WO2020148953A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides Download PDF

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WO2020148953A1
WO2020148953A1 PCT/JP2019/040133 JP2019040133W WO2020148953A1 WO 2020148953 A1 WO2020148953 A1 WO 2020148953A1 JP 2019040133 W JP2019040133 W JP 2019040133W WO 2020148953 A1 WO2020148953 A1 WO 2020148953A1
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liquid crystal
aligning agent
group
crystal aligning
solvent
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PCT/JP2019/040133
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English (en)
Japanese (ja)
Inventor
哲 平野
恵 中西
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Jsr株式会社
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Priority to CN201980087149.9A priority Critical patent/CN113260911A/zh
Priority to JP2020566104A priority patent/JP7409325B2/ja
Publication of WO2020148953A1 publication Critical patent/WO2020148953A1/fr

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    • 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
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • 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 disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal element.
  • the liquid crystal element has a liquid crystal alignment film having a function of aligning liquid crystal molecules in a liquid crystal layer in a certain direction.
  • the liquid crystal aligning film is generally formed on the substrate by applying a liquid crystal aligning agent in which a polymer component is dissolved in an organic solvent onto the surface of the substrate, and preferably by heating.
  • a liquid crystal aligning agent in which a polymer component is dissolved in an organic solvent onto the surface of the substrate, and preferably by heating.
  • the solvent component of the liquid crystal aligning agent N-methyl-2-pyrrolidone, ⁇ -butyrolactone and the like are generally used as a solvent (good solvent) having high solubility of the polymer component.
  • the size of the liquid crystal display device can be increased, or by taking a plurality of panels from one substrate, the time and cost of the manufacturing process can be reduced. Are being reduced.
  • the size of the substrate is increased, the application area of the liquid crystal aligning agent becomes large in area, so that it becomes difficult to secure the uniformity of the film quality over the entire application area.
  • a coating method by an inkjet printing method has been introduced in a manufacturing process of a large liquid crystal panel.
  • N-methyl-2-pyrrolidone and ⁇ -butyrolactone are excellent in solubility of the polymer component of the liquid crystal aligning agent, and therefore, when the liquid crystal aligning agent is applied on the substrate by the inkjet printing method in the production of a large liquid crystal panel. Therefore, it is possible to reduce the unevenness of application of the liquid crystal aligning agent.
  • N-methyl-2-pyrrolidone and ⁇ -butyrolactone are likely to cause deterioration of the inkjet head, and the inkjet head is likely to be replaced frequently.
  • the nozzle diameter of an inkjet head has become smaller. If the nozzle diameter becomes smaller, the ejection margin becomes narrower, which may cause deterioration of the inkjet head.
  • the present disclosure has been made in view of the above circumstances, and provides a liquid crystal aligning agent that has good coatability on a substrate, is less likely to deteriorate an inkjet head, and can obtain a liquid crystal element having excellent afterimage characteristics. Is the main purpose.
  • a liquid crystal aligning agent containing a compound in which a hydrogen atom bonded to a ring portion of an aromatic ring is substituted with a hydroxyalkyl group or an alkoxy group having 1 to 3 carbon atoms It was found that the above problems can be solved by doing so. Specifically, according to the present disclosure, the following means are provided. [1] A liquid crystal aligning agent containing a polymer component and a compound [A] represented by the following formula (1).
  • liquid crystal aligning agent that has good coatability on a substrate and that does not easily deteriorate an inkjet head.
  • a liquid crystal element having excellent afterimage characteristics can be manufactured.
  • the liquid crystal aligning agent of the present disclosure contains a polymer component and a solvent component. Below, each component contained in the liquid crystal aligning agent and other components optionally blended as necessary will be described.
  • Polymer component As the polymer component contained in the liquid crystal aligning agent, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polymerizable
  • the polymer include a polymer having a structural unit derived from a monomer having an unsaturated bond (hereinafter, also referred to as “polymer (Q)”) as a main skeleton.
  • the polymer component contains at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyamide, and polymer (Q). It is preferable.
  • the polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound.
  • a tetracarboxylic dianhydride examples include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and the like. ..
  • aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride
  • alicyclic tetracarboxylic acid dianhydride examples include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-Oxabicycl
  • diamine compound examples of the diamine compound used for synthesizing the polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples of these diamines include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine; and alicyclic diamines such as 1,4 -Diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc.; Examples of aromatic diamines include dodecaneoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanooxy-2,4-diaminobenzene, pentadecanooxy-2,5
  • R I is an alkanediyl group having 1 to 3 carbon atoms
  • R II is a single bond or an alkanediyl group having 1 to 3 carbon atoms
  • a is 0 or 1
  • b is 0.
  • c is an integer of 1 to 20
  • d is 0 or 1.
  • a and b are not 0 at the same time.
  • a compound represented by the following formula, a side chain type diamine such as a diamine having a cinnamic acid structure in its side chain:
  • the polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic acid dianhydride and a diamine compound together with a molecular weight modifier, if necessary.
  • the ratio of the tetracarboxylic acid dianhydride and the diamine compound used for the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of up to 2 equivalents is preferable.
  • the molecular weight modifier examples include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. Can be mentioned.
