Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
  • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
  • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
  • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
  • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
  • C07C217/86—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element comprising the liquid crystal aligning film.
• Liquid crystal display elements are used in a wide range of applications, from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors.
• various driving methods with different electrode structures and physical properties of the liquid crystal molecules used have been developed.
• -Plane Switching FFS (Fringe Field Switching), and other liquid crystal display devices using various modes are known.
• These liquid crystal display elements generally have a liquid crystal alignment film that is indispensable for controlling the alignment state of liquid crystal molecules.
• Polyamic acid and polyimide are generally used as materials for liquid crystal alignment films because of their excellent properties such as heat resistance, mechanical strength, and affinity with liquid crystals.
• the liquid crystal alignment film that is most widely used industrially is a so-called rubbing alignment treatment in which the surface of a resin film such as polyimide formed on an electrode substrate is rubbed in one direction with a cloth such as cotton, nylon, or polyester. It is made by doing.
• the rubbing orientation treatment is a useful method that is simple and excellent in productivity.
• a photo-alignment treatment method is known in which polarized radiation is applied to impart liquid crystal alignment ability.
• a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, etc. have been proposed (for example, Non-Patent Document 1, Patent Document 1, Patent Document 2).
• liquid crystal display elements In recent years, as the performance of liquid crystal display elements has improved, in addition to large-screen, high-definition liquid crystal televisions, it has been applied to in-vehicle applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors. is being considered. Therefore, the demand for higher performance, particularly higher definition, of liquid crystal display elements is increasing, and a liquid crystal alignment film capable of further improving various characteristics of liquid crystal display elements is desired.
• a washing step with a solvent may be carried out after the alignment treatment in order to remove impurities.
• solvent repelling and droplets are generated during air knife drying, resulting in locally non-uniform cleaning of the film surface. Unevenness may occur.
• the present invention has been made in view of the above circumstances, and expands the range of light irradiation amount for obtaining a liquid crystal alignment film with small variation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal alignment film.
• a liquid crystal aligning agent that is capable of forming a liquid crystal aligning film having a high water contact angle for obtaining a liquid crystal aligning film that does not cause display unevenness caused by a washing process, and the liquid crystal aligning agent
• An object of the present invention is to provide a liquid crystal display device having a film.
• the present invention provides at least one selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide that is an imidized product of the polyimide precursor.
• a liquid crystal aligning agent characterized by containing a polymer (P) of No., a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.
• a liquid crystal aligning agent that expands the range of light irradiation amount for obtaining a liquid crystal alignment film with small variation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal alignment film, and cleaning
• a liquid crystal aligning agent that forms a liquid crystal aligning film having a high water contact angle, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film to obtain a liquid crystal aligning film that does not cause display unevenness caused by the process.
• a high-performance liquid crystal display element having
• the liquid crystal aligning agent of the present invention is, as described above, a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D A ) (also referred to as a specific diamine in the present invention) and at least one polymer (P) selected from the group consisting of polyimide which is an imidized product of the polyimide precursor.
• D A diamine component containing a diamine (0) represented by the following formula (D A ) (also referred to as a specific diamine in the present invention) and at least one polymer (P) selected from the group consisting of polyimide which is an imidized product of the polyimide precursor.
• Ar, m and n are each as defined above.
• m and n are preferably 1 to 2 from the viewpoint of obtaining high liquid crystal orientation.
• the monovalent group that substitutes the hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring of Ar in the above formula (D A ) includes a halogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 2 to 3 carbon atoms. alkenyl group, alkoxy group having 1 to 3 carbon atoms, fluoroalkyl group having 1 to 3 carbon atoms, fluoroalkenyl group having 2 to 3 carbon atoms, fluoroalkoxy group having 1 to 3 carbon atoms, carboxy group, hydroxy group, number of carbon atoms 1 to 3 alkyloxycarbonyl groups, cyano groups, nitro groups and the like.
• a halogen atom an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a fluoroalkoxy group having 1 to 3 carbon atoms is preferable.
• Any hydrogen atom on the benzene ring to which the amino groups at both ends are bound may be replaced with a monovalent group, and specific examples of the monovalent group are Ar in the above formula (D A ). can be mentioned, and the same thing can be mentioned as a preferred embodiment.
