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
  • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • 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
• • 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
• • 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
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a liquid crystal aligning agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
• a liquid crystal display element As a liquid crystal display element, the major axis of nematic liquid crystal having positive dielectric anisotropy between two electrode substrates in which a liquid crystal alignment film is formed on an electrode is continuous from one substrate to the other substrate.
• IPS in-plane switching
• VA vertical
• a liquid crystal alignment film used in these liquid crystal display elements a polyimide-based liquid crystal alignment film is mainly used, and polyimide-based alignment films having various structures (for example, see Patent Document 1) have been developed.
• liquid crystal filling has been generally performed by a vacuum injection method in which a liquid crystal is filled between two substrates using a pressure difference between atmospheric pressure and vacuum.
• the liquid crystal injection port is provided only on one side of the substrate, it takes a long time to fill the liquid crystal between the substrates having a cell gap of 3 to 5 ⁇ m. It was difficult to simplify the manufacturing process. This has been a big problem particularly in the production of liquid crystal TVs and large monitors that have been put into practical use in recent years.
• a liquid crystal dropping method (ODF method) was developed in order to solve the problems in the above-described vacuum injection method.
• ODF method a liquid crystal dropping method
• a liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, bonded to the other substrate in a vacuum, and then the sealing material is UV cured to fill the liquid crystal.
• the liquid crystal dripping method has been solved by optimizing the manufacturing process so as to reduce the influence of adsorbed water and impurities, such as reducing the amount of liquid crystal dripped and improving the degree of vacuum during bonding.
• the liquid crystal display element production line becomes larger, it has become impossible to suppress display unevenness by optimizing the manufacturing process so far, and a liquid crystal alignment film that can reduce alignment unevenness more than before has been demanded.
• This alignment unevenness is caused by the adsorbed water and impurities adhering to the surface of the liquid crystal alignment film formed on the substrate being swept away by the liquid crystal dropped in the ODF process, so that the liquid crystal dropping part and the liquid crystal droplets are in contact with each other. It is thought that it occurs due to the difference in the amount of adsorbed water and impurities.
• the present invention has been made in view of the above circumstances. That is, the problem to be solved by the present invention is to provide a liquid crystal aligning agent that can reduce liquid crystal alignment unevenness generated by the ODF method. Furthermore, it is providing the liquid crystal display element which reduced the display nonuniformity resulting from the liquid crystal alignment nonuniformity which generate
• a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula [1] is reacted with a diamine component containing a diamine compound having a carboxyl group or a hydroxyl group in the molecule.
• Liquid crystal aligning agent containing the polymer obtained.
• Y 1 is a tetravalent organic group having 4 to 15 carbon atoms having a non-aromatic cyclic structure having 4 to 8 carbon atoms.
• (2) [1] in the liquid crystal aligning agent according to the above (1) having the structure Y 1 is selected from formula [11] according to the following formula [2].
• Y 2 to Y 5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different
• the formula [8 ] Y 6 and Y 7 are each independently a hydrogen atom or a methyl group, and may be the same or different.
• m1 is an integer of 1 to 4
• X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2-, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or -N (CH 3) a CO-, m @ 2 and m3 represents an integer of from 0 respectively 4, and m @ 2 + m3 is from 1 to 4
• m4 and m5 are each an integer of 1 to 5
• X 3 is a linear or branched alkyl group having 1 to 5 carbon atoms
• m6 is
• X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO— or —OCO—, wherein m2 and m3 are both integers of 1, the liquid crystal aligning agent according to (9) above.
• X 4 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —. , —COO— or —OCO—, and m7 is an integer of 1 to 2, according to (9) above.
• liquid crystal aligning agent according to any one of (1) to (14), wherein the polymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
• a liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of (1) to (15).
• a liquid crystal display device having the liquid crystal alignment film according to (16).
• the liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. Moreover, the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which can reduce the liquid crystal aligning nonuniformity generate
• a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
• the present invention relates to a tetracarboxylic dianhydride component including a tetracarboxylic dianhydride having a specific structure represented by the formula [1] (hereinafter also referred to as a specific acid dianhydride), and a carboxyl in the molecule.
• a liquid crystal aligning agent containing a polymer obtained by reacting a diamine component containing a specific diamine compound having a group or a hydroxyl group hereinafter also referred to as a specific diamine compound
• It is a liquid crystal display element which has a liquid crystal aligning film and also this liquid crystal aligning film.
• the polymer contained in the liquid crystal aligning agent of the present invention uses a specific dianhydride and a specific diamine compound having a highly polar carboxyl group or hydroxyl group as a raw material.
