Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
  • C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

• the present invention relates to liquid crystal aligning agents, liquid crystal aligning films, liquid crystal display elements, and compounds and polymers that can be used therefor.
• a liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling the orientation of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) or the like is provided for switching an electric signal supplied to the pixel electrode.
• TFT thin film transistor
• Driving methods for liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.
• TN Transmission Nematic
• VA Very Alignment
• IPS In-Plane Switching
• FFS Frringe Field Switching
• the liquid crystal alignment film that is most widely used industrially is formed on an electrode substrate, and the surface of a film made of a polymer typified by polyamic acid and/or polyimide imidized thereof is coated with cotton, nylon, or the like. It is produced by rubbing in one direction with a cloth such as polyester.
• the rubbing treatment is a simple, highly productive and industrially useful method.
• a photo-alignment method As an alignment treatment method that replaces the rubbing treatment, a photo-alignment method is known in which polarized radiation is applied to impart liquid crystal alignment ability.
• a photo-alignment method a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, and the like have been proposed (see, for example, Non-Patent Document 1 and Patent Document 1).
• Liquid crystal display elements of the IPS driving method and the FFS driving method are required to have a high contrast.
• a liquid crystal aligning agent containing a polyimide precursor or polyimide having a specific structure has been proposed.
• the object of the present invention is a liquid crystal aligning agent that can obtain a liquid crystal aligning film with small variation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal aligning film, and from the liquid crystal aligning agent It is to provide a liquid crystal alignment film obtained, a liquid crystal display element using the liquid crystal alignment film, and a compound and a polymer that can be used for them.
• the present invention includes the following aspects.
• a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, a diamine component, and an active ester compound (B) represented by the following formula (1):
• Obtained containing one or more polymers (A) selected from the group consisting of polyimide precursors and polyimides that are imidized products of the polyimide precursors,
• the polymer (A) has a group represented by the following formula (1A) derived from the active ester compound (B), Liquid crystal aligning agent.
• W is *1-NH(Boc), *1-N(Boc) 2 , and "*1-N(Boc)-*1)"
• *1 represents a bond that binds to a carbon atom.
• R represents an organic group having 1 to 30 carbon atoms excluding a Boc group and having a group having a protected amino moiety selected from the group consisting of: Boc represents a tert-butoxycarbonyl group.
• R represents an active ester-forming group. However, when R represents a group derived from N-hydroxysuccinimide, W has two or more of the above protected amino sites. ) (W has the same definition as formula (1). * represents a bond that binds to the polymer.)
• a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film with small variation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal aligning film, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and It is possible to provide a liquid crystal display device using the liquid crystal alignment film, and compounds and polymers that can be used therefor.
• the active ester compound (B) reacts with the terminal of the polymer to obtain a highly hydrophobic polymer having a protected amino group introduced to the terminal.
• the polymer having the protective amino group introduced tends to be unevenly distributed on the film surface, so that a liquid crystal alignment film with improved alignment uniformity can be obtained.
• the polymer terminal is protected by the active ester compound (B) reacting with the polymer terminal.
• halogen atom includes fluorine atom, chlorine atom, bromine atom, iodine atom and the like.
• Boc represents a tert-butoxycarbonyl group, and "*" represents a binding position.
• the liquid crystal aligning agent of the present invention contains a polymer (A) (hereinafter also referred to as a polyimide polymer (A)).
• the polymer (A) is one or more selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors.
• a polyimide precursor for the polymer (A) is obtained by reacting a tetracarboxylic acid derivative component, a diamine component, and the active ester compound (B).
• the tetracarboxylic acid derivative component includes at least one compound selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof (hereinafter collectively referred to as tetracarboxylic dianhydride-based compounds).
• the polymer (A) has a group represented by the formula (1A) derived from the active ester compound (B).
• the polyimide precursor include polyamic acid and polyamic acid ester.
• Examples of the tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
• the polymer (A) itself is also an object of the present invention independently of the liquid crystal aligning agent of the present invention.
