liquides capable de produire : un film d'alignement de cristaux liquides dans lequel une charge générée peut être abaissée en peu de temps tandis que la valeur absolue de la charge accumulée est abaissée ; et un film d'alignement de cristaux liquides dans lequel l'accumulation de charge et le papillotement attribuables à la lumière d'un rétroéclairage sont réduits.　Cet agent d'alignement de cristaux liquides contient au moins un type de polymère (P) choisi dans le groupe constitué par : un précurseur de polyimide obtenu à l'aide d'au moins un type de composant d'acide tétracarboxylique choisi dans le groupe constitué par les dianhydrides d'acide tétracarboxylique représentés par la formule (1) et leurs dérivés et un composant diamine représenté par la formule (2) ; et un polyimide qui est un produit d'imidation dudit précurseur de polyimide. (Xa représente un groupe organique tétravalent dérivé d'un dianhydride d'acide tétracarboxylique aromatique ou d'un dérivé de celui-ci. Y2 représente un groupe organique divalent ayant de 6 à 30 atomes de carbone et contenant un ou plusieurs groupes aromatiques. Des fractions Z2 représentent chacune indépendamment un groupe alkylène ayant de 1 à 6 atomes de carbone. Des fractions A2 représentent chacune indépendamment un groupe alkyle ayant de 1 à 6 atomes de carbone. Un atome d'hydrogène arbitraire dans un groupe aromatique dans Y2 peut être substitué par un groupe monovalent.)
PCT/JP2023/015956 2022-04-27 2023-04-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2023210532A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008078796A1 (fr) * 2006-12-27 2008-07-03 Nissan Chemical Industries, Ltd. Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides utilisant celui-ci et élément d'affichage à cristaux liquides
CN112225675A (zh) * 2020-09-22 2021-01-15 江苏三月科技股份有限公司 一种芳胺类化合物及其制备的液晶取向剂、液晶取向膜和液晶显示元件
CN114085680A (zh) * 2021-12-02 2022-02-25 深圳市道尔顿电子材料有限公司 一种适用于摩擦型ips的双层型聚酰亚胺液晶取向剂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008078796A1 (fr) * 2006-12-27 2008-07-03 Nissan Chemical Industries, Ltd. Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides utilisant celui-ci et élément d'affichage à cristaux liquides
CN112225675A (zh) * 2020-09-22 2021-01-15 江苏三月科技股份有限公司 一种芳胺类化合物及其制备的液晶取向剂、液晶取向膜和液晶显示元件
CN114085680A (zh) * 2021-12-02 2022-02-25 深圳市道尔顿电子材料有限公司 一种适用于摩擦型ips的双层型聚酰亚胺液晶取向剂及其制备方法

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