WO2020153659A1 - Composition d'alignement de cristaux liquides et film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides utilisant ceux-ci - Google Patents

Composition d'alignement de cristaux liquides et film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides utilisant ceux-ci Download PDF

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Publication number
WO2020153659A1
WO2020153659A1 PCT/KR2020/000805 KR2020000805W WO2020153659A1 WO 2020153659 A1 WO2020153659 A1 WO 2020153659A1 KR 2020000805 W KR2020000805 W KR 2020000805W WO 2020153659 A1 WO2020153659 A1 WO 2020153659A1
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Prior art keywords
liquid crystal
group
crystal aligning
formula
aligning agent
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PCT/KR2020/000805
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English (en)
Korean (ko)
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권순호
조정호
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주식회사 엘지화학
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Priority claimed from KR1020200005494A external-priority patent/KR102410008B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020546958A priority Critical patent/JP6992242B2/ja
Priority to CN202080001922.8A priority patent/CN111868212B/zh
Priority to EP20744241.9A priority patent/EP3750973A4/fr
Priority to US17/046,229 priority patent/US11561438B2/en
Publication of WO2020153659A1 publication Critical patent/WO2020153659A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

Definitions

  • the present invention relates to a liquid crystal aligning agent composition capable of realizing improved storage stability and electrical properties while having excellent film strength, a method of manufacturing a liquid crystal aligning film using the same, a liquid crystal aligning film using the same, and a liquid crystal display device.
  • a liquid crystal alignment film plays a role of aligning a liquid crystal in a constant direction.
  • the liquid crystal alignment layer acts as a director in the arrangement of the liquid crystal molecules, so that the liquid crystal is moved by an electric field to form an image, so that an appropriate orientation is obtained.
  • it is essential to uniformly align the liquid crystal.
  • a rubbing method is used in which a polymer film such as polyimide is applied to a substrate such as glass, and the surface is rubbed in a certain direction using fibers such as nylon or polyester.
  • the rubbing method may cause fine dust or electrostatic discharge (ESD) when the fiber and the polymer film are rubbed, which may cause serious problems in manufacturing a liquid crystal panel.
  • polyimide is mainly used for good overall performance of the liquid crystal alignment film.
  • a polyimide is formed through a heat treatment process at a temperature of 200°C or more and 230°C or less, and light irradiation is performed thereon to perform orientation treatment.
  • the liquid crystal aligning agent may affect not only the basic characteristics of liquid crystal orientation, but also electrical characteristics such as afterimages and voltage retention caused by DC/AC voltage. As a result, the need for development of a liquid crystal alignment material capable of simultaneously realizing excellent liquid crystal alignment and electrical characteristics is increasing.
  • liquid crystal aligning agent composition capable of improving alignment characteristics, storage stability, and electrical properties of an alignment layer while manufacturing an alignment layer having high film strength.
  • the present invention is to provide a liquid crystal aligning agent composition capable of realizing improved storage stability and electrical properties while having excellent film strength when synthesizing a liquid crystal alignment film.
  • liquid crystal alignment film and a liquid crystal display device including the same, which includes an alignment cured product of the liquid crystal aligning agent composition.
  • a liquid crystal aligning agent composition wherein the polymer for a liquid crystal aligning agent and the crosslinking functional group of the terminal crosslinking functional group are capped with a silicon-containing thermally-releasing protecting group, and the particle number change by Equation 1 below is 30 or less. .
  • EA 0 is the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal alignment agent composition at the first time point (0 seconds) at which the liquid crystal alignment agent composition is obtained
  • EA 1 is the first time point (0 seconds).
  • liquid crystal alignment film including an alignment hardened product of the liquid crystal aligning agent composition and a liquid crystal display device including the same are provided.
  • liquid crystal aligning agent composition according to a specific embodiment of the present invention, a liquid crystal aligning film using the same, and a liquid crystal display device will be described in more detail.
  • substitution means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and is substituted when two or more are substituted. , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted in this specification is deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; Amino group; Carboxy group; Sulfonic acid group; Sulfonamide groups; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the group consisting of heterocyclic
  • a substituent having two or more substituents may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • the alkyl group may be a straight chain or a branched chain, and carbon number is not particularly limited, but is preferably 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhex
  • the halo alkyl group means a functional group in which the halogen group is substituted with the aforementioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the haloalkyl group may be substituted or unsubstituted.
  • the group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sn), or bismuth (Bi).
  • Nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are combined, and a nitrogen oxide functional group means a functional group containing nitrogen oxide in a functional group.
  • a nitrogen oxide functional group a nitro group (-NO 2 ) or the like can be used.
  • the aryl group is a monovalent functional group derived from arenes, and is not particularly limited, but is preferably 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the aryl group may be substituted or unsubstituted.
  • the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied except that they are divalent functional groups.
  • a polyvalent functional group is a residue in the form of removing a plurality of hydrogen atoms bound to an arbitrary compound, for example, a divalent functional group, a trivalent functional group, and a tetravalent functional group.
  • a tetravalent functional group derived from cyclobutane refers to a residue in which any 4 hydrogen atoms attached to cyclobutane are removed.
  • a direct bond or a single bond means that there is no atom or atomic group at the position, and is connected by a bond line.
  • R a , or L b (a and b are integers of 1 to 20, respectively) means a case in which no separate atom is present.
  • the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by GPC method.
  • detectors and analytical columns such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied.
  • Conditions, solvents and flow rates can be applied.
  • the evaluation temperature is 40° C. and 1,2,4-trichlorobenzene is used as a solvent.
  • the flow rate was 1 mL/min
  • the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 ⁇ L, and the value of Mw can be obtained by using an assay curve formed using a polystyrene standard.
  • the molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000.
  • the present inventors when using a liquid crystal alignment agent composition that the particle number change calculated by the equation (1) satisfies a specific range, the reliability and stability of the liquid crystal alignment film is enhanced as it has uniformity even for long-term storage. It was confirmed that can be prepared.
  • liquid crystal aligning agent composition when the liquid crystal aligning agent composition is unstable, reaction between the compounds contained in the liquid crystal aligning agent composition occurs to form a by-product, and precipitation due to a decrease in solubility occurs, so the number of particles contained in the liquid crystal aligning agent composition after long-term storage Small means that the liquid crystal aligning agent composition has excellent stability and is suitable for long-term storage.
