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WO2018181566A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2018181566A1
WO2018181566A1 PCT/JP2018/012958 JP2018012958W WO2018181566A1 WO 2018181566 A1 WO2018181566 A1 WO 2018181566A1 JP 2018012958 W JP2018012958 W JP 2018012958W WO 2018181566 A1 WO2018181566 A1 WO 2018181566A1
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Prior art keywords
liquid crystal
mass
polyamic acid
crystal aligning
aligning agent
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PCT/JP2018/012958
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English (en)
Japanese (ja)
Inventor
翔一朗 中原
真文 高橋
石川　和典
夏樹 佐藤
▲べ▼　鴻基
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日産化学株式会社
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Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020197031006A priority Critical patent/KR102619748B1/ko
Priority to JP2019510034A priority patent/JP7188381B2/ja
Priority to CN201880023171.2A priority patent/CN110462505A/zh
Publication of WO2018181566A1 publication Critical patent/WO2018181566A1/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
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal alignment film capable of achieving both panel production cost and film formation quality.
  • 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 polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution
  • liquid crystal aligning agent having a high solid content is required in order to reduce the amount of liquid crystal aligning agent used and increase the production efficiency.
  • liquid crystal aligning agent that can achieve a stable film thickness even on a high definition substrate having a large level difference.
  • the above technical directions all press the storage stability of the varnish and increase the risk of causing liquid precipitation.
  • higher substrate and film adhesion is required due to higher definition of the substrate and slimming of the panel.
  • An object of the present invention is to provide a liquid crystal aligning agent that has high adhesion, does not cause precipitation even at a high solid content concentration, and can obtain a stable film thickness, and a liquid crystal alignment film using the same.
  • the present invention contains the following component (A), component (B), component (C) and component (D), and the component (C) is 20 to 50% by mass with respect to the total mass of the liquid crystal aligning agent. It is in the liquid crystal aligning agent to contain.
  • liquid crystal aligning agent that has high substrate adhesion, does not cause precipitation even at a high solid content concentration, and can obtain a stable film thickness, and a liquid crystal alignment film using the same.
  • the liquid crystal aligning agent of this invention is especially effective for application
  • the component (A) contained in the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imidized product thereof.
  • the polyimide precursor can be represented by the following formula (1).
  • X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative
  • Y 1 is a divalent organic group derived from a diamine
  • R 1 is a hydrogen atom or a carbon number of 1 to 5 Represents an alkyl group.
  • R 1 is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • a 1 and A 2 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. From the viewpoint of liquid crystal orientation, A 1 and A 2 are preferably a hydrogen atom or a methyl group.
  • the diamine used for the production of the polyimide precursor can be represented by the following formula (2).
  • a 1 and A 2 in the above formula (2) have the same definitions as A 1 and A 2 in the above formula (1), including preferred examples.
  • Examples of the structure of Y 1 are as shown in the following formulas (Y-1) to (Y-1).
  • n is an integer of 1 to 6.
  • the tetracarboxylic acid component for producing the polyimide precursor is not only tetracarboxylic dianhydride, but also its derivative tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic dialkyl ester or tetracarboxylic dialkyl ester Dihalides can also be used.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (3).
  • X 1 is a tetravalent organic group, and specific examples thereof include the following formulas (X1-1) to (X1-44).
  • R 3 to R 23 each independently represents 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, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
  • R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6).
  • (X1-1-1) is particularly preferred from the viewpoints of liquid crystal orientation and photoreaction sensitivity.
  • the polyamic acid ester which is one of the polyimide precursors used in the present invention can be synthesized by the following method (1), (2) or (3).
  • (1) When synthesizing from polyamic acid Polyamic acid ester can be synthesized by esterifying polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, it can be synthesized by reacting a polyamic acid and an esterifying agent in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C. for 30 minutes to 24 hours.
  • the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
  • the solvent used in the above reaction is ⁇ -butyrolactone, ⁇ -valerolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone or ethyl carbitol because of the solubility of the polymer. These may be used alone or in combination of two or more.
  • the 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 unlikely to occur and a high molecular weight product is easily obtained.
  • Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, it can be synthesized by reacting tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C. for 30 minutes to 24 hours.
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, 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 solvent used for the synthesis of the polyamic acid ester is preferably dehydrated, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • Polyamic acid ester can be synthesized by polycondensation of tetracarboxylic acid diester and diamine. Specifically, it can be synthesized by reacting a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C. for 30 minutes to 24 hours.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base added is preferably 2 to 4 times the mol of the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
  • the synthesis method (1) or (2) is particularly preferable.