• the polyimide polymer (A) includes, for example, a tetracarboxylic acid derivative component containing tetracarboxylic dianhydride, a diamine component, and an active ester compound ( B) can be obtained by a polymerization (polycondensation) reaction.
• the active ester compound (B) is added to the polymer solution.
• the polyimide in the polyimide polymer (A) is obtained by imidizing the polyamic acid. Furthermore, when the polyimide-based polymer (A) is a polyamic acid ester, it can be obtained by the method described later, and a polyimide is obtained by imidating the polyamic acid ester.
• tetracarboxylic dianhydride-based compound examples include aromatic tetracarboxylic dianhydrides, acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and derivatives thereof. be done.
• 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.
• An acyclic 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 need to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part thereof.
• the aromatic tetracarboxylic dianhydride or derivative thereof has at least one partial structure selected from the group consisting of a benzene ring structure, a naphthalene ring structure, and an aromatic heterocyclic structure from the viewpoint of enhancing liquid crystal orientation.
• a tetracarboxylic dianhydride or a derivative thereof is preferable.
• An 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 are bonded to the aromatic ring. Moreover, it is not necessary to consist 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 dianhydrides are selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure from the viewpoint of enhancing liquid crystal orientation among others.
• a tetracarboxylic dianhydride having at least one partial structure or a derivative thereof is preferred.
• aromatic tetracarboxylic dianhydride acyclic aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is, among others, a tetracarboxylic dianhydride represented by the following formula (2) is preferred.
• X represents a structure selected from the group consisting of the following formulas (x-1) to (x-17) and the following formulas (xr-1) to (xr-2).)
• R 1 to R 4 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, a an alkynyl group, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or represents a phenyl group, wherein R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and in formulas (xr-1) to (xr-2), j and k is an integer of 0 or 1, and A 1 and A 2 each independently represent a single bond, —O—, —CO—, —COO—, a phenylene group, a sulfonyl group, or an amide
• Preferred specific examples of the tetracarboxylic dianhydride represented by the above formula (2) include X being the above formulas (x-1) to (x-8), (x-10) to (x-11) , and (xr-1) to (xr-2).
• the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6).
• the amount of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) when producing the polyimide polymer (A) is 1 mol of the total tetracarboxylic acid derivative component to be reacted with the diamine component. On the other hand, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is still more preferable.
• the polyimide polymer (A) of the present invention is obtained by using the active ester compound (B) represented by the above formula (1). By adopting such a mode, it is possible to provide a function that the variation (non-uniformity) of the twist angle when used as a liquid crystal display device is small.
• the active ester compound (B) itself is also a subject of the present invention independently of the liquid crystal aligning agent of the present invention.
• R represents an active ester-forming group.
• the "active ester-forming group” activates the carbonyl group with respect to the coupling reaction with an amino group-containing compound that forms an amide group and other coupling reactions together with the carbonyl group to which it is attached. It refers to a chemical group that forms an ester.
• active ester-forming groups are 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), N-hydroxysuccinimide (HOSu), ethyl 2-cyano-2-(hydroxyimino)acetate.
• hydroxy compounds (oxyma), 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine (HOOBt or HODhbt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB) , 2,3,4,5,6-pentafluorophenol (HOPfp), or hydroxy compounds such as 6-chloro-1-hydroxy-1H-benzotriazole (Cl-HOBt) (for example, catalog of WATANABE Chemical, Amino (see acids and chiral building blocks to new medicine. Hereinafter, these are also collectively referred to as hydroxy compounds (Ae).).
• a group obtained by removing a hydroxy group from HOBt, HOAt, HOSu, or HOOBt is preferable, and a group obtained by removing a hydroxy group from HOBt, HOAt, or HOOBt is more preferable, from the viewpoint of suitably obtaining the effects of the present invention.
• W has two or more of the protected amino sites. Since the active ester derived from HOSu is considered to be relatively difficult to react with the terminal of the polymer, in this case, a sufficient effect can be obtained by introducing two or more protected amino sites.