• Suitable examples of the divalent aromatic group represented by Ar include 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3- Phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, biphenyl-4,4'-diyl, 2-methylbiphenyl-4,4'-diyl, 2-ethylbiphenyl-4,4'- diyl, 2-propylbiphenyl-4,4'-diyl
• Preferred examples of the above formula (D A ) include the following formulas (d A -1) to (d A -3).
• any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded, the benzene ring to which the alkylene group is bonded, the biphenyl structure, or the naphthalene ring is 1 It may be substituted with a valent group, and specific examples of the monovalent group include the monovalent groups exemplified for Ar in the above formula (D A ), and preferred embodiments include the same. can be done.
• a more preferred monovalent group as a substituent of the hydrogen atom on the benzene ring to which the amino groups at both ends in the above formulas (d A -1) to (d A -3) are bonded is a methyl group.
• the hydrogen atoms on the benzene ring to which the amino groups at both ends are bonded are substituted, it is more preferable that 1 to 2 hydrogen atoms are substituted in each benzene ring, and 1 hydrogen atom is substituted.
• At least one hydrogen atom on the benzene ring to which the amino groups at both ends are bonded is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, Alternatively, it may be substituted with a fluoroalkoxy group having 1 to 3 carbon atoms.
• m and n are each independently defined above.
• the polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyimide precursor obtained using a diamine component containing the diamine (0), or a polyimide that is an imidized product of the polyimide precursor.
• the polyimide precursor is a polymer from which a polyimide can be obtained by imidating polyamic acid, polyamic acid ester, or the like.
• a polymer (P) may be used individually by 1 type, and may be used in combination of 2 or more types.
• the polymer (P) is a polymer having at least one repeating unit selected from the group consisting of repeating units (p1) represented by the following formula (1) and imidized structural units of the repeating units (p1).
• X 1 represents a tetravalent organic group.
• Y 1 is a divalent organic group obtained by removing two amino groups from the specific diamine.
• R and Z each independently represent a hydrogen atom. Or represents a monovalent organic group.
• the monovalent organic group for R and Z in the above formula (1) includes a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO -, -COO-, -COS-, -NR 3 -, -CO-NR 3 -, -Si(R 3 ) 2 - (where R 3 is a hydrogen atom or a monovalent carbon atom having 1 to 6 carbon atoms) is a hydrogen group), a monovalent group A substituted with —SO 2 —, etc., the above monovalent hydrocarbon group, or at least one hydrogen atom bonded to a carbon atom of the above monovalent group A is a halogen Atoms
• Examples include a substituted monovalent group and a monovalent group having a heterocyclic ring.
• the monovalent organic group for R and Z in the above formula (1) includes, among others, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a tert A -butoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.
• R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
• X 1 in the above formula (1) includes, for example, a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof, which will be described later.
• Preferred embodiments of the tetracarboxylic dianhydride or derivative thereof in X 1 above include preferred embodiments of the tetracarboxylic dianhydride or derivative thereof that can be used for synthesizing the polymer (P) described later.
• a polyamic acid (P′) which is a polyimide precursor of the polymer (P), can be obtained by a polymerization reaction between a diamine component containing the diamine (0) and a tetracarboxylic acid component.
• the diamine (0) may be used alone or in combination of two or more.
• the amount of diamine (0) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, relative to the total diamine component.
• the diamine component used for producing the polyamic acid (P') may contain diamines other than diamine (0) (hereinafter also referred to as other diamines).
• diamines other diamines
• the amount of the diamine (0) used is preferably 90 mol % or less, more preferably 80 mol % or less, relative to the diamine component.
• diamines examples include other diamines listed below, but are not limited to these.
• the other diamines may be used singly or in combination of two or more.
• a diamine having a photoalignable group such as 4,4′-diaminoazobenzene or diaminotran; 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline Diamines terminated with photopolymerizable groups; 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy -2-methylpropanoyl)phenoxy)ethyl diamines having a radical polymerization initiator function such as 3,5-diaminobenzoate; 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 di
• m and n are each independently an integer of 0 to 3 and satisfy 1 ⁇ m+n ⁇ 4.
• j is an integer of 0 or 1;
• X 1 is -(CH 2 ) a - (a is an integer of 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 It 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-.
• m, n, X 1 and R 1 each independently has the above definition.
• the diamine component used in the production of the polyamic acid (P′) should contain at least one diamine selected from the group consisting of the above other diamines (a). is preferred.