  • a polymer for a liquid crystal alignment agent comprising a crosslinking agent compound in which a terminal crosslinking functional group is capped with a silicon-containing thermally-releasing protecting group, and a liquid crystal aligning agent composition having a particle number change by Equation 1 of 30 or less may be provided.
  • EA 0 is the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal alignment agent composition at the first time point (0 seconds) at which the liquid crystal alignment agent composition is obtained
  • EA 1 is the first time point (0 seconds). From the point in time after storage of the liquid crystal aligning agent composition at minus 20°C or more and 0°C or less for 30 days, the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal aligning agent composition is 30 days or more.
  • EA 0 is 0.5 ⁇ m or more, 0.5 ⁇ m or more, 100 ⁇ m or less, 0.5 ⁇ m or more, 50 ⁇ m or less at a first time point (0 seconds) at which the liquid crystal alignment agent composition is obtained. , 0.5 ⁇ m or more and 10 ⁇ m or less, or 0.5 ⁇ m or more and 5 ⁇ m or less, and EA 1 may store the liquid crystal alignment agent composition at minus 20°C or higher and 0°C or lower for 30 days from the initial time point (0 second).
  • the particle number included in the liquid crystal alignment agent composition is 0.5 ⁇ m or more, 0.5 ⁇ m or more, 100 ⁇ m or less, 0.5 ⁇ m or more, 50 ⁇ m or less, 0.5 ⁇ m or more, 10 ⁇ m or less, or 0.5 ⁇ m or more and 5 ⁇ m or less
  • EA 1 is the first time (0 seconds) 30 days from the liquid crystal alignment agent composition below 20 °C below 0 °C, below 0 °C below 20 °C below 10 °C below, below 20 °C below zero below 15 °C below 15 °C
  • the particle number included in the liquid crystal alignment agent composition may be a particle number of 0.5 ⁇ m or more.
  • EA 1 may be the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal alignment agent composition at a time point after storage under normal pressure conditions for 30 days from the initial time point (0 seconds), and the normal pressure
  • the condition is not limited as a normal atmospheric pressure, but may mean a pressure of 1 atmosphere.
  • the particle number may be measured using a particle size analyzer at a temperature of 15°C or higher and 35°C or lower and a particle class 1000 or lower.
  • the Particle class 1000 or less may mean a condition in which the number of particles having a particle diameter of 0.5 ⁇ m or more in 1 ft3 is 1000 or less.
  • the particle size analyzer It may be a device that measures the size and number of particles using a light scattering method, and may be a particle sensor in liquid.
  • the light scattering method In the light scattering method, light scattered by irradiating light onto a sample is detected by a photo detector, converted into an electrical signal, and the particle size is obtained through the size of the electrical signal, and the frequency of the electrical signal It may be a principle to obtain the number of particles through.
  • the particle number is 0.2 ⁇ m or more, 0.3 ⁇ m or more, and 0.5 ⁇ m at a temperature of 15° C. or higher and 35° C. or lower and Particle class 1000 or lower using a particle particle sensor (KS-42B, Rion Co.).
  • KS-42B Rion Co.
  • the electrical signal measured for a particle having a particle diameter of 0.5 ⁇ m is greater than the size of an electrical war signal. It can be seen from the number of electrical signals.
  • the number of each particle measured in a channel of 0.5 ⁇ m or more, 1.0 ⁇ m or more, and 2.0 ⁇ m or more is determined. You can calculate them all together.
  • the particle number change by Equation 1 may be 30 or less, 10 or less, 8 or less, 5 or less, 4 or less, or 3 or less.
  • EA 0 is the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal aligning agent composition at the first time point (0 seconds) at which the liquid crystal aligning agent composition is obtained, 30 or less, 15 It may be 12 or less, 11 or less, 10 or less, or 8 or less.
  • EA 1 is a particle size 0.5 contained in the liquid crystal alignment agent composition at a time point after the liquid crystal alignment agent composition is stored at minus 20°C or higher and below 0°C for 30 days from the initial time point (0 second).
  • the number of particles of ⁇ m or more may be 500 or less, 100 or less, 30 or less, 20 or less, 14 or less, 13 or less, or 12 or less.
  • the crosslinking agent compound included in the liquid crystal aligning agent composition of the above embodiment may be a crosslinking agent compound in which a terminal crosslinking functional group is capped with a silicon-containing thermally-releasing protecting group.
  • a terminal crosslinking functional group is capped with a silicon-containing thermally-releasing protecting group.
  • all of the terminal cross-linking functional groups may be capped with a heat-releasing protecting group.
  • a terminal crosslinking functional group refers to a functional group capable of inducing a crosslinking reaction by bonding with the polymer for the liquid crystal aligning agent, and may be, for example, a hydroxy group (-OH).
  • the silicon-containing thermally-releasing protecting group is a functional group substituted for a hydrogen atom in a terminal crosslinking functional group, and can inhibit a crosslinking reaction between a polymer for a liquid crystal aligning agent and a crosslinking agent compound.
  • the fact that the terminal cross-linking functional group was capped with a silicon-containing thermally-releasing protecting group means that the silicon-containing thermally-releasing protecting group was substituted in place of the hydrogen atom in the terminal cross-linking functional group, as described above.
  • the silicon-containing thermally desorbable protecting group may be a silicon-containing monovalent functional group.
  • the thermal desorption protecting group may be desorbed while being subjected to a drying process, an exposure process, a curing process, and the like, in which a liquid crystal alignment layer is prepared from a liquid crystal aligning agent composition, and when it is elevated to a temperature above a certain level, it is replaced with a hydrogen atom.
  • the reactivity of the cross-linking agent in the initial drying process is reduced compared to the cross-linking agent having the terminal cross-linking functional group, and cross-linking reaction starts after the exposure process for orientation It is possible to reduce the decrease in initial orientation caused by the crosslinking agent.
  • the thermally-releasing protecting group introduced at the end of the cross-linking group of the cross-linking agent compound is desorbed and removed at a temperature of about 150° C. or higher by heat treatment during the drying or firing process of the liquid crystal alignment layer, thereby recovering the end of the cross-linking group and proceeding to a smooth cross-linking reaction.
  • the mechanical properties of the alignment film can be improved.
  • the particles may include a precipitate of a crosslinking agent compound in which a terminal crosslinking functional group is capped with a thermally desorbable protecting group.
  • the precipitate means a substance formed by separating the crystalline solid by solubility from a composition in a solution state in which the crystalline solid is dissolved.