  • the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid which is one of the polyimide precursors used for this invention is compoundable by the method shown below. Specifically, it can be synthesized by reacting tetracarboxylic dianhydride and diamine at ⁇ 20 ° C. to 150 ° C. for 30 minutes to 24 hours in the presence of an organic solvent.
  • the organic solvent used in the above reaction is ⁇ -butyrolactone, ⁇ -valerolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone or ethyl due to the solubility of the monomer and polymer.
  • Carbitol is preferred, and these may be used alone or in combination.
  • the concentration of the polymer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight body is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating a polymer by pouring into a poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyimide used in the present invention can be produced by imidizing the polyamic acid ester or polyamic acid.
  • chemical imidization in which a basic catalyst is added to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
  • Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
  • a basic catalyst As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
  • the temperature for carrying out the imidization reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below and redissolved in an organic solvent to obtain a liquid crystal aligning agent. It is preferable.
  • Chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction with a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process. Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the temperature for carrying out the imidization reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
  • the liquid crystal aligning agent of the present invention is preferable.
  • the polyimide solution obtained as described above can be precipitated by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the liquid crystal aligning agent of this invention has the form of the solution in which the polyimide precursor and the polyimide were melt
  • the weight average molecular weight of the polyimide precursor and polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and 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 content (concentration) of the polymer of the liquid crystal aligning agent of the present invention can be changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the total mass of the liquid crystal aligning agent. 1 mass% or more is preferable with respect to the storage stability of a solution, and 10 mass% or less is preferable. Among them, the content of the polymer is more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass.
  • the component (B) contained in the liquid crystal aligning agent of the present invention is a non-amine Si coupling agent.
  • the non-amine Si coupling agent means a hydrolyzable silyl group-containing compound having no amino group in the molecule.
  • the content of the component (B) is preferably 0.1 to 2% by mass with respect to the polymer solid content in the liquid crystal aligning agent, because it does not interfere with the substrate adhesion of the coating film and other properties. It is more preferably 3 to 2% by mass, and particularly preferably 0.5 to 1.5% by mass. Further, two or more different types of component (B) may be used.
  • the component (C) contained in the liquid crystal aligning agent of the present invention is selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and ethyl carbitol.
  • At least one organic solvent is a solvent that contributes to the dissolution of the polymer.
  • at least one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, and N-ethyl-2-pyrrolidone is preferable.
  • the content of the component (C) is preferably 20 to 50% by mass and preferably 25 to 50% by mass with respect to the total mass of the liquid crystal aligning agent for the purpose of improving the storage stability of the solution and the film formation quality of the coating film edge. More preferred is 30 to 50% by mass.
  • the component (D) contained in the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of 1-butoxy-2-propanol, 2-butoxy-1-propanol, butyl cellosolve, butyl cellosolve acetate, and dipropylene glycol dimethyl ether. It is a seed organic solvent. This solvent is a solvent that contributes to uniform coating formation. Among these, at least one selected from 1-butoxy-2-propanol, butyl cellosolve, and butyl cellosolve acetate is preferable.
  • the content of the component (D) is preferably 5 to 40% by mass, more preferably 20 to 40% by mass with respect to the total mass of the liquid crystal aligning agent for the purpose of obtaining uniformity of the coating film and storage stability of the solution. 20 to 30% by mass is particularly preferable.
  • the component (B) is 0.3 to 2% by mass, the component (C) is 20 to 50% by mass, and the component (D) is 20% by mass with respect to the component (A). It is preferably ⁇ 40% by mass. Among them, the component (B) is 0.5 to 1.5% by mass, the component (C) is 30 to 50% by mass, and the component (D) is 20 to 30% by mass with respect to the component (A). Is particularly preferred.
  • N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N examples thereof include N-dimethylpropanamide and 4-hydroxy-4-methyl-2-pentanone.
  • N-methyl-2-pyrrolidone is preferably contained in an amount of 50% by mass or less, more preferably 25 to 30% by mass with respect to the total mass of the liquid crystal aligning agent because of high storage stability.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • the poor solvent isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-
  • the liquid crystal aligning agent of the present invention includes 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. Or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two 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, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
  • the crosslinkable compound having an oxetane group is a compound having at least two oxetane groups represented by the following formula [4A]. Specific examples include crosslinkable compounds of the formulas [4a] to [4k] described on pages 58 to 59 of WO2011 / 132751 (application: PCT / JP2011 / 059867).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A]. Specific examples include crosslinkable compounds of the formulas [5-1] to [5-42] described on pages 76 to 82 of WO2012 / 014898 (application: PCT / JP2011 / 066980).
  • 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.
  • -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin Specifically, 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.