• W in the above formula (1) is *1-NH(Boc), *1-N(Boc) 2 and "*1-N(Boc)-*1)" (*1 is bound to a carbon atom represents a bond), and represents an organic group having 1 to 30 carbon atoms excluding a Boc group, having a group having one or more protected amino sites selected from the group consisting of: When there are two or more protected amino sites, each protected amino site may be the same or different. From the viewpoint of suitably obtaining the effects of the present invention, the number of protected amino moieties is 1 or more, and from the viewpoint of the effect of liquid crystal orientation, the number of protected amino moieties is preferably 4 or less.
• the organic group having 1 to 30 carbon atoms excluding the Boc group is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 6 carbon atoms. preferable.
• W is, specifically, "W-COOH" (W is synonymous with formula (1).
• W also referred to as carboxylic acid (W).)
• W A group obtained by removing the carboxyl group from a carboxylic acid represented by is mentioned.
• the active ester compound (B) is synthesized, for example, from carboxylic acid (W) and hydroxy compound (Ae).
• the above carboxylic acid (W) has *1-NH(Boc), *1-N(Boc) 2 and “*1-N(Boc)-*1)” (*1 is a carbon atom a group having a protected amino site selected from the group consisting of:
• the carboxylic acid (W) protects the amino groups possessed by the carboxy group-containing polyamine (pA) having two or more amino groups, represented by, for example, a carboxy group-containing monoamine (mA) or a carboxy group-containing diamine. obtained by As for the protection of amino groups, some of the amino groups possessed by the amine may be protected, or all of the amino groups may be protected.
• monoamines (mA) include 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4 -aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2 -Carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-amino Aromatic monoamines such as nicotinic acid, 6-aminonic
• polyamines (pA) include diaminobenzoic acids such as 3,5-diaminobenzoic acid; carboxybiphenyl compounds such as 4,4'-diaminobiphenyl-3-carboxylic acid; 4,4'-diaminodiphenylmethane-3 -carboxylic acid or carboxydiphenylalkanes such as 4,4'-diaminodiphenylethane-3-carboxylic acid; 4,4'-diaminodiphenylether-3-carboxylic acid or 4,4'-diaminodiphenylether-3-carboxylic acid aromatic polyamines represented by carboxydiphenyl ethers such as acids; and aliphatic polyamines such as arginine, lysine, ornithine, or histidine.
• diaminobenzoic acids such as 3,5-diaminobenzoic acid
• carboxybiphenyl compounds such as 4,4'-di
• the carboxylic acid (W), monoamine (mA), and polyamine (pA) preferably have a nitrogen atom-containing heterocyclic ring or a derivative thereof, among others, from the viewpoint of suitably obtaining the effects of the present invention.
• Specific examples of the nitrogen atom-containing heterocyclic ring include aziridine, azetidine, pyrrole, imidazole, imidazolidine, pyrrolidine, piperidine, piperazine, morpholine, pyrazole, indole, benzimidazole, or carbazole.
• specific examples of derivatives of nitrogen atom-containing heterocyclic rings include compounds in which any hydrogen atom of the nitrogen atom-containing heterocyclic ring is substituted with a substituent.
• substituents examples include linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxy groups having 1 to 4 carbon atoms, hydroxy groups, halogen atoms, nitro group, cyano group, trifluoromethyl group, —NR 7 R 8 or —CONR 7 R 8 group, wherein R 7 and R 8 each independently represent a hydrogen atom, linear or branched It represents a chain alkyl group having 1 to 4 carbon atoms.
• the active ester compound represented by formula (1) above is preferably any one of the compounds represented by formulas (b-1) to (b-7) below.
• the proportion of the active ester compound (B) used when producing the polyimide polymer (A) is preferably 0.01 to 50 mol parts per 100 mol parts of the total diamine component used, and 0.1 ⁇ 30 mole parts is more preferred.
• the diamine component used for producing the polyimide precursor is not particularly limited, a diamine component containing a diamine represented by the following formula (3) is preferable.
• Ar 1 and Ar 1′ each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more A hydrogen atom may be substituted with a monovalent group
• Ar 1 and Ar 1' in the formula (3) each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring.