  • the crosslinking agent compound in which the crosslinking functional group at the terminal is capped with a thermally-releasing protecting group can be precipitated from the liquid crystal aligning agent composition by lowering solubility to form particles.
  • a crosslinking agent compound is added to the composition for a liquid crystal aligning agent in order to increase the film strength, but in the case of the existing crosslinking agent compound, the solubility of the crosslinking agent compound is poor and precipitated from the composition for the liquid crystal aligning agent, resulting in a poor storage stability of the composition for the liquid crystal aligning agent. .
  • the composition for a liquid crystal aligning agent of the above embodiment has a small amount of precipitation of the crosslinking agent compound, as the crosslinking functional group at the terminal showing excellent solubility includes a crosslinking agent compound capped with a thermally desorbable protecting group, and the liquid crystal alignment without the crosslinking agent compound
  • the liquid crystal aligning agent composition of the embodiment may include a polymer resin solution in which the polymer for the liquid crystal aligning agent and the crosslinking agent group in which the terminal crosslinking functional groups are capped with a thermally desorbable protecting group are dissolved in an organic solvent.
  • organic solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, and N-ethylpyrrolid Don, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy -N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone , Methyl isopropyl ketone, cyclohexanone, ethylene
  • the liquid crystal aligning agent composition may further include other components in addition to the organic solvent.
  • the liquid crystal aligning agent when the liquid crystal aligning agent is applied, the film thickness uniformity or surface smoothness is improved, or the adhesion between the liquid crystal alignment film and the substrate is improved, or the dielectric constant or conductivity of the liquid crystal alignment film is changed, or An additive that can increase the density of the liquid crystal alignment layer may be further included.
  • additives include various solvents, surfactants, silane-based compounds, dielectric or crosslinkable compounds, and the like.
  • liquid crystal aligning agent composition of the embodiment may be a liquid crystal aligning agent composition in which particles are dispersed in the polymer resin solution.
  • the crosslinking functional group of the terminal precipitated from the liquid crystal aligning agent composition by lowering the solubility in the polymer resin solution in which the crosslinking agent compound in which the polymer for the liquid crystal aligning agent and the crosslinking functional group of the terminal is capped with a thermally-releasing protecting group is dissolved in an organic solvent.
  • Particles comprising a crosslinking agent compound capped with a thermally releasing protecting group may be further included.
  • the cross-linking agent compound in which the terminal cross-linking functional group is capped with a heat-releasing protecting group is 0.1 wt% or more and 30 wt% or less, or 0.1 wt% or more and 20 wt% or less, or 1 wt% based on the solid content in the polymer resin solution. More than 20% by weight or less, or 1% by weight or more and 15% by weight or less, or 5% by weight or more and 15% by weight or less, or 1% by weight or more and 7% by weight or less, or 13% by weight or more and 20% by weight or less .
  • the terminal crosslinking functional group is not capped with a thermally-releasing protecting group, so that the solubility of the crosslinking agent compound is poor. Accordingly, when the crosslinking agent compound is excessively contained in the liquid crystal aligning agent composition, a part of the crosslinking agent compound is While depositing and forming particles, there was a problem that not only the storage stability of the liquid crystal aligning agent composition was poor, but also the alignment characteristics of the liquid crystal aligning film produced therefrom were poor.
  • the crosslinking agent compound in which the crosslinking functional group at the end of the one embodiment is capped with a thermally desorbable protecting group may be included in an excessive amount in the liquid crystal aligning agent composition as compared with the existing crosslinking agent compound, as it has excellent solubility, and thus the liquid crystal aligning agent composition It has excellent storage stability and the liquid crystal alignment film prepared therefrom can exhibit excellent film strength and liquid crystal alignment properties.
  • the content of the crosslinking agent compound is excessively large, as the crosslinking degree of the polymer for the liquid crystal aligning agent increases excessively, flexibility of the polymer may decrease, and storage stability due to increase in viscosity of the composition and gelation reaction in the composition may result. Therefore, the applicability to the substrate may be reduced.
  • the content of the cross-linking agent compound is too small, the effect of improving the mechanical strength and electrical properties due to the increase in the cross-linking degree of the polymer for the liquid crystal alignment agent may be difficult to realize sufficiently.
  • the liquid crystal aligning agent composition of the above embodiment may include a polymer for a liquid crystal aligning agent.
  • the polymer for the liquid crystal alignment agent is not particularly limited, but polyimide, polyimide precursor, and the like may be exemplified.
  • the liquid crystal aligning agent composition of the above embodiment may include a polymer for a liquid crystal aligning agent comprising at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit.
  • the liquid crystal aligning agent composition of the embodiment includes one or more repeating units selected from the group consisting of repeating units represented by the following Chemical Formula 3, repeating units represented by the following Chemical Formula 4 and repeating units represented by the following Chemical Formula 5 A polymer for a first liquid crystal aligning agent; And a second liquid crystal aligning polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Chemical Formula 6, a repeating unit represented by Chemical Formula 7 and a repeating unit represented by Chemical Formula 8; Can.
  • R 6 and R 7 are each independently a tetravalent organic group
  • R 8 and R 9 are each independently a divalent organic group represented by the following Chemical Formula 9
  • T is a tetravalent organic group represented by the following Chemical Formula 10, and D 1 and D 2 are each independently an alkylene group having 1 to 20 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms, and 3 to 20 carbon atoms.
  • R 10 to R 15 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms
  • L 3 is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO 2 -, -CR 16 R 17 -, -(CH 2 ) Z -, -O(CH 2 ) Z O-, -COO(CH 2 ) Z OCO-, -CONH-, phenylene or combinations thereof Any one selected from the group consisting of, wherein R 16 and R 17 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group, z is an integer of 1 to 10,
  • Y 4 to Y 6 are each independently a divalent organic group represented by the following formula (11),
  • R 18 and R 19 are each independently hydrogen, halogen, cyano, nitryl, alkyl having 1 to 10 carbons, alkenyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, 1 to 10 carbons Fluoroalkyl of, or fluoroalkoxy having 1 to 10 carbon atoms, p and q are each independently an integer of 0 to 4, L 4 is a single bond, -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -CONH-, -COO-, -(CH 2 ) y -, -O(CH 2 ) y O-, -O( CH 2 ) y -, -NH-, -NH(CH 2 ) y -NH-, -NH(CH 2 ) y O-, -OCH 2 -C(CH 3 ) 2
  • X 1 to X 6 are each independently a tetravalent action Can be.