• the amount of the other diamines used is preferably 10 to 90 mol% with respect to the total diamine components used in the production of the polymer (P). and more preferably 20 to 80 mol %.
• 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.
• tetracarboxylic dianhydrides such as carboxylic acid dialkyl ester dihalides can also be used.
• the tetracarboxylic dianhydride or derivative thereof includes an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or derivatives thereof. . Among them, it is more preferable to contain 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, or a derivative thereof.
• a tetracarboxylic dianhydride having at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, or a derivative thereof.
• the tetracarboxylic dianhydrides or derivatives thereof may be used singly or in combination of two or more.
• the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
• 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.
• An 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.
• the tetracarboxylic acid component that can be used in the production of the polyamic acid (P′) preferably includes the following tetracarboxylic dianhydrides or derivatives thereof (in the present invention, these are collectively referred to as specific tetracarboxylic acids Also called derivatives.).
• Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracar
• Preferred examples of the above specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 3
• the proportion of the above-mentioned specific tetracarboxylic acid derivative used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to the total tetracarboxylic acid components used.
• the liquid crystal aligning agent of the present invention is a liquid composition in which the polymer (P) and optionally other components are preferably dispersed or dissolved in a suitable solvent.
• the total content of the polymer components 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 total mass of 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 (P) used in the present invention is preferably 1 to 100 parts by mass, more preferably 10 to 100 parts by mass, with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. 20 to 100 parts by weight is particularly preferred.
• the liquid crystal aligning agent of the present invention may contain polymers other than the polymer (P).
• polymers other than the polymer (P) include at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not have the specific diamine and a polyimide that is an imidized product of the polyimide precursor.
• polysiloxane (Also referred to as polymer (B) in the present invention.), polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly( isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, polymers selected from the group consisting of poly(meth)acrylates, and the like. .
• 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.).
• a specific example of the poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).
• the polymer (B) is more preferable from the viewpoint of reducing afterimages derived from residual DC.
• the content of the other polymer 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 polymer contained in the liquid crystal aligning agent.
• 90 mass parts or less may be sufficient as content of the said polymer (P) with respect to a total of 100 mass parts of the polymers contained in a liquid crystal aligning agent, and 80 mass parts or less may be sufficient.
• 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.
• the amount of the specific tetracarboxylic acid derivative used is preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 50 mol % or more, relative to the total tetracarboxylic acid component used in the production of the polymer (B). More preferably mol% or more.
• Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above. Among them, diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 having at least one group selected from the group consisting of urea bond, amide bond, carboxy group and hydroxy group in the molecule '-Diaminodiphenyl ether, at least one diamine selected from the group consisting of diamines represented by the above formulas (d AL -1) to (d AL -10), and diamines having the above specific nitrogen atom-containing structure ( In the present invention, these are also referred to as specific diamines (b).) are preferably included.
• 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, of the total diamine component used in the production of the polymer (B).
• the amount used is preferably 90 mol% or less, more preferably 80 mol% or less, of the total diamine component used in the production of the polymer (B).
• a 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 the diamine component used in the polyamic acid production reaction is 0.5 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid component per 1 equivalent of the amino group of the diamine component. is 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 greater the molecular weight of the resulting polyamic acid.
• the reaction temperature in the production of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. Also, 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. The concentration of polyamic acid is 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.
• organic solvent examples include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone.
• 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 are 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 tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.
• a polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the above polyamic acid or polyamic acid ester.
• the imidization ratio is the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof).
• the imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
• the temperature is preferably 100 to 400° C., more preferably 120 to 250° C., and water produced by the imidization reaction is removed from the system. is preferred.
• Catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, preferably -20 to 250°C, more preferably stirring at 0 to 180°C. can be done.
• the amount of the basic catalyst is preferably 0.5 to 30 times the molar amount of the amic acid group, more preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is preferably 1 to 50 times the molar amount of the amic acid group. It is preferably 3 to 30 molar times.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc.
• pyridine is preferable because it has appropriate basicity for advancing the reaction.
• 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 catalyst amount, reaction temperature, and reaction time.
• the reaction solution may be put into a solvent to precipitate.
• Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
• the polymer precipitated by adding it to the solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.
• the impurities in the polymer can be reduced by repeating the operation of redissolving the recovered polymer in an organic solvent and recovering it by reprecipitation 2 to 10 times.
• Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more solvents selected from these, because the efficiency of purification is further increased.
• a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocker to end block A polymer of the type may be produced.
• the end-blocking polymer has effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion properties between the sealing agent and the liquid crystal alignment film.
• the terminal of the polyimide precursor or polyimide in the present invention include an amino group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent to be described later.
• An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.
• 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.
• the polystyrene equivalent weight average molecular weight (Mw) 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. is.
• the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
• the organic solvent contained in the liquid crystal aligning agent according to the present invention is not particularly limited as long as it uniformly dissolves the polymer (P) and other polymers added as necessary.
• 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 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 coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent.
• a solvent also referred to as a poor solvent
• the use of solvents is preferred. Specific examples of the poor solvent are given 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.
• Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, -hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl
• 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 and ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methy
• 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 polymer, and the organic solvent.
• additive components include, for example, a crosslinkable compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxy group and an alkoxy group; At least one crosslinkable compound selected from the group consisting of crosslinkable compounds having saturated groups, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and 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, ,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), etc.
• Bisphenol A type epoxy resin bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (manufactured by Mitsubishi Chemical Corporation) and the like 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 Industries, Ltd.), alicyclic epoxy resins such as Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), N,N,N',N'-tetraglycidyl-m-xylylenedi
• 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 heterocyclic ring is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. part by mass.
• Preferred specific examples of the above functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane.
• the solid content concentration in the liquid crystal aligning agent (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 preferably It is 1 to 10% by mass.
• a 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 a spin coating method is used, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable to set the solid content concentration to 3 to 9% by mass and thereby the solution viscosity to 12 to 50 mPa ⁇ s.
• the solid content concentration is preferably 1 to 5% by mass and thereby the solution viscosity to 3 to 15 mPa ⁇ s.
• the temperature for preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C.
• a liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment agent.
• the operation mode of the liquid crystal display element is not particularly limited. , an optically compensated bend method (OCB method), and various other operation modes.
• 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), steps (1) to (3), ( 4-2) and (4-4), or by a method including steps (1) to (3), (4-3) and (4-4).
• a process (1) is a process of apply
• a specific example of step (1) is as follows.
• a liquid crystal aligning agent is applied to 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 a spray method.
• the material of the substrate is not particularly limited as long as it is highly transparent, and glass, silicon nitride, plastic such as acrylic, polycarbonate, etc., can also be used.
• a reflective liquid crystal display element if only one substrate is used, 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.
• a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used.
• An IPS substrate which is a comb-teeth electrode substrate used in an IPS-type liquid crystal display element, includes, for example, a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb-teeth shape, and and a liquid crystal alignment film formed to cover the linear electrodes.
• the FFS substrate which is a comb-teeth electrode substrate used in an FFS mode liquid crystal display element, includes, for example, a base material, a plane electrode formed on the base material, an insulating film formed on the plane electrode, It has a plurality of linear electrodes formed on an insulating film and arranged in a comb shape, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.
• More preferable examples of the method of applying the liquid crystal aligning agent to the substrate to form a film include a printing method such as screen printing, offset printing, or flexo printing, a spin coating method, an inkjet method, or a spray method.
• a printing method such as screen printing, offset printing, or flexo printing
• spin coating method such as screen printing, offset printing, or flexo printing
• inkjet method such as inkjet nozzle
• spray method such as screen printing, offset printing, or flexo printing
• a spin coating method such as screen printing, offset printing, or flexo printing
• a spin coating method such as screen printing, offset printing, or flexo printing
• a spin coating method such as screen printing, offset printing, or flexo printing
• a spin coating method such as an inkjet method
• a spray method such as a flexographic printing, spin coating, or ink-jet coating and film-forming methods can be preferably used.
• a process (2) is a process of baking the liquid crystal aligning agent apply
• a specific example of step (2) is as follows. After applying the liquid crystal aligning agent on 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) oven, or polyimide typified by polyamic acid Thermal imidization of the precursor can be performed. Drying after applying a liquid crystal aligning agent and a baking process can select arbitrary temperature and time, and may be performed in multiple times. The temperature for baking the liquid crystal aligning agent can be, for example, 40 to 180.degree.
• the firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes.
• a step of baking at 150 to 300° C. or 150 to 250° C. may be added after the above step.