• One or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group, and the monovalent group includes a halogen atom, an alkyl having 1 to 3 carbon atoms, group, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, An alkyloxycarbonyl group having 2 to 3 carbon atoms, a cyano group, a nitro group and the like can be mentioned.
• the bonding position between the amino group and L 1 or L 1′ with respect to the benzene ring is preferably 1,4-position or 1,3-position, and 1 , 4-position is more preferred.
• the bonding positions of the amino group and L 1 or L 1′ with respect to the biphenyl structure are preferably 4,4′-positions or 3,3′-positions, more preferably 4,4′-positions.
• the bonding positions of the amino group and L 1 or L 1′ with respect to the naphthalene ring are preferably 1,5-positions or 2,6-positions, more preferably 2,6-positions.
• Preferred specific examples of Ar 1 and Ar 1' include a benzene ring, a biphenyl structure and a naphthalene ring.
• a preferred specific example of A is a linear alkylene group having 2 to 6 carbon atoms.
• n is an integer of 1-12, more preferably an integer of 2-12, and even more preferably an integer of 2-6.
• the sum of m1, m2 and n' is an integer of 3-12, preferably an integer of 6-12.
• Each of m1 and m2 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4.
• n′ is preferably an integer of 1-6, more preferably an integer of 2-6, and even more preferably an integer of 2-4.
• the ratio of the diamine represented by formula (3) is preferably 1 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, relative to 1 mol of the diamine component. preferable.
• the polyimide polymer (A) may contain diamines other than the diamines described above. Examples of other diamines are listed below, but the present invention is not limited to these. In addition to the diamine represented by the above formula (3), when other diamines are used in combination, the amount of the diamine represented by the formula (3) to the diamine component is preferably 90 mol% or less, and 80 mol%. The following are more preferred. Examples of other diamines are listed below, but the present invention is not limited to these. The other diamines may be used singly or in combination of two or more.
• p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1, 4-diamino-2,5-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, secondary amino group and primary
• a semi-aromatic diamine having an amino group preferably 4-(2-(methylamino)ethyl)aniline) (here, the semi-aromatic diamine refers to and the other amino group refers to a diamine not bound to an aromatic ring.), 4-(2-aminoethyl)aniline, 2-(6-amino-2-naphthyl)ethylamine, 2,2
• At least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary or tertiary amino group, typified by a diamine having a diphenylamine structure of -N(D)- (D represents a protective group that is eliminated by heating and replaced with a hydrogen atom. ) except amino groups derived from );
• m and n are each an integer of 0 to 3 (provided that 1 ⁇ m + n ⁇ 4), j is an integer of 0 or 1, and X 1 is - (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CO—N(CH 3 )—, —NH—, —O—, —CH 2 O— , —CH 2 —OCO—, —COO—, or —OCO—, wherein 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, represents an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, wherein X 2 is -O- or -
• D in -N(D)- of the other diamines described above is a carbamate-based protective group represented by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, Boc, and the like.
• Boc is particularly preferred from the viewpoint that it is efficiently desorbed by heat, is desorbed at a relatively low temperature, and is discharged as a harmless gas when desorbed.
• diamines having thermally-leaving groups include diamines selected from the following formulas (d-1) to (d-7).
• R represents a hydrogen atom or Boc.
• the diamine having the thermally-leaving group is used as the diamine component used in the production of the polyimide precursor, from the viewpoint of suitably obtaining the effect of the present invention, it is preferably 5 to 40 mol per 1 mol of the diamine component. %, more preferably 5 to 35 mol %, even more preferably 5 to 30 mol %.
• the liquid crystal aligning agent of this invention may contain other polymers other than a polymer (A).
• other polymers include a polyimide precursor and the polyimide obtained by using a tetracarboxylic acid derivative component and a diamine component without using the active ester compound (B) represented by the above formula (1) as a raw material.
• At least one polymer (Q) selected from the group consisting of polyimides that are imidized precursors, polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-malein anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate
• Examples include polymers selected from the group consisting of From the viewpoint of increasing the voltage holding ratio, the polymer (Q) is selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine having a nitrogen atom-containing structure and an imidized product of the polyimide precursor.