• the liquid crystal alignment film obtained from the liquid crystal alignment agent containing such a polymer easily adsorbs water and impurities adsorbed on the surface of the liquid crystal alignment film, and adhered to the liquid crystal alignment film surface when the liquid crystal was dropped in the ODF process. Sweeping of adsorbed water and impurities can be suppressed, and display unevenness associated therewith can be reduced.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can provide a liquid crystal display element having high display quality that does not cause liquid crystal alignment unevenness generated by the ODF method.
• the polymer used in the present invention comprises polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing a specific acid dianhydride and a diamine component containing a specific diamine compound, and dehydrating and ring-closing the polyamic acid. It is at least one polymer of the obtained polyimide.
• the tetracarboxylic dianhydride component used in the present invention includes a tetracarboxylic dianhydride represented by the formula [1], that is, a specific acid dianhydride, and a tetracarboxylic acid other than the specific acid dianhydride. Acid dianhydride can be used in combination. In the case where the tetracarboxylic dianhydride component is at least one compound selected from the group consisting of a specific acid dianhydride, the effect exhibited by the present invention can be made more remarkable, which is preferable.
• the specific acid dianhydride used in the present invention is a tetracarboxylic dianhydride represented by the following formula [1].
• Y 1 is a tetravalent organic group having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, having a non-aromatic cyclic structure (alicyclic structure) having 4 to 8 carbon atoms. If Y 1 is specifically shown in the formula [1], groups of the following formulas [2] to [11] are exemplified.
• Y 2 to Y 5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different
• Y 6 and Y 7 are each independently a hydrogen atom or a methyl group, and may be the same or different.
• a particularly preferred structure of Y 1 is Formula [2], Formula [4], Formula [5], Formula [7] or Formula [8] because of polymerization reactivity and ease of synthesis. .
• the specific acid dianhydride illustrated above can be used alone or in combination of two or more.
• pyromellitic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Tetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydrides, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,
• the diamine compound used in the present invention contains a diamine compound having a carboxyl group or a hydroxyl group in the molecule, that is, a specific diamine compound, and a diamine compound other than the specific diamine compound, that is, other diamine compounds may be used in combination. it can.
• the diamine compound is at least one compound selected from the group consisting of specific diamine compounds, the effect of the present invention can be more remarkable, which is preferable.
• the specific diamine compound of the present invention is a diamine compound having a carboxyl group or a hydroxyl group in the molecule.
• the specific structure of the diamine compound having a carboxyl group in the molecule is not particularly limited, but is preferably a compound represented by the following formula [12].
• X 1 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.
• Preferred X 1 is a structure represented by the formula [12a], having 6 to 30 carbon atoms, and additionally having 1 to 4 of arbitrary hydrogen atoms substituted with a carboxyl group.
• g represents an integer of 0 to 2
• Q represents a single bond, an ether bond, a carbonyl group, a carboxyl group, an amino group, an amide bond, or an alkylene group having 1 to 11 carbon atoms.
• the hydrogen atom may be substituted with a fluorine atom or a methyl group.
• More preferable compounds include compounds of the following formulas [13] to [17].
• m1 is an integer of 1 to 4
• X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, — CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or -N (CH 3) a CO-, m @ 2 and m3 are each an integer of 0 to 4, and m @ 2 + m3 is an integer of 1 to 4 are shown, where [15], m4 and m5 is an integer of from respectively 1 5, wherein [16], X 3 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms,
• m1 is an integer of 1 to 2
• X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO— or —OCO—
• m2 and m3 are both integers of 1.
• X 4 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO— or —OCO—, and m7 is a diamine compound which is an integer of 1 to 2.
• diamine compounds represented by the formulas [13] to [17] preferred specific examples include diamine compounds of the following formulas [18] to [28].
• X 5 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO.
• X 6 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—. , —OCH 2 —, —COO— or —OCO—.
• the specific structure of the diamine compound having a hydroxyl group in the molecule is not particularly limited, but preferred compounds include compounds of the following formulas [29] to [33].
• m8 is an integer of 1 to 4
• X 7 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, — CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or, -N (CH 3) a CO-, in m9 and m10 are each an integer of 0 to 4, and m9 + m10 is from 1 4 an integer, wherein [31], m11 and m12 are integers from each 1 5, wherein [32], X 8 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m13
• m8 is an integer of 1 to 2
• X 7 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO— or —OCO—
• both m9 and m10 are integers of 1.
• X 9 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO— or —OCO—, and m14 is a diamine compound which is an integer of 1 to 2.
• diamine compounds represented by the formulas [29] to [33] preferred specific examples include diamine compounds of the following formulas [34] to [44].
• X 10 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO.
• X 11 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—. , —OCH 2 —, —COO— or —OCO—.
• the specific diamine compound illustrated above can use together 1 type, or 2 or more types.