• the firing time 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 deteriorate.
• Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a horizontally aligned liquid crystal display device 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 liquid crystal display element such as a VA system or a PSA (Polymer Sustained Alignment) system, the formed coating film can be used as a liquid crystal alignment film as it is. may be applied. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing alignment treatment method and a photo-alignment treatment method.
• 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 coating film irradiated with polarized radiation or the coating film subjected to rubbing alignment treatment by the above method may be subjected to contact treatment using water or a solvent. Further, the film subjected to the alignment treatment may be subjected to heat treatment without being subjected to contact treatment. Furthermore, the film subjected to the contact treatment may be further subjected to heat treatment.
• 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.
• Solvents may be used singly or in combination of two or more.
• the temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C.
• the heat treatment time is preferably 1 to 30 minutes.
• Step (4) Step of producing a liquid crystal cell> Two substrates on which liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned. In the first method, first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween 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 liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used.
• a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal
• a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
• 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.
• Such additives include photopolymerizable monomers such as compounds having a polymerizable group (meth(a)acryloyl group, etc.); optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); Antioxidants; ultraviolet absorbers; dyes; antifoaming agents; polymerization initiators; Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
• MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group.
• the second method is a method called ODF (One Drop Fill) method.
• ODF One Drop Fill
• 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.
• liquid crystal filling it is desirable to remove the flow orientation at the time of liquid crystal filling by heating the liquid crystal composition to a temperature at which the used liquid crystal composition assumes an isotropic phase and then slowly cooling to room temperature.
• 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 sealant for example, an epoxy resin or the like containing a curing agent and aluminum oxide spheres as spacers can be used.
• Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
• the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates.
• a liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. is also preferably used.
• 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 polymerized by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used in a liquid crystal display element (SC-PVA type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing the liquid crystal and applying a voltage between electrodes.
• SC-PVA type liquid crystal display element manufactured through a process of arranging a liquid crystal alignment film containing the liquid crystal and applying a voltage between electrodes.
• Step (4-2) For PSA liquid crystal display device> It is carried out in the same manner as in (4) above, except that the liquid crystal composition containing a polymerizable compound is injected or dropped.
• the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.
• a method of manufacturing a liquid crystal display element may be employed in which a step of irradiating ultraviolet rays, which will be described later, is performed after performing the same as in the above (4). According to this method, a liquid crystal display device having an excellent response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device.
• the compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass.
• the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction.
• a diamine component containing a diamine having a photopolymerizable group at the end thereof which is used in the reaction.
• the polymer obtained is mentioned.
• Step (4-4) Step of irradiating with ultraviolet rays>
• the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above.
• the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
• As the light for irradiation for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable.
• a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used as the light source for the irradiation light.
• the irradiation amount of light is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .
• a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary.
• a polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
• a polarizing plate consisting of
• CA-1 a compound represented by the following formula (CA-1)
• (diamine) DA-1 to DA-7 compounds represented by the following formulas (DA-1) to (DA-7), respectively.
• Diamines included in the scope of the specific diamine of the present invention are compounds represented by the following formulas (DA-1), (DA-2) and (DA-7).
• DA-1 was used after purchasing a commercial product (manufactured by Chemieliva Pharmaceutical).
• DA-2 was synthesized by the synthesis method described in Journal of Molecular Structure (2016), 1169, 46-58.
• DA-6 and DA-7 are novel compounds that have not been published in literature, etc., and their synthesis methods are described in detail below.
• DA-6-2 (5.00 g, 9.64 mmol), DMF (50 g) and carbon-supported palladium (5% Pd carbon powder (50% water content) K type, manufactured by N.E. 50 g) was added, and the mixture was stirred at 80° C. under a hydrogen atmosphere under pressure (0.3 MPa) for 12 hours. Crystals were precipitated, so DMF (100 g) was added, and palladium on carbon was removed by filtration. IPA (150 g) was added to the obtained filtrate for crystallization to obtain DA-6 (3.76 g, 8.20 mmol, yield 85%).
• DA-7 was synthesized according to the route shown below.