• polyimide polymer (hereinafter also referred to as polyimide polymer (Q)).
• poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like.
• Anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether anhydride). maleic acid resin, manufactured by Ashland).
• Other polymers may be used singly or in combination of two or more.
• the content of the other polymer is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.
• a polymer component is a general term for other polymers other than a polymer (A) and a polymer (A) contained in a liquid crystal aligning agent. When the polymer contained in the liquid crystal aligning agent is only the polymer (A), the polymer component refers to the polymer (A).
• Examples of the tetracarboxylic acid derivative component for obtaining the polyimide polymer (Q) include tetracarboxylic acid derivative components containing the tetracarboxylic dianhydride compounds exemplified for the polyimide polymer (A). .
• the tetracarboxylic dianhydride-based compound for obtaining the polyimide polymer (Q) is preferably a tetracarboxylic dianhydride represented by the above formula (2) or a derivative thereof.
• the amount of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) is preferably 10 mol% or more, preferably 20 mol%, based on 1 mol of the total tetracarboxylic acid derivative component to be reacted with the diamine component.
• the above is more preferable.
• Polyamic acid which is one of polyimide precursors, can be produced by the following method. Specifically, a tetracarboxylic acid derivative component containing a tetracarboxylic dianhydride and the diamine component are mixed in the presence of an organic solvent at a temperature of preferably -20 to 150°C, more preferably 0 to 50°C. It can be synthesized by reaction (polycondensation reaction) for 30 minutes to 24 hours, preferably 1 to 12 hours.
• organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone can be mentioned.
• methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or propylene glycol monomethyl ether ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used. These may be used in combination of two or more.
• the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial stage of the 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 derivative component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.
• the polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring well. Further, a purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. Poor solvents include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
• a polyamic acid ester which is one of the polyimide precursors, can be obtained by (1) a method of esterifying the polyamic acid, (2) a method of reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester dichloride with a diamine component, ( 3) It can be produced by a known method such as a method of polycondensing a tetracarboxylic acid derivative component including a tetracarboxylic acid diester with a diamine.
• the above-mentioned polyamic acid and polyamic acid ester may be a terminal-modified polymer obtained by using an appropriate terminal blocking agent together with the tetracarboxylic acid derivative component and the diamine component as described above when producing them.
• Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride.
• Acid monoanhydrides such as anhydrides; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; aniline, 2-aminophenol, 3 -aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n - monoamine compounds such as hexylamine,
• the proportion of the terminal blocking agent used is preferably 40 mol parts or less, more preferably 30 mol parts or less, with respect to a total of 100 mol parts of the diamine component used. Moreover, the proportion of the terminal blocker used is preferably 0.01 mol or more, more preferably 0.1 mol or more, with respect to a total of 100 mol parts of the diamine component used.
• the polyimide used in the present invention can be produced by imidizing the above polyimide precursor by a known method.
• the ring closure rate (also referred to as imidization rate) of the functional groups of the polyamic acid or polyamic acid ester does not necessarily need to be 100%, and can be arbitrarily adjusted according to the application and purpose.
• the imidization rate of the polyimide in the polymer (A) of the present invention may be, for example, 20 to 100%, 50 to 99%, or 70 to 99% from the viewpoint of reducing the occurrence rate of display defects.
• thermal imidization is performed by heating the solution of the polyamic acid or polyamic acid ester as it is, or a catalyst (eg, catalyzed imidization by adding a basic catalyst such as pyridine, an acid anhydride such as acetic anhydride).
• a catalyst eg, catalyzed imidization by adding a basic catalyst such as pyridine, an acid anhydride such as acetic anhydride.
• the polyamic acid, polyamic acid ester and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1000 mPa s when the concentration is 10 to 15% by mass, from the viewpoint of workability. , is not particularly limited.
• the solution viscosity (mPa s) of the polymer is a polymer having a concentration of 10 to 15 mass% prepared using a good solvent for the polymer (eg, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25° C. for a solution using an E-type rotational viscometer.