  • each of X 1 to X 6 may be independently a tetravalent functional group described in Chemical Formula 10 above.
  • the polymer for the first liquid crystal aligning agent in the liquid crystal aligning agent composition according to the embodiment may be a divalent functional group represented by Formula 9 independently of Y 1 to Y 3 in the repeating units of Formulas 3 to 5.
  • T is a tetravalent functional group
  • D 1 and D 2 are each independently an alkylene group having 1 to 20 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or 6 to 6 carbon atoms. It may be either an arylene group of 20 or a heteroarylene group having 2 to 20 carbon atoms.
  • the formula (9) corresponds to a part of the repeating unit derived from a diamine having a specific structure containing an imide group or the like which is a precursor used to form a polymer for a liquid crystal aligning agent.
  • D 1 and D 2 may be each independently Formula 12 or Formula 13 below.
  • L 5 is a single bond, -O-, -SO 2 -, or -CR 20 R 21 -, wherein R 20 and R 21 are each independently hydrogen, or alkyl having 1 to 10 carbons. .
  • the formula 12 may be the following formula 12-1.
  • Chemical Formula 13 may be Chemical Formula 13-1.
  • L 5 is O, or CH 2 .
  • the example of the organic group represented by Chemical Formula 9 is not particularly limited, but may be, for example, a functional group represented by Chemical Formula 9-a or Chemical Formula 9-b.
  • T may be a functional group represented by the following Chemical Formula 10-1 or a functional group represented by the following 10-2.
  • the polymer for the first liquid crystal aligning agent in the liquid crystal aligning agent composition according to one embodiment of the repeating unit represented by Formula 3, which is an imide repeating unit, among repeating units represented by Chemical Formulas 3, 4 and 5 5 to 74 mol% or less, preferably 10 to 60 mol% or less, based on the unit.
  • the repeating unit represented by Formula 3 which is an imide repeating unit, among repeating units represented by Chemical Formulas 3, 4 and 5 5 to 74 mol% or less, preferably 10 to 60 mol% or less, based on the unit.
  • the polymer for the first liquid crystal aligning agent contains a certain amount of imide repeating unit already imidized, and thus heat treatment at high temperature By omitting the process and irradiating light immediately, a liquid crystal alignment film having excellent liquid crystal alignment and stability can be produced.
  • repeating unit represented by Chemical Formula 3 is included less than the above content range, sufficient orientation characteristics may not be exhibited, orientation stability may be deteriorated, and if the content of the repeating unit represented by Chemical Formula 3 exceeds the above range, the coating is stable. Difficult to produce an alignment solution may appear. Accordingly, it is preferable to include the repeating unit represented by Chemical Formula 3 in the above-described content range, because it is possible to provide a polymer for a liquid crystal aligning agent having excellent storage stability, electrical properties, alignment properties, and alignment stability.
  • repeating unit represented by the formula (4) or the repeating unit represented by the formula (5) may be included in an appropriate amount depending on the desired properties.
  • the repeating units represented by Chemical Formula 4 may include 0 or more and 40 mol% or less, preferably 0 or more and 30 mol% or less, based on the total repeating units represented by Chemical Formulas 3 to 5.
  • the repeating unit represented by Chemical Formula 4 has a low rate of conversion to imide during the high temperature heat treatment process after light irradiation, and thus, if it exceeds the above range, the overall imidation rate is insufficient, and thus alignment stability may be deteriorated.
  • the repeating unit represented by Chemical Formula 4 may provide a polymer for a liquid crystal aligning agent capable of realizing a high imidation rate with excellent process characteristics within the above-described range.
  • repeating units represented by Chemical Formula 5 may include 0 or more and 95 mol% or less, preferably 10 or more and 90 mol% or less, based on the total repeating units represented by Chemical Formulas 3 to 5. It is possible to provide a polymer for a liquid crystal aligning agent that exhibits excellent coating properties within such a range and has excellent process characteristics and can realize a high imidation rate.
  • At least one repeating unit selected from the group consisting of the repeating unit represented by Chemical Formula 3, the repeating unit represented by Chemical Formula 4, and the repeating unit represented by Chemical Formula 5 is tetra And a combination of carboxylic dianhydride and diamine.
  • tetracarboxylic dianhydride and diamine corresponds to the reaction product of tetracarboxylic dianhydride and diamine, and in Formulas 3 to 5, X 1 to X 3 are polyamic acid, polyamic acid ester, or polyimide synthesis It may be a tetravalent organic group derived from a tetracarboxylic dianhydride compound used, and Y 1 to Y 3 may be a divalent organic group derived from a diamine compound used in synthesizing polyamic acid, polyamic acid ester, or polyimide.
  • the tetracarboxylic acid dianhydride may be represented by the following Chemical Formula 10-a, and the content of X 0 in the following Chemical Formula 10-a may include the content described in Chemical Formula 10 as it is.
  • the diamine may be represented by the following Chemical Formula 9-1, and the contents of D 1 to D 1 and T in the following Chemical Formula 9-1 may include the contents described above in the Chemical Formula 9.
  • Y 4 to Y 6 may each independently be a divalent functional group represented by Formula 11 above. have.
  • R 18 and R 19 are each independently hydrogen, halogen, cyano, nitryl, alkyl having 1 to 10 carbons, alkenyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, 1 to 10 carbons Fluoroalkyl of, or fluoroalkoxy having 1 to 10 carbon atoms, p and q are each independently an integer of 0 to 4, L 4 is a single bond, -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -CONH-, -COO-, -(CH 2 ) y -, -O(CH 2 ) y O-, -O( CH 2 ) y -, -NH-, -NH(CH 2 ) y -NH-, -NH(CH 2 ) y O-, -OCH 2 -C(CH 3 ) 2 -
  • formula 11 may be each independently the following formula 14 or formula 15.
  • L 6 is a single bond, -O-, -SO 2 -, or -CR 26 R 27 -, wherein R 26 and R 27 are each independently hydrogen or alkyl having 1 to 10 carbons. .
  • the formula 14 may be the following formula 14-1.
  • formula 15 may be the following formula 15-1.
  • L 6 is O, or CH 2 .
  • Formula 11 is represented by Formula 15-1, and in Formula 15-1, L 6 may be -O-.
  • At least one repeating unit selected from the group consisting of the repeating unit represented by Formula 6, the repeating unit represented by Formula 7 and the repeating unit represented by Formula 8 in the liquid crystal aligning agent composition of the above embodiment is tetra And a combination of carboxylic dianhydride and diamine.