  • the use ratio of the molecular weight modifier is preferably 20 parts by mass or less based on 100 parts by mass of the total tetracarboxylic dianhydride and diamine compound used.
  • the synthesis reaction of polyamic acid is preferably carried out in an organic solvent.
  • the reaction temperature at this time is preferably ⁇ 20° C. to 150° C., and the reaction time is preferably 0.1 to 24 hours.
  • the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons.
  • Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol.
  • the amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 to 50% by mass with respect to the total amount (a+b) of the reaction solution. Is preferred.
  • the reaction solution obtained by dissolving the polyamic acid may be directly used for preparing the liquid crystal aligning agent, or the polyamic acid contained in the reaction solution may be isolated and then used for preparing the liquid crystal aligning agent.
  • the polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine compound, [III] tetracarboxylic acid. It can be obtained by a method of reacting an acid diester dihalide with a diamine compound.
  • the polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partial esterified product having both an amic acid structure and an amic acid ester structure.
  • the reaction solution obtained by dissolving the polyamic acid ester may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. Good.
  • the polyimide can be obtained, for example, by subjecting the polyamic acid synthesized as described above to dehydration ring closure to imidize.
  • the polyimide may be a complete imidized product obtained by dehydration ring closure of all of the amic acid structure of the precursor polyamic acid, dehydration ring closure of only a portion of the amic acid structure, amic acid structure and imide It may be a partial imidized product having a ring structure.
  • the imidization ratio of the polyimide is preferably 20 to 99%, more preferably 30 to 90%.
  • This imidization ratio is a percentage of the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of polyimide.
  • a part of the imide ring may be an isoimide ring.
  • the dehydration ring closure of the polyamic acid is preferably carried out by a method in which the polyamic acid is dissolved in an organic solvent, a dehydrating agent and a dehydration ring closure catalyst are added to this solution, and heating is carried out if necessary.
  • a dehydrating agent acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used.
  • the amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid.
  • the dehydration ring-closing catalyst for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used.
  • the amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used.
  • the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature for the dehydration ring closure reaction is preferably 0 to 180°C.
  • the reaction time is preferably 1.0 to 120 hours.
  • the reaction solution containing the polyimide may be used as it is for preparing the liquid crystal aligning agent, or may be used for preparing the liquid crystal aligning agent after isolating the polyimide.
  • Polyimide can also be obtained by imidization of polyamic acid ester.
  • the polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound.
  • the silane compound include tetramethoxysilane, methyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyl.
  • Examples thereof include dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and trimethoxysilylpropylsuccinic anhydride.
  • the hydrolyzable silane compounds may be used alone or in combination of two or more.
  • “(Meth)acryloxy” is meant to include “acryloxy” and “methacryloxy”.
  • the hydrolysis/condensation reaction is carried out by reacting one or more silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent.
  • the amount of water used is preferably 1 to 30 mol per 1 mol of the silane compound (total amount).
  • the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds and zirconium compounds.
  • the amount of the catalyst used varies depending on the type of the catalyst, reaction conditions such as temperature, and the like, but is, for example, 0.01 to 3 times the mol of the total amount of the silane compound.
  • Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, alcohols and the like, and it is preferable to use a water-insoluble or slightly water-soluble organic solvent.
  • the use ratio of the organic solvent is preferably 10 to 10,000 parts by mass with respect to 100 parts by mass in total of the silane compound used in the reaction.
  • the above reaction is preferably carried out by heating with an oil bath or the like. The heating temperature at that time is preferably 130° C. or lower, and the heating time is preferably 0.5 to 12 hours.
  • the organic solvent layer separated from the reaction solution is dried with a desiccant, if necessary, and then the solvent is removed to obtain the target polyorganosiloxane.
  • the method for synthesizing the polyorganosiloxane is not limited to the above hydrolysis/condensation reaction, and for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol may be used.
  • a liquid crystal aligning agent contains a polyorganosiloxane having a side chain having a functional functional group such as a photo-alignment group or a pretilt angle imparting group
  • an epoxy group-containing silane compound is used as at least a part of the raw material.
  • a polyorganosiloxane having an epoxy group in a side chain is synthesized by polymerization, and then an epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid having a functional functional group to obtain a target polyorganosiloxane.
  • Polyamide can be obtained by a method of reacting a dicarboxylic acid and a diamine compound, or the like.
  • the dicarboxylic acid is preferably subjected to acid chloride formation using a suitable chlorinating agent such as thionyl chloride and then subjected to a reaction with a diamine compound.
  • the dicarboxylic acid used in the synthesis of the polyamide is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid and fumaric acid; cyclobutane.
  • Alicyclic dicarboxylic acids such as dicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-carboxycinnamic acid, Aromatic dicarboxylic acids such as 3,3′-[4,4′-(methylenedi-p-phenylene)]dipropionic acid and 4,4′-[4,4′-(oxydi-p-phenylene)]dibutyric acid And the like.
  • the diamine compound used for the synthesis include the diamine compounds exemplified in the explanation of polyamic acid.
  • the dicarboxylic acid and diamine compounds may each be used alone or in combination of two or more.
  • the reaction of the dicarboxylic acid and the diamine compound is preferably carried out in an organic solvent in the presence of a base.
  • the use ratio of the dicarboxylic acid and the diamine compound is preferably such that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine compound.