• the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ⁇ 500,000.
• 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. With such a molecular weight range, it is possible to ensure good liquid crystal orientation of the liquid crystal display element.
• the liquid crystal aligning agent of this invention is used in order to produce a liquid crystal aligning film, and takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of the present invention, it is preferable that the liquid crystal aligning agent is a coating liquid containing the above-described polymer component and a solvent.
• the content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed. 1 mass % or more is preferable with respect to the whole quantity of a point and a liquid crystal aligning agent, and 10 mass % or less is preferable from the point of the storage stability of a solution.
• the content of the polymer (A) in the liquid crystal aligning agent is preferably 10 parts by mass or more with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. Yes, more preferably 20 parts by mass or more, and still more preferably 50 parts by mass or more.
• the content of the polymer (A) is preferably 10 to 90 parts by mass, preferably 20 to 80 parts by mass, with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Parts by mass are more preferred.
• the solvent contained in the liquid crystal aligning agent is not particularly limited as long as it uniformly dissolves the polymer component.
• Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide and ⁇ -butyrolactone.
• ⁇ -valerolactone 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 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-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2 -pyrrolidone (these are collectively referred to as "
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and ⁇ -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 solvent contained in the liquid crystal aligning agent is a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent is used in addition to the above solvent. is preferred. Specific examples of the poor solvent used in combination 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, 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 according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.
• 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 are preferred.
• Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- Pyrrolidone, ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N
• the liquid crystal aligning agent of the present invention may additionally contain components (hereinafter also referred to as additive components) other than the polymer component and the solvent.
• additive components include compounds for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as cross-linking compounds), adhesion between the liquid crystal alignment film and the substrate, and adhesion between the liquid crystal alignment film and the sealing agent. Adhesion aids for increasing the dielectric constant and electrical resistance of the liquid crystal alignment film, dielectrics and conductive substances.
• crosslinkable compound examples include a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group.
• crosslinkable compound (c-1) and (c-2) include the following compounds.
• epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane.
• Polymers and oligomers having an oxazoline group such as compounds described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597;
• compounds having a cyclocarbonate group N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N' ,-Di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine and paragraphs [0025] to [0030] and [0032] of WO2011/155577 compounds of;
• Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B
• crosslinkable compounds are examples of crosslinkable compounds, and are not limited to these.
• components other than those described above disclosed on pages 53 [0105] to 55 [0116] of WO2015/060357 may be used.
• the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. , more preferably 1 to 15 parts by mass.
• adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N -ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropylprop
• the content of the adhesion aid in the liquid crystal aligning agent is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer component contained in the liquid crystal aligning agent, and more It is preferably 0.1 to 20 parts by mass.
• dielectric or conductive substances include monoamines having nitrogen-containing aromatic heterocycles such as 3-picolylamine.
• the content of the dielectric or conductive substance in the liquid crystal aligning agent is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is preferred, and more preferably 0.1 to 20 parts by mass.
• the liquid crystal aligning film of the present invention is formed using the liquid crystal aligning agent of the present invention.
• the method for producing a liquid crystal alignment film of the present invention includes, for example, applying the above liquid crystal alignment agent to a substrate, baking the substrate, and irradiating the resulting film with polarized radiation.
• a preferred embodiment of the method for producing a liquid crystal alignment film of the present invention includes, for example, the step of applying the liquid crystal alignment agent to the substrate (step (1)), and the step of baking the applied liquid crystal alignment agent (step (2)). and a method for producing a liquid crystal alignment film, which optionally includes a step (step (3)) of subjecting the film obtained in step (2) to orientation treatment.
• the substrate to which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can also be used. In that case, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed, in terms of process simplification.
• an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes.
• Screen printing, offset printing, flexographic printing, inkjet method, spray method, etc. can be used as methods for applying the liquid crystal aligning agent to the substrate and forming a film.
• the coating method and the film-forming method by the inkjet method can be preferably used.
• a process (2) is a process of baking the liquid crystal aligning agent apply
• a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven is used to evaporate the solvent or heat the amic acid or amic acid ester in the polymer. imidization can be performed.