• p-xylylene dichloride 7.0 g, 40 mmol
• DMAc 140 g
• 4-nitro-m-cresol 14 g, 84 mmol
• potassium carbonate 16.5 g, 120 mmol
• DA-7-1 (15.5 g, 38 mmol) obtained above, DMF (466 g), and carbon-supported platinum (3% Pt carbon powder (50% water content) were added to a 1 L four-necked flask. , manufactured by Evonik, 1.5 g) was added and the mixture was replaced with a hydrogen atmosphere, and then stirred at 50° C. for 18 hours to react. After completion of the reaction, carbon-supported platinum was removed using a membrane filter, and the filtrate was concentrated. IPA (150 g) was added to precipitate crystals, which were filtered off after stirring at room temperature. The obtained crystals were cake-washed with IPA (75 g) and dried under reduced pressure at 40° C.
• DA-3 (0.541 g, 5.00 mmol), DA-2 (1.98 g, 5.00 mmol) and NMP (18.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-2) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 14,600 and an Mw of 45,600.
• DA-3 (0.541 g, 5.00 mmol), DA-7 (1.74 g, 5.00 mmol) and NMP (16.7 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.13 g, 9.49 mmol) and NMP (15.6 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-6) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 11,900 and an Mw of 30,400.
• Table 1 shows the specifications of the polyamic acid solution obtained in the above synthesis example.
• the numbers in parentheses for the tetracarboxylic acid component and the diamine component are the amounts (mol parts) of each tetracarboxylic acid component and each diamine component used with respect to the total amount of 100 mol parts of the diamine component used in each polymerization step. represents
• Table 2 shows the specifications of the liquid crystal aligning agents obtained in the above examples and comparative examples.
• liquid crystal aligning agents (AL-1) to (AL-6) obtained as described above did not show any abnormalities such as turbidity or precipitation, and were confirmed to be homogeneous solutions. Evaluation of in-plane uniformity of contrast and evaluation of water contact angle were performed using the obtained liquid crystal aligning agent.
• liquid crystal aligning agent obtained above, a liquid crystal cell was produced in the following procedure. After each liquid crystal aligning agent was filtered through a filter with a pore size of 1.0 ⁇ m, it was applied to a glass substrate with ITO electrodes (length 40 mm ⁇ width 30 mm ⁇ thickness 0.7 mm) by a spin coating method and placed on a hot plate at 80° C. for 60 seconds. After drying, it was baked in an infrared heating furnace at 230° C. for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm.
• the coating film surface is irradiated with linearly polarized ultraviolet light having a wavelength of 254 nm and an extinction ratio of 26:1 through a polarizing plate at 400 mJ/cm 2 , 600 mJ/cm 2 or 800 mJ/cm 2 to perform an orientation treatment. Further, it was baked in an infrared heating furnace at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film (first glass substrate). A substrate with a liquid crystal alignment film (second glass substrate) was obtained in the same manner as described above, except that the alignment treatment was performed so that the alignment direction was orthogonal to that of the first glass substrate.
• the above two substrates are set as a set, and a bead spacer with a diameter of 4 ⁇ m (manufactured by Nikki Shokubai Kasei Co., Ltd., Shinshikyu, SW-D1) is applied on one of the liquid crystal alignment films, leaving a liquid crystal injection port.
• a sealant (XN-1500T, manufactured by Mitsui Chemicals, Inc.) was printed, and another substrate was attached so that the alignment direction of the liquid crystal alignment film surfaces facing each other was 0°. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell.
• Liquid crystal MLC-3019 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120° C. for 1 hour and then used for evaluation.
• the coated 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, and further baked in an infrared heating furnace at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film. got
• the contact angle of water on this substrate was measured using a fully automatic contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.). As evaluation criteria, the case where the water contact angle was greater than 50° was evaluated as “ ⁇ ”, and the case where the water contact angle was 50° or less was evaluated as “x”. Table 3 shows the results.
• the liquid crystal alignment films obtained using the liquid crystal aligning agents (AL-1), (AL-2) and (AL-6) of Examples 1 to 3 are those of Comparative Examples 1 to 3.
• the film showed good in-plane uniformity in a wide exposure range and had a high water contact angle.
• the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is widely used in liquid crystal display elements of various operation modes. It can also be used for a film or a liquid crystal alignment film for a transmission scattering type liquid crystal light control device.
• the liquid crystal display device of the present invention can be effectively applied to devices having various functions, such as liquid crystal televisions, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, and digital cameras. , mobile phones, smart phones, various monitors, information displays, etc.

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