  • the reaction temperature is preferably 0°C to 200°C, and the reaction time is preferably 0.5 to 48 hours.
  • the organic solvent for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used.
  • tertiary amines such as pyridine, triethylamine and N-ethyl-N,N-diisopropylamine can be preferably used.
  • the amount of the base used is preferably 2 to 4 mol per 1 mol of the diamine compound.
  • the solution obtained by the above reaction may be directly used for preparing the liquid crystal aligning agent, or may be used for preparing the liquid crystal aligning agent after isolating the polyamide contained in the reaction solution.
  • Examples of the monomer having a polymerizable unsaturated bond include compounds having a (meth)acryloyl group, a vinyl group, a vinylphenyl group, a styryl group, a maleimide group and the like. Specific examples of such compounds include unsaturated carboxylic acids such as (meth)acrylic acid, ⁇ -ethylacrylic acid, maleic acid, fumaric acid and vinylbenzoic acid: alkyl (meth)acrylate, cycloalkyl (meth)acrylate.
  • Unsaturated carboxylic acid esters such as 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 3,4-epoxybutyl, acrylic acid 4-hydroxybutyl glycidyl ether: Unsaturated polycarboxylic acid anhydrides such as maleic anhydride: (Meth)acrylic compounds such as styrene, methylstyrene, aromatic vinyl compounds such as divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; N-methylmaleimide, N -Maleimide group-containing compounds such as -cyclohexylmaleimide and
  • the polymer (Q) can be obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator.
  • a polymerization initiator examples include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2) , 4-dimethylvaleronitrile) and the like are preferable.
  • the proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all the monomers used in the reaction.
  • the polymerization reaction is preferably carried out in an organic solvent.
  • Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds and the like, with diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate being preferred.
  • the reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 to 36 hours.
  • the amount (a) of the organic solvent used is such that the total amount (b) of the monomers used in the reaction is 0.1 to 60 mass% with respect to the total amount (a+b) of the reaction solution. Is preferred.
  • the polymer solution obtained by the above reaction may be directly used for the preparation of the liquid crystal aligning agent, or the polymer (Q) contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal aligning agent.
  • the polymer used for preparing the liquid crystal aligning agent preferably has a solution viscosity of 10 to 800 mPa ⁇ s, and more preferably 15 to 500 mPa ⁇ s, which is prepared and measured under the conditions described below.
  • the solution viscosity (mPa ⁇ s) is a concentration of 10 mass prepared by using a good solvent for the polymer ( ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc. in the case of polyamic acid, polyamic acid ester and polyimide).
  • the polystyrene-equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) can be appropriately selected according to the type of the polymer, but is preferably 1,000 to 500,000. Yes, and more preferably 2,000 to 300,000.
  • the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, and more preferably 5 or less.
  • the polymer used for preparing the liquid crystal aligning agent may be one kind or a combination of two or more kinds.
  • the polymer component contained in the liquid crystal aligning agent is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane, from the viewpoint of liquid crystal aligning property, affinity with liquid crystal, and mechanical strength. It is preferable that it contains at least one selected. It is particularly preferable that the polymer component contains at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester as a main component.
  • the main component is a component having the largest content on a mass basis, and for example, a component having a content of 50 mass% or more.
  • the polymer component at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester, preferably contains 50% by mass or more, and 60% by mass or more based on the total amount of the polymer components. It is more preferable that the content is 80% by mass or more.
  • the liquid crystal aligning agent of the present disclosure contains a compound [A] represented by the following formula (1).
  • (R 2 )x-Ar 1 -R 1 (1) Ar 1 is a (x+1)-valent aromatic ring group, and R 2 is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
  • x is 0 or 1.
  • R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • the (x+1)-valent aromatic ring group of Ar 1 is a group obtained by removing (x+1) hydrogen atoms from the ring portion of the aromatic ring.
  • the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle. Specific examples of the aromatic ring include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring and an anthracene ring; and an aromatic heterocycle such as a pyrrole ring, a pyridine ring, a pyrimidine ring and a pyridazine ring.
  • Ar 1 is preferably a group obtained by removing (x+1) hydrogen atoms from the ring portion of a benzene ring or a 5-membered heterocyclic ring, and (x+1) from the ring portion of a benzene ring or a furan ring. It is particularly preferable that it is a group in which the hydrogen atom of is removed.
  • examples of the hydroxyalkyl group having 1 to 3 carbon atoms include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group and 2-hydroxypropyl group. , 3-hydroxypropyl group, and 2-hydroxy-1-methylethyl group.
  • examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group.
  • R 1 is preferably linear.
  • the alkyl group having 1 to 3 carbon atoms may be linear or branched, but is preferably linear.
  • R 2 is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • R 2 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. It is preferable that x is 0.
  • Compound [A] is a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) It is particularly preferable that it is at least one selected from the group consisting of (In the formulas (1-1) to (1-3), n and r are each independently an integer of 1 to 3, m is an integer of 0 to 2. R 3 is a carbon number of 1 to 3. Is an alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and y is 0 or 1.)
  • R 3 The bonding position of R 3 is not particularly limited, but it is preferably ortho to the group “—(CH 2 ) n —OH” or the group “—O—(CH 2 ) m —CH 3 ”. It is preferable that y is 0.
