WO2018216939A1 - Polymer for liquid crystal aligning agent, liquid crystal aligning agent comprising same, and liquid crystal alignment film and liquid crystal display device using same liquid crystal aligning agent - Google Patents

Polymer for liquid crystal aligning agent, liquid crystal aligning agent comprising same, and liquid crystal alignment film and liquid crystal display device using same liquid crystal aligning agent Download PDF

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Publication number
WO2018216939A1
WO2018216939A1 PCT/KR2018/005505 KR2018005505W WO2018216939A1 WO 2018216939 A1 WO2018216939 A1 WO 2018216939A1 KR 2018005505 W KR2018005505 W KR 2018005505W WO 2018216939 A1 WO2018216939 A1 WO 2018216939A1
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Prior art keywords
liquid crystal
formula
polymer
crystal aligning
aligning agent
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PCT/KR2018/005505
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French (fr)
Korean (ko)
Inventor
권순호
조정호
민성준
이상미
구기철
윤준영
윤형석
임윤빈
김성구
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170150898A external-priority patent/KR102162502B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2019541142A priority Critical patent/JP6962518B2/en
Priority to US16/488,203 priority patent/US11287700B2/en
Priority to CN201880006473.9A priority patent/CN110168054B/en
Publication of WO2018216939A1 publication Critical patent/WO2018216939A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a polymer suitable for use in a liquid crystal aligning agent having excellent liquid crystal alignment property and electrical properties, a liquid crystal aligning agent comprising the same, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display device comprising the liquid crystal aligning film.
  • the liquid crystal aligning agent 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 appropriate direction when the image is formed.
  • liquid crystal aligning agent polyimide, polyamide, polyester, and the like are widely known.
  • polyimide is particularly used in many liquid crystal display devices because of its excellent heat resistance, affinity with liquid crystal, mechanical strength, and the like.
  • liquid crystal alignment agents can affect not only the basic characteristics of liquid crystal alignment, but also electrical characteristics such as afterimage and voltage retention caused by DC / AC voltage. It has been found that the need for the development of a liquid crystal alignment material that can simultaneously realize excellent liquid crystal alignment and electrical properties is increasing.
  • the monomers used to prepare the liquid crystal alignment agent may be changed or Although various attempts have been made to improve the physical and chemical properties by changing the structure of the liquid crystal aligning agent through a method of combining a plurality of other monomers, the situation has not yet reached a breakthrough in physical properties.
  • the present invention is to provide a polymer suitable for use in a liquid crystal aligning agent because of excellent liquid crystal alignment and electrical properties.
  • the present invention liquid crystal aligning agent, with the liquid crystal alignment jeyong polymer.
  • An object of the present invention is to provide a liquid crystal alignment film and a liquid crystal display device.
  • a repeater represented by the following Chemical Formula 1 A unit, a repeating unit represented by the following Chemical Formula 2 and a repeating unit selected from the group consisting of a repeating unit represented by the following Chemical Formula 3, a polymerizer for a liquid crystal aligning agent Is provided.
  • R 1 and R 2 are each alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X 1 to X 3 are each independently a tetravalent organic group, Y 1 to Y 3 is Each independently represent a divalent organic group represented by Formula 4,
  • A is a group 15 element, 3 ⁇ 4 is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 1 to 3, at least one of Z 4 is nitrogen, the rest is carbon.
  • substitution means that another functional group is bonded to the 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 a substituent may be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted &quot means ' hydrogen hydrogen; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group ; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, 0 and S atoms, or two or more substituents of the above-described substitu
  • the substituent to which two or more substituents are linked 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 linked.
  • +, or ⁇ means a bond connected to another substituent
  • a direct bond means a case where no separate atom is present in the portion represented by L.
  • the alkyl group may be straight or branched chain, 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 include 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, nuclear chamber, n-nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylnuclear, cyclopentylmethyl,
  • the fluoroalkyl group having 1 to 10 carbon atoms may have one or more hydrogens of the alkyl group having 1 to 10 carbon atoms substituted with fluorine, and the fluoroalkoxy group having 1 to 10 carbon atoms may have at least one hydrogen of the alkoxy group having 1 to 10 carbon atoms. It may be substituted with fluorine.
  • Halogen may be fluorine (F), chlorine (C1), bromine (Br) or iodine (I).
  • Group 15 elements are nitrogen (N), phosphorus (P), arsenic (As), tin (Sb) or Bismuth (Bi).
  • Nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and a nitrogen oxide functional group means a functional group including nitrogen oxide in a functional group.
  • a nitrogen oxide functional group means a functional group including nitrogen oxide in a functional group.
  • the oxides of nitrogen functional groups may be used a nitro group (-N0 2) or the like. Accordingly, the present inventors, through experiments, using a polymer for a liquid crystal aligning agent comprising the repeating units of the above formulas 1 to 3 prepared from the semi-ungmul containing a diamine compound having a specific structure containing a nitrogen atom, to maintain a high voltage at a high temperature The present invention was completed after confirming that it can have a decrease in contrast ratio and an afterimage phenomenon.
  • liquid crystal comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 Polymers for the alignment agent may be provided.
  • the polymer according to one embodiment includes the repeating unit of Formula 1 to 3 above.
  • X 1 to X 3 may be various tetravalent organic groups as described above
  • Y 1 to Y 3 may be various divalent organic groups as described above.
