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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention provides a liquid crystal alignment film having excellent rubbing resistance even when using a low-temperature baking process, having a desired voltage holding ratio (VHR), having reliability, a liquid crystal alignment agent for forming the liquid crystal alignment film, and the liquid crystal alignment
• VHR voltage holding ratio
• the present invention relates to a liquid crystal display element including a film.
• liquid crystal alignment film As the liquid crystal alignment film, a so-called polyimide-based liquid crystal alignment film, which is obtained by applying and baking a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution, is widely used.
• a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution
• the conventional liquid crystal alignment film can obtain good reliability and rubbing resistance by baking a polyimide precursor at a high temperature of, for example, 200 ° C. or more to obtain a polyimide.
• flexible liquid crystal elements using a PET film or a polycarbonate film as a base material have been studied because of their excellent design properties.
• Patent Document 1 In order to improve the color reproducibility of a liquid crystal display, a method of mixing quantum dots with a color filter has also been proposed (Patent Document 1). On the other hand, quantum dots still have insufficient reliability to heat and light, and there is a problem that it is difficult to raise the firing temperature of the substrate. Therefore, a low-temperature baking process has been studied from the request of heat resistance of a substrate to which a liquid crystal aligning agent is applied and / or prevention of deterioration of the substrate or a member provided on the substrate. In addition, a liquid crystal alignment film material suitable for a low-temperature firing process has been proposed (Patent Document 2).
• the liquid crystal alignment film obtained even after undergoing a low-temperature baking process has a desired voltage holding ratio and is a reliable liquid crystal alignment film.
• An object of the present invention is to provide a liquid crystal alignment film that has a liquid crystal alignment film that is excellent in rubbing resistance, has a desired voltage holding ratio, and has reliability even after undergoing a low-temperature baking process.
• the objective of this invention is providing the liquid crystal aligning agent which forms this liquid crystal aligning film, and a liquid crystal display element provided with this liquid crystal aligning film in addition to the said objective.
• the objective of this invention is providing the manufacturing method of the said liquid crystal aligning film in addition to the said objective or the said objective.
• Liquid crystal aligning agent containing the following (A) component; (B) component; and (C) component: (A) component: At least 1 type of polymer chosen from the group which consists of a polyimide precursor and the polyimide obtained by imidation reaction of this polyimide precursor; (B) component: a compound represented by the following formula (N-1); Component (C): At least one specific solvent selected from the group consisting of the following formulas (1) to (8).
• R 1 and R 2 are the same or different and each represents a linear or branched alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms.
• R 3 and R 4 are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.
• R 5 represents a z-valent linear or branched aliphatic hydrocarbon group having 1 to 24 carbon atoms or a z-valent alicyclic hydrocarbon group having 3 to 24 carbon atoms.
• any of a cycloalkane group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 5 to 12 carbon atoms, (thio) ether, carbonyl, or tertiary amine between carbon-carbon bonds in the aliphatic hydrocarbon group May be inserted, and this aliphatic hydrocarbon group may have one group selected from epoxy and halogen.
• any of (thio) ether, carbonyl, and tertiary amine may be inserted between carbon-carbon bonds in the alicyclic hydrocarbon group, and one of the single bonds that do not constitute a ring is It may be replaced with an alkylene group having 1 to 12 carbon atoms.
• z is an integer of 1 to 6.
• R 11 to R 16 and R 20 to R 21 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 17 to R 19 each represents an alkyl group having 1 or 2 carbon atoms.
• N in the formula (7) represents an integer of 1 to 3.
• a liquid crystal alignment film obtained even after undergoing a low-temperature baking process has excellent rubbing resistance, has a desired voltage holding ratio, and can provide a reliable liquid crystal alignment film.
• the present invention can provide a liquid crystal aligning agent that forms the liquid crystal alignment film and a liquid crystal display device including the liquid crystal alignment film.
• a method for producing the liquid crystal alignment film can be provided in addition to or in addition to the above effects.
• the present application provides a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display device including the liquid crystal aligning film.
• the liquid crystal aligning agent of this application contains (A) component; (B) component; and (C) component.
• ⁇ (A) component >> The component (A) is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by imidization reaction of the polyimide precursor.
• the polyamic acid according to the present invention can be obtained by reacting a diamine compound with tetracarboxylic dianhydride.