• p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2 , 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4, 4,4'
• diamine examples include a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of these in the side chain of the diamine.
• R 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• R 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH—
• R 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• R 4 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
• R 5 represents one or more carbon atoms. 22 or less alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group.
• R 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 — or —CH 2 —
• R 7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
• R 8 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 —, —CH 2 —, —O— or —NH—, wherein R 9 is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group .
• diaminosiloxanes represented by the following formula [DA27] can also be exemplified.
• m is an integer of 1 to 10.
• the other diamine compounds exemplified above can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
• the polymer used in the present invention is at least one polymer of polyamic acid and polyimide.
• This polyamic acid is a polyamic acid obtained by reaction of a tetracarboxylic dianhydride component containing a specific acid dianhydride and a diamine component containing a specific diamine compound.
• the polyimide is a polyimide obtained by dehydrating and ring-closing the polyamic acid. Both the polyamic acid and the polyimide are useful as a polymer for obtaining a liquid crystal alignment film.
• the content of the specific diamine compound in the diamine component is preferably 5 mol% to 100 mol%. More preferably, it is 10 mol% to 100 mol%, More preferably, it is 10 mol% to 80 mol%, Most preferably, it is 20 mol% to 80 mol%.
• the content of the specific acid dianhydride in the tetracarboxylic dianhydride component is preferably 5 mol% to 100 mol%. More preferably, it is 10 mol% to 100 mol%, More preferably, it is 20 mol% to 100 mol%, Most preferably, it is 50 mol% to 100 mol%.
• a known polymerization method can be used for the polyamic acid used in the present invention.
• a tetracarboxylic dianhydride component and a diamine compound are reacted in an organic solvent.
• the reaction between the tetracarboxylic dianhydride and the diamine compound is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is produced.
• the organic solvent used in that case will not be specifically limited if the produced
• a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
• water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
• a solution in which the diamine compound is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
• a method of adding by dispersing or dissolving a method of adding a diamine compound to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine compound. And any of these methods may be used.
• the tetracarboxylic dianhydride or the diamine compound when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
• the temperature at the time of synthesizing the polyamic acid can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
• the ratio of the number of moles of the diamine component to the number of moles of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
• the polyimide used in the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
• the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose.
• Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
• the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
• the catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
• Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose. Particularly preferably, it is 50% or more.
• the reaction solution may be poured into a poor solvent and precipitated.
• the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
• the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
• impurities in the polymer can be reduced.
• it is preferable to use three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent because the purification efficiency is further increased.
• the molecular weights of the polyamic acid and polyimide used in the present invention are weight average molecular weights measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film, workability when forming the coating film, and uniformity of the coating film. 5,000 to 1,000,000, respectively, more preferably 10,000 to 150,000.
• the liquid crystal aligning agent of this invention is a coating liquid for producing a liquid crystal aligning film
• the main component consists of the resin component for forming a resin film, and the organic solvent which dissolves this resin component.
• the resin component is a resin component containing the polymer used in the present invention. In that case, the content of the resin component is 1% by mass to 20% by mass, preferably 2% by mass to 10% by mass.
• all of the above resin components may be a polymer used in the present invention, or the polymer of the present invention may be used in combination with another polymer.
• the content of the polymer other than the polymer of the present invention in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.
• examples of such other polymers include polyamic acid or polyimide obtained by reacting other acid dianhydrides other than the specific acid dianhydride with other diamine compounds other than the specific diamine compound.
• the organic solvent for dissolving the resin component is not particularly limited. Specific examples include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide.
• Tetramethyl urea pyridine, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, Examples thereof include ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvents may be mixed and used.
• the concentration of the specific polyimide solution is not particularly limited. However, since it is easy to mix uniformly with the specific amine compound, the specific polyimide concentration in the solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. Preferably, it is 3 to 10% by mass.
• the liquid crystal aligning agent of this invention may contain components other than the above.
• examples thereof may include a solvent and a compound that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal aligning film and the substrate, and the like.
• Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.
• butyl cellosolve propylene glycol monomethyl ether or ethyl lactate is more preferred.
• Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.).
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
• Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
• the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
• the amount is preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
• liquid crystal aligning agent of the present invention in addition to the above, as long as the effects of the present invention are not impaired, a dielectric or conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal aligning film, Furthermore, a crosslinkable compound for the purpose of increasing the hardness and density of the film when the liquid crystal alignment film is formed may be added.
• the concentration of the solid content in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal aligning film. From the reason that it can be obtained, the content is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or without alignment treatment in vertical alignment applications.
• the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
• an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
• the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
• Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.
• liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
• Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
• the molecular weight of the polyimide in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex.