  • This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. These preferably have an average of 3 to 6 methyl
  • Examples of the melamine derivative or benzoguanamine derivative include MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and an average of 5.8 methoxymethyl groups are substituted per triazine ring.
  • glycoluril examples include butoxymethylated glycoluri
  • 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, there are crosslinkable compounds of the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of WO2011 / 132751 (application: the same as before).
  • 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.
  • the 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 this invention can contain the compound which improves the uniformity of the film thickness at the time of apply
  • examples of 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.
  • 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 a compound which is published on pages 69 to 73 of WO2011 / 132751 (application: same as before) as a compound which promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device.
  • Nitrogen-containing heterocyclic amines of [M1] to formula [M156] can also be added. This amine may be added directly to the liquid crystal aligning agent, but it is preferable to add it after making 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.
  • An imidization accelerator or the like for the purpose may be added.
  • the liquid crystal alignment film is a film obtained by applying a liquid crystal aligning agent to a substrate, drying and baking.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and may be a glass substrate, a silicon nitride substrate, or a plastic substrate such as an acrylic substrate or a polycarbonate substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is used from the viewpoint of simplification of the process.
  • an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.
  • the solvent can be evaporated by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention.
  • a condition of baking at 50 to 120 ° C. for 1 to 10 minutes and then baking at 150 to 300 ° C. for 5 to 120 minutes is mentioned in order to sufficiently remove the contained solvent.
  • the thickness of the liquid crystal alignment film after baking is too thin, the reliability of the liquid crystal display element may be lowered, and thus it is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
  • the liquid crystal alignment treatment agent of the present invention is applied to a substrate and baked, and then subjected to alignment treatment by a rubbing treatment performed by a conventional apparatus or method, photo-alignment treatment, or no alignment treatment for vertical alignment applications. Therefore, it can be used as a liquid crystal alignment film.
  • a liquid crystal display element having a passive matrix structure As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example.
  • an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
  • a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
  • These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a SiO 2 —TiO 2 film formed by a sol-gel method.
  • a liquid crystal alignment film is formed on each substrate, the other substrate is overlaid on one substrate so that the liquid crystal alignment film faces each other, and the periphery is bonded with a sealant.
  • a spacer is usually mixed in the sealant, and it is preferable to spray a spacer for controlling the substrate gap on the in-plane portion where no sealant is provided.
  • a part of the sealant is provided with an opening that can be filled with liquid crystal from the outside.
  • a liquid crystal material is injected into the space surrounded by the two substrates and the sealing agent through the opening provided in the sealing agent, and then the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • the liquid crystal material either a positive liquid crystal material or a negative liquid crystal material may be used, but a negative liquid crystal material is preferable.
  • a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer. As described above, by using 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.
  • NMP N-methyl-2-pyrrolidone
  • BCS Butyl cellosolve
  • GBL ⁇ -butyrolactone
  • ⁇ Viscosity> As for the viscosity of the polymer solution, an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) was used to collect a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24), temperature 25 ° C. Measured with ⁇ Measurement method of solid content concentration> 1.0 g of the solution was measured in an aluminum cup and subjected to heat treatment at 200 ° C. for 2 hours, then the amount of solid remaining on the cup was measured, and the solid content concentration of the solution was measured. ⁇ Evaluation of long-term storage stability> When the liquid crystal alignment agent is stored in a freezer at ⁇ 20 ° C.
  • the viscosity change during this period is within ⁇ 1 mPa ⁇ s, and the liquid appearance is also free from turbidity and precipitation. . Those having viscosity change, turbidity, and precipitation were evaluated as “bad”.
  • the liquid crystal aligning agent is filtered through a membrane filter having a pore size of 1.0 ⁇ m, spin-coated on a nitrogen silicon substrate, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and then baked at 230 ° C. for 15 minutes.
  • a 100 nm polyimide film is produced.
  • the polyimide film prepared on the nitrogen silicon substrate was stored for 24 hours in an environment of a temperature of 70 ° C. and a humidity of 80%. Then, after leaving at room temperature for 3 hours, adhesiveness was evaluated according to JIS K5600.
  • the polyimide film was scratched with a cutter knife at intervals of 2 mm to create 100 squares, and a cellophane tape was pressure-bonded thereon and peeled off instantaneously to examine the peeling state of the polyimide film from the nitrogen silicon substrate.
  • a cellophane tape was pressure-bonded thereon and peeled off instantaneously to examine the peeling state of the polyimide film from the nitrogen silicon substrate.
  • the coating can be performed without any in-plane unevenness.