  • the combination of the tetracarboxylic acid dianhydride and diamine corresponds to the reaction product of tetracarboxylic acid dianhydride and diamine, wherein in Formulas 6 to 8, X 4 to X 6 are polyamic acid, polyamic acid ester or polyimide synthesis It may be a tetravalent organic group derived from a tetracarboxylic dianhydride compound used, and Y 4 to Y 6 may be a divalent organic group derived from a diamine compound used in synthesizing polyamic acid, polyamic acid ester, or polyimide.
  • the tetracarboxylic acid dianhydride may be represented by the following Chemical Formula 10-a, and the content of X 0 in the following Chemical Formula 10-a may include the content described in Chemical Formula 10 as it is.
  • the diamine may be represented by the following Formula 11-1, R 18 to R 19 in the following Formula 11-1, L 4 , p, q, k, m and n are the same as described above in Formula 11 It can contain.
  • the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent is about 1:2 or more and 1:5 or less, preferably about 1:2 or more and 1:4 or less, Or 1:2 or more and 1:3 or less.
  • the weight average molecular weight of the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent may be 1000 g/mol or more and 200000 g/mol or less.
  • the crosslinking agent compound in which the terminal crosslinking functional group according to the above embodiment is capped with a thermally desorbing protecting group may be a crosslinking agent compound having a specific chemical structure represented by the following Chemical Formula 1-1.
  • A is a monovalent to tetravalent functional group
  • j is an integer of 1 to 4
  • L 1 and L 2 are the same or different from each other, and each independently an alkylene group having 1 to 10 carbon atoms or carbon number
  • R 1 and R 2 is a silicon-containing monovalent functional group each independently.
  • A is a monovalent to tetravalent functional group
  • j may be an integer of 1 to 4.
  • the A is a functional group located at the center of the cross-linking agent compound, and the terminal functional group contained in A may be bound by j groups represented by braces [[]" in Chemical Formula 1.
  • A is a monovalent functional group.
  • A is a divalent functional group.
  • A is a trivalent functional group.
  • j is 4, A is a tetravalent functional group.
  • j is 2, and A may be an alkylene group having 1 to 10 carbon atoms, specifically, a butylene group.
  • L 1 and L 2 are the same as or different from each other, and each independently is one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, preferably L 1 and L 2 respectively It may be independently an alkylene group having 1 to 5 carbon atoms, for example, an ethylene group.
  • R 1 And R 2 is a functional group substituted for a hydrogen atom at the end of a hydroxy group (-OH), which is a crosslinkable functional group of the crosslinking agent compound, and crosslinking reaction between a polyimide or a precursor polymer thereof and the crosslinking agent compound represented by Formula 1-1 Can be suppressed.
  • R 1 and R 2 is subjected to a drying process, an exposure process, a curing process, etc. for preparing a liquid crystal alignment film from a liquid crystal aligning agent composition, and may be desorbed while being replaced with a hydrogen atom when elevated to a temperature of 150° C. or higher.
  • a crosslinking agent compound added together with a polymer for a liquid crystal aligning agent such as the liquid crystal aligning agent composition of the above embodiment, has a crosslinkable functional group of hydroxy group (-OH) at R 1 and When substituted with a specific functional group of R 2 , not only the film strength of the liquid crystal aligning agent composition rises, but also excellent electrical properties are realized.
  • the terminal of the one crosslinkable functional group a hydroxy group (-OH), R 1 and When substituted with a silicon-containing functional group of R 2 , As the silicon-containing functional group is included, it is confirmed that the reactivity of the cross-linking agent in the initial drying process decreases, and the cross-linking reaction starts after the exposure process for orientation, reducing the decrease in initial orientation caused by the cross-linking agent than the existing hydroxy group (-OH) terminal cross-linking agent. Did.
  • the imidization conversion rate increases in the process of imidization after exposure for orientation, the rearrangement rate may increase, and orientation may be increased.
  • R 1 introduced at the end of the crosslinkable functional group of the crosslinker compound, and
  • the functional group of R 2 is heat-treated at a temperature of 90° C. or higher, the desorption is removed and the hydroxyl group at the end of the cross-linkable functional group is recovered to facilitate a smooth cross-linking reaction, and at temperatures below 150° C., the cross-linking reaction by the cross-linking functional group is suppressed.
  • the structure of the crosslinking agent compound represented by Formula 1-1 is maintained, so that the crosslinking reaction between the polymer for liquid crystal aligning agent and the crosslinking agent compound represented by Formula 1-1 is maintained. This can be suppressed. And, after the drying process, exposure process, curing process, etc. for producing a liquid crystal alignment film from the liquid crystal aligning agent composition, R 1 and As the functional group of R 2 is replaced with a hydrogen atom, a crosslinking reaction between the polymer for liquid crystal aligning agent and the crosslinking agent compound represented by Chemical Formula 1 may proceed.
  • the liquid crystal aligning agent composition of the above embodiment can sufficiently improve the dispersibility of the crosslinking agent compound and the polymer for the liquid crystal aligning agent by inhibiting the crosslinking reactivity of the crosslinking agent compound added in the composition, and the manufacturing process of the liquid crystal aligning film to another embodiment described below Among them, the strength of the alignment layer is improved through a crosslinking reaction between the crosslinking agent compound and the polymer for the liquid crystal aligning agent in the composition, and excellent alignment characteristics and electrical characteristics can be realized in the finally produced liquid crystal alignment cell.
  • R 1 and R 2 may each independently be a silicon-containing monovalent functional group.
  • the silicon-containing monovalent functional group may be a functional group represented by the following Chemical Formula 2.
  • R 3 to R 5 may each independently be hydrogen, or alkyl having 1 to 10 carbons.
  • R 3 to R 5 may be an alkyl group having 1 to 10 carbon atoms, preferably a methyl group.
  • A is an alkylene group having 1 to 10 carbon atoms, and j may be 2. That is, the crosslinking agent compound represented by Chemical Formula 1-1 may include a compound represented by Chemical Formula 1-a.
  • A' is an alkylene group having 1 to 10 carbon atoms
  • L 7 to L 10 is each independently an alkylene group having 1 to 5 carbon atoms
  • R 22 to R 25 may each independently be a silicon-containing monovalent functional group
  • A′ is a butylene group having 4 carbon atoms
  • L 7 to L 10 are all ethylene groups having 2 carbon atoms
  • R 22 to R 25 are all functional groups represented by Formula 2 (R 3 to And R 5 is a methyl group).