  • Preferred specific examples of the compound [A] include compounds represented by the following formulas (1-1-1) to (1-1-3) as the compounds represented by the above formula (1-1).
  • compounds represented by the following formulas (1-2-1) to (1-2-4) are respectively represented by the above formula (1-3)
  • Examples of the compound represented by are the compounds represented by the following formulas (1-3-1) to (1-3-6).
  • the compounds represented by the above formulas (1-1-1) and (1-2-1) are preferable because they are more excellent in ink jet coatability, and are more resistant to deterioration of the ink jet head.
  • Compounds represented by the above formulas (1-1-1) and (1-3-1) are preferable.
  • one type may be used alone, or two or more types may be used in combination.
  • the content ratio of the compound [A] is preferably 100 parts by mass or more, more preferably 300 parts by mass or more, and still more preferably 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the liquid crystal aligning agent. It is 600 parts by mass or more.
  • the content ratio of the compound [A] is preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less.
  • the compound [A] Since the compound [A] has excellent solubility in the polymer component of the liquid crystal aligning agent, it is used as an alternative solvent for N-methyl-2-pyrrolidone (NMP) which is generally used as a good solvent for the polymer component. It is useful.
  • NMP N-methyl-2-pyrrolidone
  • the content ratio of NMP in the liquid crystal aligning agent is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 1 mass% with respect to the total amount of the solvent component of the liquid crystal aligning agent. % Or less.
  • the liquid crystal aligning agent may further contain a component different from the polymer component and the compound [A] (hereinafter, also referred to as “other component”), if necessary.
  • the liquid crystal aligning agent is an ether-based solvent, an alcohol-based solvent, a chain ester-based solvent, together with the polymer component and the compound [A], for the purpose of enhancing the wettability and spreading property of the liquid crystal aligning agent.
  • at least one solvent selected from the group consisting of ketone solvents hereinafter, also referred to as “solvent [B]”.
  • solvent [B] examples include ether solvents such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve).
  • ether solvents such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve).
  • alcohol solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, 3-methoxy-3-methylbutanol, benzyl alcohol.
  • chain ester solvents for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl pro Peonate, isoamyl isobutyrate, etc.;
  • the ketone solvent for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methylcyclohexanone, 4-methylcyclohexanone, diisobutyl ketone, etc., respectively.
  • ketone solvent for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopen
  • the solvent [B] at least one selected from the group consisting of ether solvents, alcohol solvents, and ketone solvents is preferable among the above, from the viewpoint that the effect of improving coatability can be further enhanced, and the solvent has 8 or less carbon atoms. At least one selected from the group consisting of ether solvents, alcohol solvents and cyclic ketone solvents is more preferable.
  • the solvent [B] is ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl.
  • Particularly preferred is one selected from the group consisting of ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol and cyclopentanone.
  • 1 type can be used individually or in combination of 2 or more types.
  • the liquid crystal aligning agent is a solvent different from the solvent [B] (hereinafter, also referred to as "other solvent") for the purpose of further enhancing the solubility of the polymer component and the wettability and spreadability of the liquid crystal aligning agent. May be further included.
  • the other solvent include aprotic polar solvents, halogenated hydrocarbon solvents, hydrocarbon solvents and the like.
  • Specific examples of the other solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, gammabutyrolactone and propylene carbonate.
  • the other solvent is preferably an aprotic polar solvent and is selected from the group consisting of gamma butyrolactone, N-ethyl-2-pyrrolidone, propylene carbonate, and 1,3-dimethyl-2-imidazolidinone. More preferably, it is at least one kind.
  • 1 type can be used individually or in combination of 2 or more types.
  • the content ratio of the compound [A] is such that the solvent (compound [A], solvent [B]) contained in the liquid crystal aligning agent is suitably suppressed from the viewpoint of suitably suppressing deterioration of the inkjet head while improving the coating property of the liquid crystal aligning agent.
  • other solvents is preferably 10% by mass or more.
  • the content ratio is more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more, based on the total amount of the solvent.
  • the content ratio of the compound [A] is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the solvent contained in the liquid crystal aligning agent. Is.
  • the content ratio of the solvent [B] is preferably 5% by mass or more, and more preferably 10% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent. % Or more. Further, the content ratio of the solvent [B] is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less based on the total amount of the solvent of the liquid crystal aligning agent.
  • the content ratio of the other solvent is preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass or less with respect to the total amount of the solvent contained in the liquid crystal aligning agent. Is more preferable, and particularly preferably 50% by mass or less.
  • liquid crystal aligning agent examples include, in addition to the above components, for example, an epoxy group-containing compound (eg, N,N,N′,N′-tetraglycidyl-m-xylenediamine, N,N,N).
  • an epoxy group-containing compound eg, N,N,N′,N′-tetraglycidyl-m-xylenediamine, N,N,N.
  • the ratio D of the components in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent other than the solvent is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 1 to 10% by mass. It is a range.
  • the ratio D is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film.
  • the ratio D exceeds 10% by mass, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property tends to deteriorate. It is in.
  • the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above.
  • the liquid crystal element can be effectively applied to various uses, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television.
  • a display device such as an information display, a light control film, a retardation film, or the like. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited.