• GPC normal temperature gel permeation chromatography
• the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 manufactured by Kusano Kagaku Co., Ltd.) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture). The solution was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
• JNW-ECA500 JNW-ECA500
• the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is the proton peak integrated value derived from the NH group of the amic acid
• y is the peak integrated value of the reference proton
• ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). Is the number ratio of the reference proton to.
• This reaction solution was poured into methanol (600 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• the imidation ratio of this polyimide was 80%, the number average molecular weight was 19,500, and the weight average molecular weight was 62,200.
• This deposit was wash
• the imidation ratio of this polyimide was 88%, the number average molecular weight was 17,700, and the weight average molecular weight was 65,700.
• polyimide powder (I) This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (I).
• the imidation ratio of this polyimide was 88%, the number average molecular weight was 18,000, and the weight average molecular weight was 72,900.
• Example 1 By adding NMP (12.5 g) and BCS (25.5 g) to the polyamic acid solution (A) (10.0 g) obtained in Synthesis Example 1, and stirring at 25 ° C. for 2 hours, a liquid crystal aligning agent [1] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
• the liquid crystal aligning agent [1] obtained above is spin-coated on a glass substrate with an ITO electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked for 15 minutes in a 220 ° C. hot air circulation oven.
• a liquid crystal alignment film having a thickness of 100 nm was prepared. After preparing two substrates with the liquid crystal alignment film and spraying a spacer of 6 ⁇ m on the surface of the liquid crystal alignment film, the sealant is printed and bonded together, and then the sealant is cured to be emptied. A cell was produced.
• a liquid crystal MLC-6608 manufactured by Merck Japan Co., Ltd.
• the liquid crystal aligning agent [1] obtained above is spin-coated on a glass substrate with an ITO electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked for 15 minutes in a 220 ° C. hot air circulation oven.
• a liquid crystal alignment film having a thickness of 100 nm was prepared.
• the contact angle between pure water and methylene iodide was measured.
• the literature [JOURNAL OF APPLIED POLYMER SCIENCE VOL. 13, PP. 1741-1747 (1969)].
• K. According to the method of OWENS et al. Surface free energy (also referred to as surface tension) polarity term was calculated.
• the contact angle was measured by dropping 3 ⁇ l of water and 1 ⁇ l of methylene iodide onto the coating film using a contact angle measuring device CA-W (manufactured by Kyowa Interface Chemical Co., Ltd.) and measuring the contact angle after 5 seconds. Asked. The results are shown in Table 2 described later.
• NMP (24.3 g) was added to the polyimide powder (B) (5.0 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
• NMP (12.3g) and BCS (41.5g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [2].
• Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
• a liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [2]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• NMP (24.3 g) was added to the polyimide powder (C) (5.1 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours.
• NMP (27.1g) and BCS (26.3g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [3].
• Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
• a liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [3]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• Example 4 NMP (24.2 g) was added to the polyimide powder (D) (5.0 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 40 hours. NMP (26.0 g) and BCS (27.5 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [4]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [4]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• Example 5 NMP (25.0 g) was added to the polyimide powder (E) (5.0 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.5g) and BCS (37.1g) were added to this solution, and the liquid crystal aligning agent [5] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [5]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• NMP (24.5 g) was added to the polyimide powder (F) (5.1 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 ° C. for 40 hours.
• NMP (28.1g) and BCS (25.1g) were added to this solution, and the liquid crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
• a liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [6]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• Example 7 NMP (24.1 g) was added to the polyimide powder (G) (5.0 g) obtained in Synthesis Example 7, and the mixture was dissolved by stirring at 70 ° C. for 40 hours. NMP (22.0 g) and BCS (31.5 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [7]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent [7]. As a result, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• NMP (24.0 g) was added to the polyimide powder (H) (5.0 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 40 hours.
• NMP (22.0 g) and BCS (41.1 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [8]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
• the liquid crystal aligning agent [8] obtained above is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then baked in a hot air circulation oven at 220 ° C. for 15 minutes.
• a liquid crystal alignment film having a thickness of 100 nm was prepared.
• the surface of the coating film was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.5 mm to obtain a substrate with a liquid crystal alignment film.
• Example 9 NMP (25.1 g) was added to the polyimide powder (I) (5.1 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C. for 40 hours. NMP (22.2g) and BCS (40.9g) were added to this solution, and the liquid crystal aligning agent [9] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. A liquid crystal cell was produced in the same manner as in Example 8 using the obtained liquid crystal aligning agent [9]. As a result, the liquid crystal was uniformly aligned, and no alignment defects were observed. Further, the surface free energy polarity term was evaluated in the same manner as in Example 1. The results are shown in Table 2 described later.
• the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which can reduce the liquid crystal alignment nonuniformity generate
• IPS vertical alignment type and horizontal alignment type

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