  • crosslinking agent compound represented by the above formula 1-a A'is a butylene group having 4 carbon atoms, L 7 to L 10 are all ethylene groups having 2 carbon atoms, and R 22 to R 25 are all functional groups represented by Formula 2 (R 22 to And R 25 is an ethyl group).
  • the liquid crystal alignment layer may include an alignment cured product of the liquid crystal aligning agent composition of the embodiment.
  • the alignment cured product means a material obtained through an alignment process and a curing process of the liquid crystal aligning agent composition of the embodiment.
  • liquid crystal aligning agent composition comprising a polymer for a liquid crystal aligning agent and a crosslinking agent compound in which a terminal crosslinking functional group is capped with a thermally-releasing protecting group, and the particle number change by Equation 1 is 30 or less is used, a liquid crystal A liquid crystal alignment film with improved alignment and stability can be produced.
  • the liquid crystal alignment film may be a film strength of 2H or more, or 3H or more, or 4H or more measured by raising a weight of 50g using a pencil hardness tester in a method based on ASTM D3363 test standard.
  • the thickness of the liquid crystal alignment layer is not particularly limited, for example, it can be freely adjusted within a range of 0.01 ⁇ m or more and 1000 ⁇ m or less.
  • the thickness of the liquid crystal alignment layer is increased or decreased by a specific value, physical properties measured in the liquid crystal alignment layer may also be changed by a certain value.
  • an example of a method of manufacturing the liquid crystal alignment layer is not particularly limited, for example, forming a coating layer by applying a liquid crystal alignment agent composition to a substrate (step 1); Drying the coating film (step 2); Orienting the coating film by irradiating light or rubbing (step 3); And a step (step 4) of heat-treating and curing the alignment-treated coating film, a method of manufacturing a liquid crystal alignment film may be used.
  • Step 1 is a step of forming a coating film by applying the above-described liquid crystal aligning agent composition to a substrate.
  • the contents of the liquid crystal aligning agent composition include all of the contents described above in one embodiment.
  • the method of applying the liquid crystal aligning agent composition to the substrate is not particularly limited, and for example, methods such as screen printing, offset printing, flexo printing, and inkjet may be used.
  • the liquid crystal aligning agent composition may be dissolved or dispersed in an organic solvent.
  • organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, and N-ethylpyrrolid Don, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy -N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone ,
  • the liquid crystal aligning agent composition may further include other components in addition to the organic solvent.
  • the film thickness uniformity or surface smoothness is improved, or the adhesion between the liquid crystal alignment film and the substrate is improved, or the dielectric constant or conductivity of the liquid crystal alignment film is changed.
  • an additive that can increase the density of the liquid crystal alignment layer may be further included. Examples of such additives include various solvents, surfactants, silane-based compounds, dielectric or crosslinkable compounds, and the like.
  • Step 2 is a step of drying the coating film formed by applying the liquid crystal aligning agent composition to a substrate.
  • the step of drying the coating film may use methods such as heating and vacuum evaporation of the coating film, and is preferably performed at 50°C or higher and 150°C or lower, or at 60°C or higher and 140°C or lower.
  • step 3 the coating film is irradiated with light to perform alignment treatment.
  • the coating film in the alignment treatment step may refer to a coating film immediately after the drying step, or may be a coating film after heat treatment after the drying step.
  • the "coating film immediately after the drying step” means that light is irradiated immediately without proceeding to the heat treatment at a temperature higher than the drying step after the drying step, and other steps other than the heat treatment can be added.
  • a step of irradiating light after a high temperature heat treatment is essentially performed for imidization of the polyamic acid.
  • the alignment film is formed by heat-curing and curing the alignment-treated coating film immediately after irradiating the light without including the heat treatment step. Can be produced.
  • light irradiation may be to irradiate polarized ultraviolet light having a wavelength of 150 nm or more and 450 nm or less.
  • the intensity of the exposure varies depending on the type of the polymer for the liquid crystal aligning agent, and energy of 10 mJ/cm 2 or more and 10 J/cm 2 or less, preferably energy of 30 mJ/cm 2 or more and 2 J/cm 2 or less can be irradiated. .
  • a polarizing device using a substrate coated with a dielectric anisotropic material on the surface of a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, or a polarizing plate on which aluminum or metal wire is deposited, or quartz glass
  • the alignment treatment is performed by irradiating polarized ultraviolet rays selected from among polarized ultraviolet rays by passing or reflecting a Brewster polarizer or the like by reflection.
  • the polarized ultraviolet light may be irradiated perpendicularly to the substrate surface, or may be irradiated by tilting the incident angle at a specific angle.
  • the alignment ability of the liquid crystal molecules is imparted to the coating film.
  • the rubbing treatment in the alignment treatment may use a method using a rubbing cloth. More specifically, the rubbing treatment may rub the surface of the coating film after the heat treatment step in one direction while rotating the rubbing roller having the cloth of the rubbing cloth attached to the metal roller.
  • the step 4 is a step of curing by heat-treating the alignment-treated coating film.
  • a crosslinking agent compound represented by Chemical Formula 1-2 may be included in the alignment-treated coating film.
  • A, j, L 1, and L 2 is as defined in Chemical Formula 1-1 of the above embodiment.
  • the crosslinker compound represented by Chemical Formula 1-2 may be a result of a substitution reaction of a crosslinker compound represented by Chemical Formula 1-1.
  • the terminal of the hydroxy group (-OH), which is a crosslinkable functional group has R 1 and Although R 2 is substituted with a specific functional group, R 1 and 1 in the crosslinker compound represented by Chemical Formula 1-1 as the temperature rises to 90° C. or higher in the step of heat-treating and curing the oriented coating film
  • the functional group of R 2 may be substituted with a hydrogen atom to produce a crosslinker compound represented by Chemical Formula 1-2.
  • the crosslinking agent compound represented by Chemical Formula 1-2 is included in the liquid crystal aligning agent composition of the above embodiment, the crosslinking agent compound is hardly evenly dispersed in the composition and the storage stability is also reduced as some crosslinking reactions proceed from within the composition.
  • the present invention suppresses the crosslinking reaction in the composition by adding the crosslinking agent compound represented by Formula 1-1 in the liquid crystal aligning agent composition, and then heat-treating the alignment-treated coating film to cure it. It can be induced to convert the crosslinker compound represented by -1 to a crosslinker compound represented by Formula 1-2. Accordingly, in the composition, the dispersibility and stability of the crosslinking agent compound can be increased, and in the alignment layer, an effect of improving the film strength can be realized through the formation of a crosslinked structure.