  • TN type For example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB. It can be applied to various operation modes such as (Optically Compensated Bend) type.
  • a method of manufacturing a liquid crystal element will be described by taking a liquid crystal display element as an example.
  • the liquid crystal display element can be manufactured by, for example, a method including the following steps 1 to 3.
  • step 1 the substrate used differs depending on the desired operation mode.
  • Steps 2 and 3 are common to each operation mode.
  • a liquid crystal aligning agent is applied onto a substrate, and the applied surface is preferably heated to form a coating film on the substrate.
  • a glass such as float glass or soda glass
  • a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly(alicyclic olefin)
  • a transparent conductive film made of tin oxide (SnO 2 ) (registered trademark of PPG Co., USA), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ). Etc.
  • a TN type, STN type, or VA type liquid crystal element two substrates provided with a patterned transparent conductive film are used.
  • a substrate provided with an electrode formed of a comb-shaped patterned transparent conductive film or a metal film, and a counter substrate provided with no electrode To use.
  • a metal film a film made of a metal such as chromium can be used.
  • the coating of the liquid crystal aligning agent on the substrate is preferably performed by an offset printing method, a spin coating method, a roll coater method, a flexo printing method or an inkjet printing method on the electrode formation surface.
  • the liquid crystal aligning agent has good wettability and spreadability, and in that it can suppress deterioration of the resin member constituting the inkjet head, excellent printability can be exhibited when the inkjet printing method is adopted, and product yield is improved. It is preferable in that the decrease can be suppressed and a liquid crystal alignment film having high performance can be obtained.
  • preheating is preferably performed for the purpose of preventing the liquid crystal aligning agent applied from dripping.
  • the prebake temperature is preferably 30 to 200° C., and the prebake time is preferably 0.25 to 10 minutes.
  • a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermal imidization of the amic acid structure of the polymer.
  • the baking temperature is preferably 80 to 300° C., and the post bake time is preferably 5 to 200 minutes.
  • the thickness of the film thus formed is preferably 0.001 to 1 ⁇ m.
  • a treatment for imparting a liquid crystal aligning ability to the coating film formed in the above step 1 is carried out.
  • the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.
  • the orientation treatment for example, a rubbing treatment of rubbing the coating film in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, or irradiating a coating film formed on a substrate with a liquid crystal aligning agent with light irradiation.
  • a photo-alignment treatment for imparting a liquid crystal aligning ability to the coating film may be mentioned.
  • the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film is subjected to alignment treatment (rubbing treatment, optical alignment treatment). Etc.) may be given.
  • the liquid crystal aligning agent suitable for the vertical alignment type liquid crystal display element can also be suitably used for the PSA (Polymer sustained alignment) type liquid crystal display element.
  • a liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed as described above, and disposing the liquid crystal between the two substrates facing each other.
  • a liquid crystal cell for example, (1) two substrates are arranged so as to face each other with a gap (spacer) so that the liquid crystal alignment films face each other, and the periphery of the two substrates is sealed with a sealant.
  • a method of applying an agent and further dropping liquid crystal at a predetermined number of points on the surface of the liquid crystal alignment film, and then bonding the other substrate so that the liquid crystal alignment film faces and spreading the liquid crystal over the entire surface of the substrate ODF method.
  • It is desirable that the produced liquid crystal cell is further heated to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal.
  • a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used.
  • a photo spacer, a bead spacer, or the like can be used.
  • the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable.
  • a nematic liquid crystal or a smectic liquid crystal may be added with, for example, a cholesteric liquid crystal, a chiral agent, or a ferroelectric liquid crystal.
  • a polymerizable monomer is placed together with a liquid crystal between a pair of substrates, and a light irradiation is performed after a liquid crystal cell is constructed and a voltage is applied between the pair of electrodes.
  • the polarizing plate examples include a polarizing film in which a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between cellulose acetate protective films, or a polarizing plate composed of the H film itself.
  • H film a polarizing film in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between cellulose acetate protective films
  • a polarizing plate composed of the H film itself is obtained.
  • the weight average molecular weight Mw of the polymer, the imidization ratio of polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods.
  • the necessary amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthetic scale shown in the following synthesis examples as needed.
  • the weight average molecular weight Mw is a polystyrene conversion value measured by GPC under the following conditions.
  • Imidization rate of polyimide The polyimide solution was poured into pure water, the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and 1 H-NMR was measured at room temperature using tetramethylsilane as a reference substance.
  • the imidization ratio [%] was calculated by the following mathematical formula (1).
  • Imidization rate [%] (1-(A 1 /(A 2 ⁇ ))) ⁇ 100
  • a 1 is a peak area derived from a proton of an NH group appearing in the vicinity of a chemical shift of 10 ppm
  • a 2 is a peak area derived from another proton
  • ⁇ is a precursor of a polymer (polyamic acid).
  • Solution viscosity of polymer solution The solution viscosity (mPa ⁇ s) of the polymer solution was measured at 25° C. using an E-type rotational viscometer.
  • Epoxy equivalent The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
  • a small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa ⁇ s.
  • NMP was added to the obtained polyamic acid solution to obtain a solution having a polyamic acid concentration of 7% by mass, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110° C. for 4 hours. ..
  • the solvent in the system was replaced with new NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system by this operation.