• the diamine used for the polymerization of the polyamic acid of the present invention can be generalized by the following formula (1).
• a 1 and A 2 in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms
• Y 1 is a divalent organic group.
• a 1 and A 2 are preferably a hydrogen atom or a methyl group.
• a diamine of the following formula (DA-1) may be used.
• Y d is preferably a divalent organic group represented by the following formulas (Y-1) to (Y-171).
• X 1 is a sulfur atom, an oxygen atom or —NH—
• R 8 and R 9 are each independently a divalent organic group, and at least one of R 8 and R 9 is One has an aromatic ring, and at least one bond in “—CO—X 1 —” is bonded to the aromatic ring, preferably described in paragraphs [0047] to [0048] of JP-A-2015-135464.
• R 1 and R 2 are each an ethylene group, —COO—, —OCO—, —NHCO—, —N (CH 3 ) CO—.
• n is an integer of 1 to 6.
• Y-1 to Y-6, Y-8, Y-9, Y-14 to Y are used from the viewpoint of solubility of a polyimide precursor or a polyimide obtained by imidizing the polyimide precursor in a solvent.
• Y-20, Y-26 to Y-28, Y-32, Y-38 to Y-42, Y-49 to Y-60, Y-64 to Y-69, Y-72, Y-77 Y-84, Y-86, Y-156, Y-160 to Y-163, Y-165 are preferred, Y-8, Y-9, Y-14, Y-16, Y-17, Y-20 Y-26 to 28, Y-32, Y-38, Y-68, Y-72, Y-77, Y-84, Y-160, Y-161, Y-165 are more preferable.
• One preferred embodiment of the diamine that can be used in the present invention is a diamine having an alkyl group or fluorine-containing alkyl group in the side chain represented by the following formulas [Sd-1] to [Sd-4]. .
• each A 1 independently represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
• the diamine is preferable in terms of accelerating the curing rate of the liquid crystal alignment film, and more preferably used in combination with a diamine that imparts vertical alignment described later. These diamines are preferably at least 10 mol%, more preferably at least 20 mol%, based on the total diamine component used in the liquid crystal aligning agent.
• diamine that can be used in the present invention is represented by the following formulas [2a-1] to [2a-9] (n is each independently an integer of 2 to 12). Diamines.
• Another preferred embodiment of the diamine that can be used in the present invention includes a diamine having a heterocyclic ring represented by the following formula (bs).
• X 1 is at least one divalent organic group selected from the group consisting of —O—, —NQ 1 —, —CONQ 1 —, —NQ 1 CO—, —CH 2 O—, and —OCO—
• Q 1 is A hydrogen atom or an alkyl group having 1 to 3 carbon atoms
• X 2 represents a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group.
• X 3 is a single bond, or —O—, —NQ 2 —, —CONQ 2 —, —NQ 2 CO—, —COO—, —OCO—, and —O (CH 2 ) m— (m is an integer of 1 to 5)
• Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
• X 4 is a nitrogen-containing aromatic heterocycle
• n is an integer of 1 to 4, preferably a combination described in Tables 1 to 3 in paragraphs [0036] to [0038] of International Publication No. WO2009 / 093707 It is.
• Another preferred embodiment of the diamine that can be used in the present invention includes a diamine having a photoreactive group represented by the following formula (PV-0).
• X 2 represents a substituent, and is a group having a structure represented by the following formula (2A) or the following formula (2B).
• R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (however, any hydrogen atom may be substituted with a fluorine atom), or Represents an alkoxy group having 1 to 18 carbon atoms (wherein any hydrogen atom may be substituted with a fluorine atom).
• a and B each independently represent a single bond or any one of the ring structures represented by the following formulae. However, any hydrogen atom in the ring structure may be substituted with an alkoxy group having 1 to 10 carbon atoms.
• T 1 to T 4 each independently represents a single bond, an ether, an ester, an amide or a ketone bond.
• S represents a single bond or an alkylene group having 1 to 10 carbon atoms.
• diamines that can be used in the present invention are represented by the formulas [2-1] to [2-31] described in paragraphs [0033] to [0042] of International Publication WO2013 / 125595.