  • the step of heat-treating and curing the alignment-treated coating film is a step performed after irradiation with light, even in a method of manufacturing a liquid crystal alignment film using a polymer for a liquid crystal aligning agent containing a polyamic acid or a polyamic acid ester. It is distinguished from the heat treatment step applied to the substrate and prior to irradiating light or imidizing the liquid crystal aligning agent while irradiating light.
  • the heat treatment may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and is preferably performed at 150°C or more and 300°C or less, or 200°C or more and 250°C or less.
  • heating means such as a hot plate, a hot air circulation path, an infrared furnace, and is preferably performed at 150°C or more and 300°C or less, or 200°C or more and 250°C or less.
  • the step of drying the coating film may further include the step of heat-treating the coating film immediately after the drying step at a temperature equal to or higher than the drying step.
  • the heat treatment may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and is preferably performed at 150°C or more and 250°C or less.
  • the liquid crystal aligning agent can be imidized.
  • the method of manufacturing the liquid crystal alignment film includes the steps of applying the above-described liquid crystal alignment agent to a substrate to form a coating film (step 1); Drying the coating film (step 2); Heat-treating the coating film immediately after the drying step at a temperature equal to or higher than the drying step (step 3); The heat-treated coating film may be irradiated with light or subjected to rubbing treatment to perform alignment treatment (step 4) and heat-curing the orientation-treated coating film (step 5).
  • liquid crystal display device including the above-described liquid crystal alignment film is provided.
  • the liquid crystal alignment layer may be introduced into a liquid crystal cell by a known method, and the liquid crystal cell may be introduced into a liquid crystal display device by a known method.
  • the liquid crystal aligning film is prepared from a liquid crystal aligning agent composition including a crosslinking agent compound in which the polymer for the liquid crystal aligning agent and the crosslinking functional group at the terminal are capped with a thermally desorbable protecting group, and can realize excellent stability along with excellent physical properties. Accordingly, a liquid crystal display device capable of exhibiting high reliability is provided.
  • the liquid crystal alignment display device has a voltage holding ratio (VHR) of 85% or more, 85% or more, 99% or less, 88% or more, and 99% or less measured using a TOYO CORPORATION 6254C device at 1Hz and 60°C. , 89% or more and 99% or less, 90% or more and 99% or less, or 94% or more and 99% or less.
  • VHR voltage holding ratio
  • the present invention may provide a liquid crystal aligning agent composition capable of realizing improved storage stability and electrical properties while having excellent film strength when synthesizing a liquid crystal alignment film, a method of manufacturing a liquid crystal aligning film using the same, and a liquid crystal aligning film and a display device using the same.
  • Diamine DA-1 was synthesized according to the following scheme.
  • 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (1,3-dimethylcyclobuthane-1,2,3,4-tetracarboxylic dianhydride, DMCBDA) and 4-nitroaniline (4 -nitroaniline) was dissolved in DMF (Dimethylformamide) to prepare a mixture. Then, the mixture was reacted at for about 12 hours to prepare an amic acid. Then, the amic acid was dissolved in DMF, acetic anhydride and sodium acetate were added to prepare a mixture. Subsequently, the amic acid contained in the mixture was imidized at about 90° C. for about 4 hours. After the imide thus obtained was dissolved in DMAc (Dimethylacetamide), Pd/C was added and a mixture was prepared. This was reduced for 20 minutes under a hydrogen pressure of 45° C. and 6 bar to prepare diamine DA-1.
  • DMF Dimethylformamide
  • N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide N,N,N',N'-Tetrakis (2-hydroxyethyl)adipamide
  • 5 g (15.6 mmol) and chlorotrimethyl
  • silane Chlorotrimethylsilane
  • 17.3 g (125 mmol) of potassium carbonate (K 2 CO 3 ) was added and stirred for 10 hours under a nitrogen atmosphere at 0°C.
  • DA-1 prepared in Preparation Example 1 was completely dissolved in 77.3 g of anhydrous N-methyl pyrrolidone (NMP). Then, 2.92 g (0.013 mmol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal.
  • DMCBDA 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride
  • the polymer P-1 , 6 g for the liquid crystal aligning agent prepared in Synthesis Example 1 and the polymer Q-1 , 14 g for the liquid crystal aligning agent prepared in Synthesis Example 2 were NMP 12.4 g and n- 7.6 g of butoxyethanol was added to obtain a 5 wt% solution. Then, N1,N1,N6,N6-tetrakis(2-(trimethylsilyloxy)ethyl)adipamide obtained in Preparation Example 2 as a crosslinking agent was added to the solution at 5% by weight based on the solid content included in the total solution, and 25 Stir at 16°C for 16 hours. The obtained solution was pressure-filtered with a filter having a pore size of 0.1 ⁇ m made of poly(tetrafluorene ethylene) to prepare a liquid crystal aligning agent composition.
  • Liquid crystal aligning agent by spin coating on the upper and lower substrates for the voltage retention ratio (VHR) patterned with ITO electrodes with a thickness of 60 nm and an area of 1 cm X 1 cm on a square glass substrate having a size of 2.5 cm X 2.7 cm The composition was applied. Subsequently, the substrate coated with the liquid crystal aligning agent was placed on a hot plate at about 70° C. and dried for 3 minutes to evaporate the solvent.
  • VHR voltage retention ratio
  • ultraviolet rays at 254 nm were irradiated at an exposure amount of about 0.1 to 1 J/cm 2 by using an exposure machine with a linear polarizer attached to each of the upper and lower plates. Thereafter, the alignment-treated upper/lower plates were fired (cured) in an oven at about 230° C. for 30 minutes to obtain a liquid crystal alignment film having a film thickness of 0.1 ⁇ m.
  • a sealing agent impregnated with a ball spacer having a size of 4.5 ⁇ m was applied to the edge of the top plate except for the liquid crystal injection hole. Then, after aligning the liquid crystal alignment films formed on the upper and lower plates so that the alignment directions were parallel to each other, the upper and lower plates were bonded, and an empty cell was prepared by UV and heat curing the sealing agent. Then, liquid crystal was injected into the empty cell and the injection hole was sealed with a sealing agent to prepare a liquid crystal alignment cell.