  • the imidization ratio was about 68.
  • a solution containing 26% by weight of polyimide (PI-1) was obtained.
  • a small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 45 mPa ⁇ s.
  • the reaction solution was poured into a large excess of methanol to precipitate the reaction product.
  • the precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-1).
  • a solution containing a polyamic acid was obtained.
  • a small amount of the obtained polyamic acid solution was sampled, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 60 mPa ⁇ s.
  • 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110° C. for 4 hours.
  • the solvent in the system was replaced with new ⁇ -butyrolactone (GBL) to obtain about 2,500 g of a solution containing 15% by mass of polyimide (PI-2) having an imidization ratio of about 95%. Obtained. A small amount of this solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 70 mPa ⁇ s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-2).
  • GBL ⁇ -butyrolactone
  • a small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 mass% was 75 mPa ⁇ s.
  • imidization was performed in the same manner as in Synthesis Example 1 above to obtain a solution containing 26% by mass of polyimide (PI-4) having an imidization ratio of about 50%.
  • a small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 40 mPa ⁇ s.
  • the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-4).
  • a small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 80 mPa ⁇ s.
  • imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) having an imidization ratio of about 65%.
  • a small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 50 mPa ⁇ s.
  • the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-5).
  • polyamic acid (PA-4) A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa ⁇ s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-4).
  • PA-4 polyamic acid
  • polyamic acid (PA-6) A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 mass% was 85 mPa ⁇ s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-6).
  • PA-6 polyamic acid
  • the weight average molecular weight Mw of the obtained polyamic acid ester (PAE-1) was 34,000.
  • the weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500 and the epoxy equivalent was 180 g/mol. Then, in a 200 mL three-necked flask, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-(dodecyloxy)benzoic acid as a reactive compound, and a catalyst. was charged with 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.), and the reaction was carried out at 100° C. for 48 hours with stirring.
  • EPS-1 reactive polyorganosiloxane
  • UCAT 18X trade name, manufactured by San-Apro Co., Ltd.
  • the coating conditions were 2,500 times/(nozzle/minute) and two reciprocations (total 4 times) with a discharge amount of 250 mg/10 seconds.
  • the substrate was heated at 50° C. to form a coating film having an average film thickness of 0.1 ⁇ m.
  • the obtained coating film was visually observed under irradiation of an interference fringe measurement lamp (sodium lamp) to evaluate unevenness and cissing. Further, the same operation as above was performed except that the heating temperature at the time of forming the coating film was changed from 50° C. to 60° C. and 80° C., and the presence or absence of unevenness and cissing of the coating film was observed.
  • the mass of the sample piece after the sample piece was immersed in the solvent was measured, and the mass ratio ⁇ increased from the mass W1 before immersion was calculated by the following mathematical expression (2).
  • ⁇ [%] ((W2-W1)/W1) ⁇ 100 (2)
  • the evaluation was “good A ( ⁇ )” when the ratio ⁇ was less than 10%, “good B ( ⁇ )” when 10% or more and less than 30%, and 30% or more and less than 50%. In each case, it was evaluated as “Fair ( ⁇ )” and when it was 50% or more, it was evaluated as “Poor (X)”. It should be noted that the lower the ratio ⁇ , the better the solvent to be evaluated is because it is less likely to swell the inkjet head constituent member. As a result of the evaluation, in this example, the color change was “good”, the presence or absence of cracks was “good”, the presence or absence of dissolution was “good”, and the mass change was “good”.
  • a liquid crystal aligning agent (S-1) was applied onto a glass substrate with a transparent electrode consisting of a pair (two sheets) of ITO film using a spinner, and prebaked for 1 minute on a hot plate at 80° C. I went. Then, the solvent was removed by heating (post-baking) at 200° C. for 1 hour in an oven purged with nitrogen to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 ⁇ m.
  • the coating film was rubbed by a rubbing machine having a roll around which a rayon cloth was wound, with a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a foot pressing length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. Note that this rubbing treatment is a weak rubbing treatment performed for the purpose of controlling the collapse of the liquid crystal and performing alignment division by a simple method.
  • An epoxy resin adhesive containing 3.5 ⁇ m diameter aluminum oxide spheres was applied by screen printing to the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other. Then, they were overlapped and pressure-bonded, and heated at 150° C. for 1 hour to thermally cure the adhesive. Next, after filling a negative liquid crystal (MLC-6608 made by Merck) into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive to remove the flow alignment at the time of liquid crystal injection. This was heated at 150° C. for 10 minutes and then gradually cooled to room temperature. Further, a liquid crystal display element was manufactured by bonding two polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.
  • MLC-6608 negative liquid crystal
  • the pretilt angle of the liquid crystal display device obtained by forming the liquid crystal alignment film at different post-baking temperatures 120° C., 180° C. and 230° C. was measured according to the method of 1.
  • the variation characteristics were evaluated.
  • the measurement of the pretilt angle is based on a method described in a non-patent document (T. J. Scheffer et. al. J. Appl. Phys. vo. 19, p. 2013 (1980)), and He-Ne laser light is used.
  • the value of the tilt angle of the liquid crystal molecule from the substrate surface measured by the crystal rotation method using was used as the pretilt angle [°].