• the diamines shown can be exemplified, and these diamines are preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 20 mol% or more with respect to the entire diamine component. preferable. From the viewpoint of increasing the curing rate, 90 mol% or less is preferable, and 80 mol% or less is more preferable. More preferred diamines are at least one selected from the following formulas [2a-24] to [2a-33].
• R 1 s when they are ortho to one of the amino groups, R 1 s independently represent —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —. And at least one linking group selected from —CH 2 OCO—, and when in the meta position with respect to two amino groups, R 1 represents —CONH—, —NHCO, in addition to the linking group shown above. Represents at least one linking group selected from — and —CH 2 —, wherein each R 2 independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a straight chain having 1 to 22 carbon atoms.
• Cy represents a chain or branched alkoxy group, and Cy is a group selected from a 4,4′-biphenyldiyl group, a 4,4′-phenylcyclohexyl group, and a 4,4′-dicyclohexyl group.
• R 3 represents —O— or —CH 2 O—
• Cy2 has the same meaning as Cy
• each R 7 independently represents a linear or branched group having 3 to 12 carbon atoms.
• the cis-trans isomerism of 1,4-cyclohexylene indicates the trans isomer.
• 4- (2- (methylamino) ethyl) aniline or a diamine described in JP 2010-97188 A can be used.
• the photoreactive diamines the following compounds are preferable from the viewpoint of photoreactivity and the like.
• n represents an integer of 0 to 18.
• tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include the following groups [1] to [5].
• R 3 to R 23 are each Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a monovalent having 1 to 6 carbon atoms containing a fluorine atom
• R M represents a hydrogen atom or a methyl group
• Xa is a tetravalent organic group represented by the following formulas (Xa-1) to (
• aromatic tetracarboxylic dianhydrides for example, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid dianhydrides, acid dianhydrides represented by the following formulas (Xb-1) to (Xb-10); and
• the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
• acid dianhydrides X1-1 to X1-3, X1-5 to X1-12, Xa-, from the viewpoint of solubility in a solvent of a polyimide precursor or a polyimide obtained by imidizing the polyimide precursor.
• Xa-3, Xb-13, X6 to X8, Xb-1, Xb-7 to Xb-9, Xb-13, X1-44, X1-47 to X1-52 are preferred, or X1-1 to X1-3, X1-5 to X1-12, Xa-1 to Xa-3, Xb-7 to Xb-9, X1-44, and X1-49 are more preferable.
• the polyamic acid used in the present invention can be synthesized by a known method (for example, see International Publication WO2014 / 034792).
• the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more. It may be used.
• the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight body is easily obtained.
• polyamic acid ester The polyamic acid ester used in the present invention can be obtained as follows.
• the polyamic acid ester used in the present invention is (1) synthesized from a polyamic acid, (2) synthesized a polyamic acid ester from a tetracarboxylic acid diester and a diamine, or (3) a tetracarboxylic acid diester dichloride and a diamine.
• synthesis by reaction it can be synthesized by any known method (for example, see International Publication WO2014 / 034792).
• Examples of the tetracarboxylic acid diester include the following reaction formula (wherein R 1 is an alkyl group having 1 to 5 carbon atoms, and A is a tetravalent organic group derived from the tetracarboxylic dianhydride).
• R 1 is an alkyl group having 1 to 5 carbon atoms
• A is a tetravalent organic group derived from the tetracarboxylic dianhydride.
• the compound represented by [5-p-1] is preferable from the viewpoint of obtaining a high molecular weight and low-dispersion polyamic acid ester.
• the tetracarboxylic acid diester dichloride can be produced, for example, by a known method of chlorinating the tetracarboxylic acid dialkyl ester (see, for example, International Publication WO2010 / 092989).
• tetracarboxylic acid diester dichloride is represented by the formula [5-Cl] (in the above formula (5-Cl), A is the same as A in the above formula (5). Is preferred).
• the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the viewpoint of solubility of the polyamic acid ester, and these may be used alone or in combination.
• the polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
• the polyimide used in the present invention can be obtained by a known method (for example, see International Publication WO2013 / 125595).
• the polyimide may be a complete imidized product obtained by dehydrating and ring-closing all of the amic acid structure that the polyamic acid had or the amic acid ester structure that the polyamic acid ester had, and it may have an amic acid or amic acid ester structure. It may be a partially imidized product in which only a part is dehydrated and closed and an amic acid structure or an amic acid ester structure and an imide ring structure coexist.