  • the liquid crystal aligning agent composition the liquid crystal alignment layer, and the liquid crystal were prepared in the same manner as in Example 1, except that the crosslinking agent was added at 10% by weight based on the solid content included in the total solution.
  • An orientation cell was prepared.
  • a liquid crystal aligning agent composition a liquid crystal alignment layer, and a liquid crystal were prepared in the same manner as in Example 3, except that the crosslinking agent was added in an amount of 15% by weight based on the solid content included in the total solution.
  • An orientation cell was prepared.
  • Example 1 A liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as described above.
  • a liquid crystal aligning agent composition a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as in Example 1, except that the crosslinking agent of Preparation Example 2 was not added.
  • N,N,N',N'-Tetrakis(2-hydroxyethyl)adipamide of Comparative Preparation Example 1 is based on the solid content included in the total solution.
  • a liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as in Example 1, except that 3% by weight was added.
  • N,N,N',N'-Tetrakis(2-hydroxyethyl)adipamide of Comparative Preparation Example 1 is based on the solid content included in the total solution.
  • a liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as in Example 1, except that 8% by weight was added.
  • Example 1 A liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as described above.
  • Polarizing plates were attached to the upper and lower plates of the liquid crystal alignment cells obtained in Examples and Comparative Examples so that they were perpendicular to each other. At this time, the polarization axis of the polarizing plate attached to the lower plate was made to be parallel to the alignment axis of the liquid crystal alignment cell. Then, a liquid crystal alignment cell with a polarizing plate was placed on a backlight having a brightness of 7,000 cd/m 2 , and light leakage was observed with the naked eye. At this time, if the alignment characteristics of the liquid crystal alignment film are excellent and the liquid crystals are well arranged, light is not transmitted through the upper and lower polarizing plates vertically attached to each other and dark without defects. In this case, the alignment characteristic is'good', and when light leakage such as liquid crystal marks or bright spots is observed, it is indicated in Table 2 below.
  • VHR voltage retention ratio
  • the film strength of the alignment films was measured, and the results are shown in Table 2 below. Specifically, the film strength of the alignment film was measured using a pencil hardness tester and raising the weight of 50 g using a pencil of various hardness in a method based on the ASTM D3363 test standard.
  • the particle number change was measured by following Formula (1).
  • EA 0 is the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal aligning agent composition at the first time point (0 second) at which the liquid crystal aligning agent composition was obtained,
  • EA 1 is the number of particles having a particle diameter of 0.5 ⁇ m or more contained in the liquid crystal aligning agent composition at a time point after the liquid crystal aligning agent composition is stored at a temperature condition of approximately 17° C. for 30 days from the initial time point (0 second).
  • the particle number is a liquid particle sensor (KS-42B, Rion, light source wavelength 780nm, light source output 40mW, flow rate 10mL/min, maximum particle number 1200/mL, simultaneous measurement loss 5%, DC12V) Then, the particle number was measured for five channels of 0.2 ⁇ m or more, 0.3 ⁇ m or more, 0.5 ⁇ m or more, 1.0 ⁇ m or more, and 2.0 ⁇ m or more under conditions of 23° C. and Particle class 1000 or less, and then 0.5 ⁇ m or more and 1.0 ⁇ m. Above, it can be calculated by adding all the numbers of each particle measured in a channel of 2.0 ⁇ m or more.
  • the liquid crystal aligning agent composition of the embodiment containing the crosslinking agent of Preparation Example 2 together with the polyimide-based polymer in the composition exhibits excellent liquid crystal aligning properties and at the same time has a high film strength of 3H or more and 4H or less. It was confirmed that the voltage retention was very high, 88% or more and 94% or less. For this reason, it was confirmed that the alignment cell prepared from the liquid crystal aligning agent composition of the above embodiment has excellent alignment properties and film strength, and at the same time, realizes excellent electrical properties.
  • the voltage retention was found to be at the same level as that of the liquid crystal aligning agent composition of Example, but the particle number change was 550 or more. Compared to the example, it showed a significant change in the number of particles, and it was confirmed that the long-term storage stability of the composition for a liquid crystal alignment agent was significantly inferior to that of the present example.
  • liquid crystal aligning agent composition of the present example containing the crosslinking agent of Preparation Example 2 showed a particle number change of 9 or less, and the number of particles of the same level as the liquid crystal aligning agent composition of Comparative Example 1 containing no crosslinking agent. It was confirmed that it showed a change.
  • the alignment film obtained from the liquid crystal aligning agent composition of Reference Example 1 using the crosslinking agent represented by the formula (A) has a film strength of 1H, which results in a very poor film strength and a voltage retention of 68%, compared to the above embodiment. It was confirmed that it was greatly reduced.
  • liquid crystal aligning agent composition of the present embodiment containing the crosslinking agent of Preparation Example 2 exhibits a remarkably small particle number change, and has excellent long-term storage stability, and at the same time, realizes excellent orientation, film strength, and excellent electrical properties. Confirmed.

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Abstract

La présente invention concerne une composition d'alignement de cristaux liquides comprenant un polymère d'alignement de cristaux liquides et un composé de réticulation comportant un groupe fonctionnel terminal de réticulation coiffé d'un groupe de protection contre la rupture thermique, ladite composition changeant en nombre de particules à un niveau inférieur ou égal à un niveau prédéfini pendant le stockage ; un procédé de fabrication d'un film d'alignement de cristaux liquides utilisant cette composition ; un film d'alignement de cristaux liquides utilisant celle-ci ; et un dispositif d'affichage à cristaux liquides.
PCT/KR2020/000805 2019-01-21 2020-01-16 Composition d'alignement de cristaux liquides et film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides utilisant ceux-ci WO2020153659A1 (fr)

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JP2020546958A JP6992242B2 (ja) 2019-01-21 2020-01-16 液晶配向剤組成物、これを用いた液晶配向膜および液晶表示素子
CN202080001922.8A CN111868212B (zh) 2019-01-21 2020-01-16 液晶取向剂组合物、以及使用其的液晶取向膜和液晶显示器
EP20744241.9A EP3750973A4 (fr) 2019-01-21 2020-01-16 Composition d'alignement de cristaux liquides et film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides utilisant ceux-ci
US17/046,229 US11561438B2 (en) 2019-01-21 2020-01-16 Liquid crystal alignment agent composition, and liquid crystal alignment film, and liquid crystal display using the same

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WO2022102281A1 (fr) * 2020-11-13 2022-05-19 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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