  • the evaluation is “good ( ⁇ )” when ⁇ is 0.2° or less, “good ( ⁇ )” and 0.5° when larger than 0.2° and less than 0.5°.
  • a liquid crystal cell for evaluation was produced by the same method as described above.
  • the liquid crystal cell for evaluation was placed under the condition of 60° C., and an alternating voltage of 10 V was applied to the electrode 1 for 300 hours without applying a voltage to the electrode 2.
  • a voltage of AC 3V was applied to both the electrode 1 and the electrode 2, and the difference ⁇ T [%] in light transmittance between the electrodes was measured.
  • the AC afterimage characteristic is “good ( ⁇ )”, when it is 2% or more and less than 3%, it is “OK”, and when it is 3% or more, it is “good”. It was evaluated as “poor (x)”. As a result, this example was evaluated as “good”.
  • Examples 2 to 9 and Comparative Examples 1 to 10 A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the compounding formulations were as shown in Table 1 below. Further, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal aligning agent. The evaluation results are shown in Table 2 below.
  • Example 10 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-10) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below.
  • the liquid crystal aligning agent (S-10) is mainly used for manufacturing a horizontal alignment type liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-10) was used. The results are shown in Table 2 below.
  • a rubbing FFS type liquid crystal display element A glass substrate in which a flat plate electrode (bottom electrode), an insulating layer and a comb-teeth-shaped electrode (top electrode) are laminated in this order on one surface, and a counter glass substrate in which no electrode is provided
  • the liquid crystal aligning agent (S-10) was applied onto each surface using a spinner, and heated (prebaked) on a hot plate at 80° C. for 1 minute. Then, it was dried (post-baked) for 1 hour in an oven at 200° C. in which the inside of the chamber was replaced with nitrogen to form a coating film having an average film thickness of 0.08 ⁇ m.
  • the surface of the coating film was rubbed with a rubbing machine having a roll around which a rayon cloth was wound, at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm/sec, and a foot pressing length of 0.4 mm.
  • ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film.
  • an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 ⁇ m was applied by screen printing, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film was formed.
  • nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting liquid crystal, this was heated at 120° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell.
  • the rubbing directions of the substrates were antiparallel.
  • the polarizing plates were attached so that the polarization directions of the two polarizing plates were parallel and orthogonal to the rubbing direction.
  • the line width of the electrodes was 4 ⁇ m and the distance between the electrodes was 6 ⁇ m.
  • four-system drive electrodes of electrode A, electrode B, electrode C, and electrode D were used as the top electrodes.
  • the bottom electrode acts as a common electrode that acts on all the four-system drive electrodes, and each of the four-system drive electrode regions becomes a pixel region. 4. Evaluation of rubbing FFS type liquid crystal display device The post-bake margin, the AC afterimage characteristic and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the rubbing FFS type liquid crystal display element or the liquid crystal cell manufactured according to the method of 1. was used. The results are shown in Table 2 below.
  • Example 11 and 12 Liquid crystal aligning agents (S-11) and (S-12) were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. Further, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agents (S-11) and (S-12) were used, respectively, and the same as in Example 10. Then, a rubbing FFS type liquid crystal display element or liquid crystal cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 13 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-13) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below.
  • the liquid crystal aligning agent (S-13) is mainly used for manufacturing a PSA type liquid crystal display device. 2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-13) was used. The results are shown in Table 2 below.
  • Liquid Crystal Composition 5% by mass of a liquid crystal compound represented by the following formula (L1-1) is represented by 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.), and represented by the following formula (L2-1).
  • a liquid crystal composition LC1 was obtained by adding 0.3% by mass of a photopolymerizable compound described above and mixing them.
  • an alternating current of 10 V with a frequency of 60 Hz was applied between the electrodes, and while the liquid crystal was driven, an ultraviolet irradiation device using a metal halide lamp as a light source was used to emit 50 Irradiation was performed at an irradiation dose of 000 J/m 2 .
  • this irradiation amount is a value measured using a photometer that measures the wavelength at 365 nm as a reference.
  • a liquid crystal display element was manufactured by bonding two polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other. 5.
  • Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below.
  • inkjet coating properties and long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used, and in the same manner as in Example 14, a PSA type liquid crystal display element or liquid crystal cell. was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 16 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-16) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below.
  • the liquid crystal aligning agent (S-16) is mainly used for manufacturing an optical vertical alignment type liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-16) was used. The results are shown in Table 2 below.
  • This irradiation amount is a value measured using a photometer that measures the wavelength at 313 nm. 4. Evaluation of vertically aligned liquid crystal display device 3. The post-bake margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the liquid crystal display device or liquid crystal cell of the optical vertical alignment type manufactured according to the method described in 1 above was used. The results are shown in Table 2 below.
  • Example 17 and 18 Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. In addition, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used. A liquid crystal cell was manufactured and post-bake margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated. The results are shown in Table 2 below.
  • Example 19 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-19) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below.
  • the liquid crystal aligning agent (S-19) is mainly used for manufacturing an optical horizontal type liquid crystal display element.
  • the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-19) was used. The results are shown in Table 2 below.