• the polyimide to be used preferably has an imidization ratio of 20% or more, and is preferably 90% or less, and more preferably 60% or less, from the viewpoint of ensuring solubility in a solvent.
• This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of amic acid structures or amic acid ester structures of polyimide and the number of imide ring structures, expressed as a percentage.
• a part of the imide ring may be an isoimide ring.
• the component (A) may be at least one polymer selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester.
• the component (A) comprises at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dichloride, and a diamine. It is a polymer obtained by making these react.
• the tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dichloride are preferably the aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic It is preferable to include at least one structure selected from the group consisting of acid dianhydrides and their tetracarboxylic acid diesters and tetracarboxylic acid diester dichlorides.
• the amount of these preferred compounds (T) used (the total amount when two or more are used) is 10 mol% with respect to the total amount of tetracarboxylic dianhydride and its derivative used for the synthesis of polyamic acid.
• the content is 20 mol% or more, and more preferably 30 mol% or more.
• the molecular weight of the polyamic acid, polyamic acid ester and polyimide described in the present invention is preferably 2,000 to 500,000 in weight average molecular weight, more preferably 5,000 to 300,000, still more preferably 10, 000 to 100,000.
• the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
• the component (A) may be 1 to 15% by weight, preferably 1 to 8% by weight, more preferably 1.5 to 7% by weight when the total amount of the liquid crystal aligning agent is 100% by weight.
• the liquid crystal aligning agent of this application contains (B) component.
• Component (B) is a compound represented by the following formula (N-1).
• R 1 and R 2 are the same or different and each represents a linear or branched alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms.
• the alkylene group and / or the cycloalkylene group may have at least one group selected from the group consisting of ethers and tertiary amines.
• the alkylene group may be a saturated or unsaturated alkylene group.
• R 1 and R 2 may be a linear alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and a saturated linear alkylene group having 1 to 2 carbon atoms is particularly preferable.
• R 3 and R 4 are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.
• the alkyl group may have at least one group selected from the group consisting of ethers and tertiary amines.
• the alkyl group may be a saturated or unsaturated alkyl group.
• R 3 and R 4 may be a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a hydrogen atom.
• R 5 represents a z-valent aliphatic hydrocarbon group having 1 to 24 carbon atoms or a z-valent alicyclic hydrocarbon group having 3 to 24 carbon atoms. Any of a cycloalkane group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 5 to 12 carbon atoms, (thio) ether, carbonyl, or tertiary amine between carbon-carbon bonds in the aliphatic hydrocarbon group May be inserted, and this aliphatic hydrocarbon group may have one group selected from epoxy and halogen.
• Any of (thio) ether, carbonyl, and tertiary amine may be inserted between the carbon-carbon bonds in the alicyclic hydrocarbon group, and one of the single bonds that do not constitute a ring is the number of carbon atoms. May be substituted with 1 to 12 alkylene groups; z is an integer of 1 to 6.
• Examples of the cycloalkane group having 3 to 12 carbon atoms of R 5 include groups in which two hydrogen atoms have been removed from any of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, norbornane, and adamantane.
• Examples of the aromatic hydrocarbon group having 5 to 12 carbon atoms of R 5 include groups in which two hydrogen atoms have been removed from any one of benzene, biphenyl, pyridine, pyrazine, naphthalene, furan, imidazole, oxazole, thiazole and furan. be able to.
• Examples of the alkylene group having 1 to 12 carbon atoms of R 5 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and a vinylene group.
• R 5 When z is 1 and R 5 is a monovalent aliphatic hydrocarbon group having 1 to 24 carbon atoms, R 5 may be an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, and And alkynyl groups having 2 to 24 carbon atoms. z is equal to or greater than 2, when R 5 is a divalent or more aliphatic hydrocarbon group having 1 to 24 carbon atoms, as R 5, z aliphatic hydrocarbon group of the monovalent carbon atoms 1-24 -1 hydrogen atoms are removed to form a bond.
• R 5 is a monovalent alicyclic hydrocarbon group having 3 to 24 carbon atoms, as R 5, a cycloalkyl group, a decahydronaphthyl group, a monovalent group such as an adamantyl group Can be mentioned.