  • the dropping pitches were compared when coating was performed under the condition that the film thickness after the main baking was 100 nm. At this time, the one having a wide dropping pitch has a small amount of dropping liquid per unit distance. A sample having a long dropping pitch was evaluated as “good”, and a sample having a short dropping pitch was determined as “bad”.
  • Polyamic acid B1 In a 2000 ml flask with a stirrer and a nitrogen inlet tube, 156.1 g (0.545 mol) of DA-5 was added, NMP 1593.0 g was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 116.7 g (0.535 mol) of CA-1 was added, 398 g of NMP was further added, and the mixture was stirred for 20 hours while heating at 50 ° C. in a nitrogen atmosphere, and the polyamic acid solution ( Viscosity: 510 mPa ⁇ s) was obtained. To 535.7 g of this polyamic acid solution, 264.3 g of NMP and 200.0 g of BCS were added and stirred to obtain a polyamic acid solution (B1). The solid content concentration was 6.0% by mass.
  • Polyamic acid B6 In a 2000 ml flask with a stirrer and a nitrogen inlet tube, 142.1 g (0.550 mol) of DA-3 was added, 1466.8 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution under water cooling, 108.0 g (0.495 mol) of CA-1 was added, and 366.7 g of NMP was further added. The mixture was stirred for 20 hours while heating at 50 ° C., and the polyamic acid solution (viscosity: 89 mPa ⁇ s) was obtained. To 606.1 g of this polyamic acid solution, 93.9 g of NMP and 300.0 g of BCS were added and stirred to obtain a polyamic acid solution (B6). The solid content concentration was 6.0% by mass.
  • Example 6 165.4 g of polyamic acid solution B5 and 176.7 g of A5 were mixed, 0.9 g of NMP, 431.2 g of GBL, 25.8 g of GBL solution containing 1.0% by mass of AD-2 and 200.0 g of BCS were added. For 2 hours to obtain 1000 g of a liquid crystal aligning agent (C6). 1.0 g of this solution was measured on an aluminum cup, and the solid content concentration when treated at 200 ° C. for 2 hours was 4.3% by mass. Its viscosity was 11 mPa ⁇ s.
  • C6 liquid crystal aligning agent
  • Example 7 Mix 124.0 g of polyamic acid solution B5 and 206.2 g of A5, add 12.8 g of NMP, 426.9 g of GBL, 30.1 g of GBL solution containing 1.0 mass of AD-2 and 200.0 g of BCS. It stirred for 2 hours and obtained 1000g of liquid crystal aligning agents (C7). 1.0 g of this solution was measured on an aluminum cup, and the solid content concentration when treated at 200 ° C. for 2 hours was 4.3% by mass. The viscosity was 11 mPa ⁇ s.
  • the liquid crystal aligning agents of Examples 1 to 13 showed good results in any of long-term frozen storage stability, adhesion evaluation, and coating property evaluation.
  • the liquid crystal aligning agents of Comparative Examples 1 to 10 could not achieve good results in all evaluations. It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2017-72075 filed on March 31, 2017 are cited herein as disclosure of the specification of the present invention. Incorporate.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne : un agent d'alignement à cristaux liquides qui a une adhérence élevée à des substrats, qui ne précipite pas même à une concentration élevée en solides, et qui fournit une épaisseur de film stable; et un film d'alignement de cristaux liquides qui utilise cet agent d'alignement de cristaux liquides. L'agent d'alignement de cristaux liquides contient les composants suivants (A) à (D) et contient un composant (C) à 20 à 50 % en masse par rapport à la masse globale de l'agent d'alignement de cristaux liquides. (A) : au moins un polymère choisi dans le groupe constitué par les précurseurs de polyimide et les polyimides qui sont les produits d'imidation des précurseurs de polyimide. (B) : un agent de couplage Si non amine. (C) : au moins un solvant organique choisi dans le groupe constitué de la gamma-butyrolactone, de la gamma-valérolactone, de la N-éthyl-2-pyrrolidone, de la N-butyl-2-pyrrolidone, et de l'éthylutol. (D) : au moins un solvant organique choisi dans le groupe constitué du 1-butoxy-2-propanol, du 2-butoxy-1-propanol, de la cellophane butyle, de l'acétate de butyle et de l'acétate de butyle, et de l'éther diméthylique de dipropylène glycol.
PCT/JP2018/012958 2017-03-31 2018-03-28 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2018181566A1 (fr)

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JP2019510034A JP7188381B2 (ja) 2017-03-31 2018-03-28 液晶配向剤、液晶配向膜、及び液晶表示素子
CN201880023171.2A CN110462505A (zh) 2017-03-31 2018-03-28 液晶取向剂、液晶取向膜和液晶表示元件

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