  • optical FFS type liquid crystal display element In addition to using a liquid crystal aligning agent (S-19) and performing rubbing treatment, the film was irradiated with polarized ultraviolet rays using a Hg-Xe lamp and a Glan-Taylor prism. An optical FFS type liquid crystal display element was produced in the same manner as in the method described in “3. Production of rubbing FFS type liquid crystal display element” in Example 10. Irradiation of polarized ultraviolet rays was performed from a direction perpendicular to the substrate, the irradiation amount was 10,000 J/m 2 , and the polarization direction was orthogonal to the rubbing direction in Example 10.
  • This irradiation amount is a value measured using a photometer that measures the wavelength at 254 nm. 4. Evaluation of optical FFS type liquid crystal display device
  • the post-bake margin, the AC afterimage characteristic, and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the optical FFS type liquid crystal display element or the liquid crystal cell manufactured according to the method described in 1. was used. The results are shown in Table 2 below.
  • Example 20 to 24 Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. Further, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used, and in the same manner as in Example 21, an optical FFS type liquid crystal display element or liquid crystal was used. The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 26 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-26) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below.
  • the liquid crystal aligning agent (S-26) is mainly used for manufacturing a TN mode type liquid crystal display device. 2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-26) was used. The results are shown in Table 2 below.
  • a TN type liquid crystal display device was manufactured in the same manner as in Example 1 except that the polarization direction was parallel to the rubbing direction of each substrate. 4. Evaluation of TN type liquid crystal display device The post-bake margin, the AC afterimage characteristic, and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the TN type liquid crystal display element or the liquid crystal cell manufactured according to the method described in 1. was used. The results are shown in Table 2 below.
  • the numerical value of the polymer component indicates the blending ratio (parts by mass) of each polymer to 100 parts by mass in total of the polymer components used for preparing the liquid crystal aligning agent.
  • the numerical value of the solvent composition indicates the compounding ratio (mass ratio) of each compound to the total amount of the solvent (compound [A], solvent [B] and other solvent) used for the preparation of the liquid crystal aligning agent.
  • the compound abbreviations are as follows.
  • the liquid crystal aligning agent containing the compound [A] has a good coating property on the substrate, does not easily deteriorate the inkjet head, and can obtain a liquid crystal element having excellent afterimage characteristics. It was Further, it was revealed that the liquid crystal aligning agent can also improve the post-baking margin.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un agent d'alignement de cristaux liquides qui présente une bonne aptitude au revêtement sur un substrat mais n'est pas susceptible de détériorer une tête à jet d'encre, et qui permet d'obtenir un élément à cristaux liquides qui présente d'excellentes caractéristiques d'image rémanente. Selon la présente invention, un agent d'alignement de cristaux liquides est configuré pour contenir un composant polymère et un composant (A) qui est représenté par la formule (1).　(1) : (R2)x-Ar1-R1 (Dans la formule (1), Ar1 représente un groupe cyclique aromatique ayant une valence de (x + 1) ; R2 représente un groupe alkyle ayant de 1 à 3 atomes de carbone, un groupe hydroxyalkyle ayant de 1 à 3 atomes de carbone ou un groupe alcoxy ayant de 1 à 3 atomes de carbone ; x représente 0 ou 1 ; et R1 représente un groupe hydroxyalkyle ayant de 1 à 3 atomes de carbone ou un groupe alcoxy ayant de 1 à 3 atomes de carbone.)
PCT/JP2019/040133 2019-01-17 2019-10-10 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides WO2020148953A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé
WO2023286733A1 (fr) * 2021-07-12 2023-01-19 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09265096A (ja) * 1996-03-27 1997-10-07 Japan Synthetic Rubber Co Ltd 液晶配向剤
JP2002322278A (ja) * 2001-04-26 2002-11-08 Hitachi Cable Ltd 溶剤可溶ポリイミド組成物
JP2012180483A (ja) * 2011-03-02 2012-09-20 Jnc Corp 分子中にアミノ基及び側鎖を具備する高分子と溶剤とを含有する組成物、並びに新規物質
WO2019159470A1 (fr) * 2018-02-13 2019-08-22 Jsr株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément de cristaux liquides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI633128B (zh) * 2011-05-27 2018-08-21 日產化學工業股份有限公司 Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element
JP2014059545A (ja) * 2012-08-21 2014-04-03 Jsr Corp 液晶配向剤、液晶配向膜及び液晶表示素子
KR20220147158A (ko) * 2016-09-29 2022-11-02 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09265096A (ja) * 1996-03-27 1997-10-07 Japan Synthetic Rubber Co Ltd 液晶配向剤
JP2002322278A (ja) * 2001-04-26 2002-11-08 Hitachi Cable Ltd 溶剤可溶ポリイミド組成物
JP2012180483A (ja) * 2011-03-02 2012-09-20 Jnc Corp 分子中にアミノ基及び側鎖を具備する高分子と溶剤とを含有する組成物、並びに新規物質
WO2019159470A1 (fr) * 2018-02-13 2019-08-22 Jsr株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément de cristaux liquides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé
JP7174199B1 (ja) * 2021-04-02 2022-11-17 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
JP2022190112A (ja) * 2021-04-02 2022-12-22 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
JP7436606B2 (ja) 2021-04-02 2024-02-21 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
WO2023286733A1 (fr) * 2021-07-12 2023-01-19 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides

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TWI819102B (zh) 2023-10-21

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