• R 5 is z-1 from the monovalent alicyclic hydrocarbon group having 3 to 24 carbon atoms. The hydrogen atom is removed to form a bond.
• an epoxy compound having a structure represented by the following formulas (N-2-1) to (N-2-4) is preferable.
• each X independently represents a single bond, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group.
• Y represents a methylene group, an ethylene group, a trimethylene group, a vinylene group, an oxy group, or a thio group.
• Z represents a cyclopentanediyl group, a cyclohexanediyl group, or a norbornanediyl group.
• the component (B) is 1 to 30% by weight, preferably 2 to 20% by weight, more preferably 2 to 15% by weight, and still more preferably 2% with respect to 100% by weight of the component (A). It should be ⁇ 10% by weight.
• the liquid crystal aligning agent of the present application contains at least one specific solvent selected from the group consisting of the following formulas (1) to (8) as the component (C).
• R 11 to R 16 and R 20 to R 21 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 17 to R 19 each represents an alkyl group having 1 or 2 carbon atoms.
• N in the formula (7) represents an integer of 1 to 3.
• the amount of the component (C) is 70% by weight or more, preferably 70 to 100% by weight, more preferably 80 to 100% by weight.
• the liquid crystal aligning agent of the present application may optionally contain components other than the components (A) to (C) described above.
• a-22, a-13 to a-21, a-24, a-26, a-27, a-31, a-34, a-37, a-38 are preferred, and a-22 and a-37 are more preferred.
• Examples of components other than the components (A) to (C) include crosslinkable compounds.
• the crosslinkable compound has, for example, at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.
• a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond can be included, but is not limited thereto. In addition, it is good to have 2 or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
• crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraphenylglycidyl ether ethane, and triphenylglycidyl.
• the crosslinkable compound having an oxetane group is a compound having at least two oxetane groups represented by the following formula [4A].
• crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
• the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].
• Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
• a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
• the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol
• Examples of the melamine derivative or benzoguanamine derivative include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
• MX-750 which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
• MW-30 manufactured by Sanwa Chemical Co., Ltd.
• Methoxymethylated ethoxyme Benzomethylamine methoxymethyl butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxymethyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide).
• glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.
• Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, the crosslinkable compounds of the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27) can be mentioned. It is done.
• crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
• Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl
• E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring
• E 2 Represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
• crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, or may combine 2 or more types.
• the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
• the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymer component. More preferred is 1 to 50 parts by mass.
• the liquid crystal aligning agent of the present invention can use a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied.
• the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include surfactants described in paragraph [0117] of International Publication No. WO2016 / 047771.
• F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
• the amount of the surfactant used 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 all the polymer components contained in the liquid crystal aligning agent.
• the liquid crystal aligning agent is disclosed in International Publication No. WO2011 / 132751 (published 2011.10.27) on pages 69 to 73 as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device.
• Nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] can also be added.
• the amine compound may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine compound after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
• the solvent is not particularly limited as long as the specific polymer (A) is dissolved.
• the liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal aligning film, and a compound that promotes charge removal.
• a polymer other than the polymer described in the present invention, a silane coupling agent for the purpose of improving the adhesion between the alignment film and the substrate, and further when firing the coating film An imidization accelerator for the purpose of efficiently progressing imidization by heating of the polyimide precursor may be added to.
• the liquid crystal aligning agent of the present application has a form of a solution containing the above-mentioned components (A) to (C).
• the liquid crystal aligning agent used in the present invention has a form of a solution in which a polymer having a specific structure is dissolved in an organic solvent.
• the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but it is 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film. It is preferable to be 10% by weight or less from the viewpoint of storage stability of the solution.
• the liquid crystal aligning agent of this application changes suitably solid content concentration (ratio which the total weight of components other than (C) component of a liquid crystal aligning agent accounts to the total weight of a liquid crystal aligning agent) by the setting of the thickness of the coating film to form.
• solid content concentration ratio which the total weight of components other than (C) component of a liquid crystal aligning agent accounts to the total weight of a liquid crystal aligning agent
• it is preferably 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film, and preferably 10% by weight or less from the viewpoint of storage stability of the solution.
• the particularly preferable solid content concentration range varies depending on the method of applying the liquid crystal aligning agent to the substrate.