• the drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any desired temperature and time, and may be performed multiple times.
• the temperature for evaporating the solvent of the liquid crystal aligning agent can be, for example, 40 to 180° C.
• the temperature of the heating means may be 40 to 150° C. from the viewpoint of shortening the process.
• the firing time is not particularly limited, it is, for example, 1 to 10 minutes, preferably 1 to 5 minutes.
• the temperature of the heating means is, for example, 150 to 300. C., preferably in the temperature range of 150-250.degree.
• the baking time in the thermal imidization step is not particularly limited, but is, for example, 5 to 40 minutes, preferably 5 to 30 minutes.
• the thickness of the film after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may be lowered.
• Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a vertical alignment type liquid crystal display element such as a VA system or a PSA (Polymer Sustained Alignment) system, the formed coating film can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment ability imparting treatment. may be applied.
• a rubbing treatment method may be used, but a photo-alignment treatment method is preferable.
• Examples of the photo-alignment treatment include a method in which the surface of the film is irradiated with radiation polarized in a certain direction, and in some cases, heat treatment is performed to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). be done.
• liquid crystal alignment also referred to as liquid crystal alignment ability
• radiation ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.
• the radiation dose is preferably 1 to 10,000 mJ/cm 2 , more preferably 100 to 5,000 mJ/cm 2 .
• the substrate having the film-like material may be irradiated with heating at 50 to 250° C. in order to improve liquid crystal orientation.
• the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a fixed direction.
• the liquid crystal alignment film irradiated with polarized radiation can be subjected to a contact treatment using a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
• the solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material by irradiation with radiation.
• Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
• water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate are preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate.
• Solvents may be used singly or in combination of two or more.
• the above contact treatment includes immersion treatment and spray treatment (also called spray treatment).
• the treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products produced from the film-like material by irradiation with radiation. Among them, it is more preferable to perform the immersion treatment for 1 minute to 30 minutes.
• the solvent used in the contact treatment may be at room temperature or heated, but is preferably 10 to 80°C, more preferably 20 to 50°C.
• ultrasonic treatment or the like may be performed as necessary.
• rinsing also called rinsing
• a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone
• baking either one of rinsing and baking may be performed, or both may be performed.
• the firing temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and still more preferably 200 to 230°C.
• the firing time is preferably 10 seconds to 30 minutes, more preferably 1 minute to 10 minutes.
• the heat treatment of the radiation-irradiated coating film is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.
• the liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention.
• the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a horizontal electric field type liquid crystal display element such as an IPS type or an FFS type liquid crystal display element from the viewpoint of obtaining high liquid crystal orientation, and is particularly suitable for an FFS type liquid crystal display element. It is useful as a liquid crystal alignment film.
• the liquid crystal display element is produced by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, producing a liquid crystal cell by a known method, and arranging the liquid crystal in the liquid crystal cell. can be done. Specifically, the following two methods are mentioned.
• the first method first, two substrates are arranged facing each other with a gap (cell gap) between them so that the respective liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.
• the second method is a technique called the ODF (One Drop Fill) method.
• a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip.
• the other substrate is attached 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 liquid crystal composition used is further heated to a temperature at which it assumes an isotropic phase, and then slowly cooled to room temperature, so that the flow orientation at the time of filling the liquid crystal should be removed.
• the coating film is subjected to the rubbing treatment, the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
• the alignment directions are arranged to face each other at a predetermined angle, for example, perpendicular or antiparallel.
• Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
• the liquid crystal composition is not particularly limited, and is a composition containing at least one liquid crystal compound (liquid crystal molecule) and having a positive dielectric anisotropy (positive liquid crystal composition, also referred to as positive liquid crystal). ) or a liquid crystal composition having a negative dielectric anisotropy (also referred to as a negative liquid crystal composition or negative liquid crystal), but a negative liquid crystal material is preferable.
• the above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane,
• a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structure, or a bimesogenic compound in which a terphenyl structure is linked by an alkyl 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 liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation.
• additives include photopolymerizable monomers such as compounds having a polymerizable group described below, optically active compounds (eg S-811 manufactured by Merck & Co.), antioxidants, ultraviolet absorbers, dyes, antiseptics. foaming agents, polymerization initiators, polymerization inhibitors, and the like.
• Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
• the negative liquid crystal for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC- 7029 and the like.
• MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group. Next, a polarizing plate is installed.
• a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer.
• the polarizing plate include a polarizing plate in which a polarizing film called "H film” in which iodine is absorbed while stretching orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate composed of the H film itself.
• NMP N-methyl-2-pyrrolidone
• BCS butyl cellosolve (ethylene glycol monobutyl ether)
• AD-1 to AD-6 are novel compounds that have not been published in literature, etc., and their synthesis methods will be described in detail below.
• AD-7 a commercial product (manufactured by Merck) was purchased and used.
• Boc 2 O di-tert-butyl dicarbonate
• THF tetrahydrofuran
• DMF N,N-dimethylformamide
• EDC 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
• BOP reagent benzotriazolyl-N-hydroxytris (dimethylamino)phosphonium hexafluorophosphide salt
• AD-1-1 (1.75 g, 4.96 mmol) and THF (12.3 g) in a flask, add EDC (1.16 g, 7.44 mmol), and cool to room temperature (25° C.). and stirred for 30 minutes. After that, a solution of 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine (0.816 g, 5.00 mmol) dissolved in THF (5.3 g) was added, 25° C.) for 15 hours. After completion of the reaction, ethyl acetate (18 g) and pure water (18 g) were added for liquid separation, and the organic layer was washed twice with pure water.
• AD-6 was obtained ( Yield: 4.70 g, 12.3 mmol, Yield: 93%). From the 1 H-NMR results shown below, this solid was confirmed to be AD-6.
• Example 1 Liquid crystal aligning agent (AL-1) to (AL-7) was obtained.
• the sample solutions prepared above are summarized in Table 1 below.
• a liquid crystal cell having the structure of an FFS mode liquid crystal display element was produced.
• a substrate with electrodes was prepared.
• a glass substrate having a rectangular shape of 35 mm ⁇ 40 mm and a thickness of 0.7 mm was used as the substrate.
• an ITO electrode thinness: 50 nm, electrode width: 20 mm long, 10 mm wide
• a SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method was formed.
• the SiN film of the second layer has a film thickness of 300 nm and functions as an interlayer insulating film.
• a comb-shaped pixel electrode formed by patterning an ITO film is arranged as a third layer, and two pixels of a first pixel and a second pixel are formed.
• the size of each pixel was 10 mm long and about 5 mm wide.
• the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.
• the pixel electrode of the third layer has a comb shape in which a plurality of electrode elements each having a width of 3 ⁇ m and having a central portion 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 bounded by a line connecting bent portions of a plurality of electrode elements.
• the coating film surface was irradiated with 500 mJ/cm 2 of linearly polarized ultraviolet light having a wavelength of 254 nm and an extinction ratio of 26:1 through a polarizing plate for alignment treatment, and then baked in an IR oven at 230° C. for 30 minutes.
• a substrate with a liquid crystal alignment film was obtained.
• the liquid crystal alignment film formed on the substrate with the electrode is aligned so that the direction of equally dividing the interior angle of the bent portion of the pixel is orthogonal to the alignment direction of the liquid crystal, and the liquid crystal alignment film is formed on the second glass substrate.
• liquid crystal alignment obtained using liquid crystal alignment agents AL-1 to AL-7 of Examples 1 to 7 containing polyamic acids terminally modified with terminal modifiers AD-1 to AD-7 The film had better in-plane uniformity of contrast than the liquid crystal alignment film obtained using the liquid crystal alignment agent AL-C1 of Comparative Example 1, which did not contain terminally modified polyamic acid.
• the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention can be suitably used for various liquid crystal display elements, typified by liquid crystal display elements of the IPS drive system and the FFS drive system. These display elements are not limited to liquid crystal displays intended for display, and are also useful in light control windows and optical shutters for controlling the transmission and blocking of light.

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