• the polymer concentration is particularly preferably in the range of 1.5 to 4.5% by weight.
• the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
• the solid content concentration is particularly preferably in the range of 1 to 5% by weight, and thereby the solution viscosity is preferably in the range of 3 to 15 mPa ⁇ s.
• the molecular weight of the polyimide precursor and polyimide that are the component (A) of the present application is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably, in terms of weight average molecular weight. It should be 10,000 to 100,000.
• the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000. .
• liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention.
• the step of applying the liquid crystal aligning agent of the present invention onto a substrate to form a coating film, and the coating film is not in contact with the liquid crystal layer or the liquid crystal layer there is provided a method for producing a liquid crystal alignment film, comprising a step of irradiating the coating film with light in contact.
• liquid crystal display device comprising the liquid crystal alignment film according to the present invention or the liquid crystal alignment film obtained by the production method of the present invention. Details are shown below.
• the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent.
• the operation mode of the liquid crystal display element according to the present invention is not particularly limited. For example, a TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type. (IPS type), FFS (Fringe Field Switching) type, optical compensation bend type (OCB type), etc., can be applied.
• the liquid crystal display device according to the present invention can be manufactured, for example, by steps including the following steps (1-1) to (1-3).
• step (1-1) the substrate to be used varies depending on the desired operation mode.
• step (1-2) and step (1-3) are common to each operation mode.
• the liquid crystal aligning agent of this invention is apply
• (1-1A) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is formed, and each transparent conductive film is formed. On the surface, the liquid crystal aligning agent prepared above is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method.
• the substrate for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used.
• a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of US PPG) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 -SnO 2 ), etc. Can be used.
• a method of forming a pattern by photo-etching a method of using a mask having a desired pattern when forming a transparent conductive film; And so on.
• a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.
• preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent.
• the prebake temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., and particularly preferably 40 to 100 ° C.
• the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.
• a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed.
• the firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., more preferably 120 to 250 ° C.
• the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the thickness of the film thus formed is preferably 0.001 to 1 ⁇ m, more preferably 0.005 to 0.5 ⁇ m.
• an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided.
• a liquid crystal aligning agent is apply
• the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (1-1A).
• the metal film for example, a film made of a metal such as chromium can be used.
• a treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1-1) is performed.
• the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
• the alignment ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment in which the coating film is irradiated with polarized or non-polarized radiation. Processing.
• the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film. May be.
• ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation applied to the coating film.
• the radiation When the radiation is polarized light, it may be linearly polarized light or partially polarized light.
• irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof.
• the direction of irradiation is an oblique direction.
• a light source to be used for example, 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.
• Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating.
• the irradiation dose is preferably 10 to 5,000 mJ / cm 2, more preferably 30 to 2,000 mJ / cm 2.
• the temperature at the time of heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
• the light irradiation film obtained in the above step can be used as a liquid crystal alignment film as it is. Also good.
• the firing temperature at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
• the firing time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the photo-alignment process here corresponds to a light irradiation process in a state where it is not in contact with the liquid crystal layer.
• the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or a surface of the liquid crystal alignment film.
• a resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. .
• a liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer Sustained Alignment) type liquid crystal display element.
• Step (1-3): Construction of liquid crystal cell (1-3A) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates facing each other.
• the first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded.
• a liquid crystal cell is manufactured by injecting and filling the liquid crystal into the cell gap partitioned by the step of sealing the injection hole.
• the second method is a method called an ODF (One Drop Fill) method.
• ODF One Drop Fill
• an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface.
• the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell.
• the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.
• an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
• the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable.
• Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used.
• cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck)
• a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
• the liquid crystal can also contain additional anisotropic dyes.
• the term “dye” can mean a substance capable of intensively absorbing or deforming light in the visible light region, for example, at least partly or entirely within the wavelength range of 400 nm to 700 nm.
• isotropic dye may mean a substance capable of anisotropic absorption of light in at least a part or the entire range of the visible light region.
• the color sensation of the liquid crystal cell can be adjusted through the use of the dye as described above.
• the kind of the anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used.
• the ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the intended physical properties.
• the ratio of the anisotropic dye is 0.01 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal compound. However, the above ratio can be changed to an appropriate range if necessary.
• a liquid crystal cell is constructed in the same manner as in (1-3A) except that a photopolymerizable compound is injected or dropped together with liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
• the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
• the light to be irradiated for example, ultraviolet rays including visible light having a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable.
• a light source of irradiation light for example, 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.
• the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating.
• the irradiation dose of light preferably less than 100 mJ / cm 2 or more 20,000mJ / cm 2, more preferably 100 ⁇ 10,000mJ / cm 2.
• a liquid crystal cell is prepared in the same manner as (1-3A) above. Then, a method of manufacturing a liquid crystal display element may be adopted by performing a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. According to this method, the PSA mode can be realized with a small amount of light irradiation.
• the light irradiation to the liquid crystal cell may be performed in a state where the liquid crystal is driven by applying a voltage, or may be performed in a state where a low voltage is applied so as not to drive the liquid crystal.
• the applied voltage can be, for example, 0.1 to 30 V direct current or alternating current.
• the description of (1-3B) above can be applied to the conditions of light to be irradiated.
• the light irradiation process here corresponds to a light irradiation process in a state of contact with the liquid crystal layer.
• the liquid crystal display element according to the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
• a polarizing plate to be bonded to the outer surface of the liquid crystal cell a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films
• the polarizing plate which consists of can be mentioned.
• the liquid crystal display device can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones. It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.
• various display devices such as various monitors, liquid crystal televisions, and information displays.
• the liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film excellent in the uniformity of the film thickness within the coating surface and the linearity and dimensional stability of the coating peripheral portion. Further, by using the liquid crystal aligning agent of the present invention, the voltage holding ratio becomes a desired value, and a liquid crystal alignment film having excellent rubbing resistance and reliability can be obtained.
• ⁇ Diamine compound> p-PDA p-phenylenediamine
• DBA 3,5-diaminobenzoic acid
• PCH7 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
• APC12 1,3-diamino -4- (dodecanoxy) benzene
• PBCH5 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
• DA-3 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane
• NMP N-methyl-2-pyrrolidone
• GBL ⁇ -butyllactone
• BCS Butyl cellosolve
• CHN Cyclohexanone
• CPN Cyclopentanone
• PGME Propylene glycol monomethyl ether
• EC Ethyl carbitol
• DME Diethylene glycol dimethyl ether
• the molecular weight of the polymer in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200, Shodex column (KD-803, KD-805) manufactured by Senshu Scientific.
• GPC room temperature gel permeation chromatography
• the molecular weight of the polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805) (manufactured by Shodex). Measured.
• GPC normal temperature gel permeation chromatography
• the imidation ratio of polyimide in the synthesis example was measured as follows. Polyimide powder (20 mg) was put into an NMR sample tube (NMR sampling tube standard ⁇ 5 (manufactured by Kusano Kagaku)) and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixed product) (0. 53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
• This deposit was wash
• the imidation ratio of this polyimide was 51%, the number average molecular weight was 16,100, and the weight average molecular weight was 37,200.
• Example 5 GBL (6.3 g) and PGME (17.3 g) were added to 1 g of the polyimide powder (A) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C. for 15 hours to obtain a polyimide solution. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution. Next, a 10 wt% PGME solution (0.5 g) of TETRAD-C was added to this polyimide solution and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (5).
• Examples 6 to 8 GBL (6.3 g), PGME (12.5 g), and 1 g of each of the polyimide powders (A), (B), and (C) obtained in Synthesis Example 1, Synthesis Example 2, and Synthesis Example 3, and DME (5.0 g) was added and stirred at 70 ° C. for 15 hours to obtain a polyimide solution.
• any of the polyimide solutions no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
• a 10 wt% PGME solution (0.3 g) of TETRAD-C was added to these polyimide solutions and stirred at room temperature for 30 minutes to obtain liquid crystal aligning agents (6) to (8).
• PGME (18.9g) and EC (5.0g) were added to 1g of polyimide powder (A) obtained by the synthesis example 1, and the polyimide solution was obtained by stirring at 70 degreeC for 15 hours. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• a 10 wt% PGME solution (0.3 g) of TETRAD-C was added to these polyimide solutions and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (9).
• Example 14 To 10 g of the polyamic acid solution (D) obtained in Synthesis Example 4, CHN (7.5 g), PGME (20.6 g), and a 10 wt% PGME solution (0.75 g) of TETRAD-C were added, and at room temperature.
• the liquid crystal aligning agent (14) was obtained by stirring for 30 minutes. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• the solvent drying rate was evaluated, the rubbing resistance was evaluated, the liquid crystal display device was produced, and the liquid crystal alignment was evaluated.
• Example 15 To 10 g of the polyamic acid solution (D) obtained in Synthesis Example 4, CPN (7.5 g), PGME (20.6 g), and a 10 wt% PGME solution (0.75 g) of TETRAD-C were added, and at room temperature. The liquid crystal aligning agent (15) was obtained by stirring for 30 minutes. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• Example 16 To 10 g of the polyamic acid solution (F) obtained in Synthesis Example 6, BCS (7.5 g), PGME (20.6 g), and a 10 wt% PGME solution (0.75 g) of TETRAD-C were added, and at room temperature. The liquid crystal aligning agent (16) was obtained by stirring for 30 minutes. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• Example 17 To 10 g of the polyamic acid solution (D) obtained in Synthesis Example 4, BCS (7.5 g), PGME (20.6 g), and a 10 wt% PGME solution (0.75 g) of TETRAD-C were added, and at room temperature. The liquid crystal aligning agent (16) was obtained by stirring for 30 minutes. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• NMP (16.2 g) and BCS (7.5 g) were added to 1 g of the polyimide powder (A) obtained in Synthesis Example 1, and a polyimide solution was obtained by stirring at 70 ° C. for 15 hours. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• a 10 wt% NMP solution (0.3 g) of TMBIP was added to these polyimide solutions and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (18).
• NMP (16.2 g) and BCS (7.5 g) were added to 1 g of the polyimide powder (A) obtained in Synthesis Example 1, and a polyimide solution was obtained by stirring at 70 ° C. for 15 hours. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• a 10 wt% NMP solution (0.3 g) of GT401 was added to these polyimide solutions, and the mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (19).
• NMP (16.2 g) and BCS (7.5 g) were added to 1 g of the polyimide powder (A) obtained in Synthesis Example 1, and a polyimide solution was obtained by stirring at 70 ° C. for 15 hours. No abnormality such as turbidity or precipitation was observed in this polyimide solution, and it was confirmed that the polyimide solution was a uniform solution.
• a 10 wt% NMP solution (0.5 g) of TMBIP and a 10 wt% NMP solution (0.3 g) of PTSA are added to these polyimide solutions, and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (21). It was.
• the liquid crystal aligning agent of the present invention obtained in Examples (1) to (17) and Comparative Examples (1) to (5) was spin coated on a glass substrate with a transparent electrode, and the solvent was used for 120 seconds on a hot plate at 50 ° C. After drying, baking was performed on a hot plate at 120 ° C. for 5 minutes to form a coating film having a thickness of 100 nm.
• This coating film surface 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 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
• the surface of the liquid crystal alignment film in the vicinity of the center of the substrate was randomly observed with a laser microscope set at a magnification of 100 times, and the rubbing scratches and rubbing residue (about the observation visual field of about 6.5 mm square) The rubbing resistance was evaluated from the average value of the amount of deposits).
• the results are summarized in Table 1.
• the evaluation criteria were determined as follows. Evaluation criteria ⁇ : Rubbing scratches and rubbing residues 20 or less ⁇ : Rubbing scratches and rubbing residues 20 to 40 ⁇ : Rubbing scratches and rubbing residues 40 or more
• the surface of the coating film is rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. It was. Two substrates were prepared, and 4 ⁇ m bead spacers were sprayed on the liquid crystal alignment film of one of the substrates, and then a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was applied.
• a sealing agent XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.
• an empty cell was produced by thermosetting the sealant at 120 ° C. for 90 minutes.
• a negative type liquid crystal (MLC-3022, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
• the isotropic phase treatment is performed at 120 ° C. for 1 hour, and then the cell is observed with a polarizing microscope. There is no alignment defect such as light leakage or domain generation in any liquid crystal cell, and uniform liquid crystal alignment is achieved. It was confirmed that it was obtained.
• the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used for display elements of various liquid crystal modes. These elements are also useful in liquid crystal displays for display purposes, and in light control windows and optical shutters for controlling transmission and blocking of light.

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