  • Y 1 to Y 3 may be defined as a divalent organic group represented by Formula 4 to provide a polymer for a liquid crystal aligning agent having a variety of structures that can express the above-described effect.
  • A is a group 15 element, 3 ⁇ 4 is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 1 to 3, at least one of 1 to ⁇ 4 , that is, at least one is nitrogen, The rest is carbon.
  • the group 15 element may be nitrogen ( ⁇ ), phosphorus ( ⁇ ), arsenic (As), tin (Sb) or bismuth (Bi).
  • R 3 is a functional group bonded to A, wherein The number of displayed numbers can be combined with element A.
  • A is nitrogen, 3 ⁇ 4 is hydrogen, a may be 1.
  • Formula 4 is a repeating unit derived from diamine which is a precursor used to form a polymer for a liquid crystal aligning agent, and may be due to the use of an asymmetric diamine as described below.
  • one of ⁇ ⁇ to ⁇ 4 may be nitrogen and the rest may be carbon
  • one of ⁇ or 3 ⁇ 4 is nitrogen and the rest is carbon
  • ⁇ 2 and ⁇ 4 are Carbon. That is, the ring comprising a ⁇ ⁇ to 4 in the general formula (4) may have a pyridine (pyr dine i) structure. Accordingly, the liquid crystal display device to which the polymer for liquid crystal aligning agent of the above embodiment is applied may implement high voltage retention and liquid crystal alignment.
  • the functional group represented by Formula 4 is two aromatic ring compounds
  • the heteroaromatic ring compound and the aromatic ring compound Preferably, only the amine group and hydrogen are bonded to each of the heteroaromatic ring compound and the aromatic ring compound, and other substituents are not introduced.
  • Substituents to the heteroaromatic ring compound or the aromatic ring compound for example, when a fluoroalkyl group is introduced, there is a technical problem that the brightness fluctuation is increased and the afterimage property is poor and the voltage retention rate is significantly reduced.
  • Chemical Formula 4 may include one or more functional groups selected from the group consisting of Chemical Formulas 4-1, 4-2, and 4-3.
  • the repeating unit of Formula 4 includes at least one functional group selected from the group consisting of Formulas 4-1, 4-2, and 4-3, thereby achieving better liquid crystal alignment.
  • X 1 ' to X 3 are each independently represented by the formula (5) It may include a tetravalent organic group. That is, X 1 to X 3 may each independently correspond to any one of the tetravalent organic groups described in the following Formula 5.
  • L 2 is a direct bond, -0-, -CO—, -S-, -S0-, -S0 2 —,- CRioRn-, -C0NH-, -C00-,-(CH 2 ) b- , -0 (CH 2 ) b 0-, -C00- (CH 2 ) b -0C0-, phenylene or a combination thereof
  • R 10 and R u are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms
  • b is an integer of 1 to 10.
  • the ⁇ ⁇ to X 3 are each independently an organic group represented by the following Chemical Formula 5-1 derived from pyromel lit ic di anhydride (PMDA); The following derived from 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-biphenylphenyltracarboxylic acid dianhydride, BPDA) An organic group of Formula 5-2; An organic group represented by the following Chemical Formula 5-3 derived from 1,2,4,5-cyclotetracarboxylic acid tetraanhydride (1,2,4,5 ′ Cyclohexanetetracarboxylic Dihydride, HPMDA); Or an organic group of formula ' 5-4 ' derived from 1,3-dimethyl-cyclobutane _1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA).
  • Chemical Formula 5-1 derived from pyromel lit ic di anhydride (PMDA); The following derived from 3,
  • the polymer is 0 mol% to 80 mol%, preferably 0.1 mol of the repeating units represented by Formula 1, which is an imide repeating unit, among the repeating units represented by Formulas 1, 2, and 3 % To 65 mol% may be included.
  • the repeating unit represented by the formula (1) is included less than the content range does not exhibit a sufficient orientation characteristics, the orientation stability may be lowered, and if the content of the repeating unit represented by the formula (1) exceeds the range solubility Problems may appear that are difficult to produce a stable alignment liquid coatable. Accordingly, it is preferable to include the repeating unit represented by the formula (1) in the above-described content range because it can provide a polymer for liquid crystal aligning agent excellent in all of storage stability, electrical properties, orientation characteristics and orientation stability.
  • repeating unit represented by Formula 2 or the repeating unit represented by Formula 3 may be included in an appropriate content according to the desired properties.
  • the repeating unit represented by Chemical Formula 2 may include 0 mol% to 50 mol%, preferably 0.01 mol% to 30 mol% with respect to all the repeating units represented by Chemical Formulas 1 to 3. Since the repeating unit represented by the formula (2) has a low rate of conversion to imide during the high temperature heat treatment process after light irradiation, when it exceeds the above range, the overall imidation ratio may be insufficient and the orientation stability may be lowered. Accordingly, the repeating unit represented by Formula 2 may provide a polymer for a liquid crystal aligning agent that exhibits proper solubility within the above-described range and may realize excellent imidation ratio while having excellent process characteristics.
  • the repeating unit represented by Chemical Formula 3 may include 10 mol% to 100 mol, preferably 30 mol% to 99.8 mol%, based on the total repeating units represented by Chemical Formulas 1 to 3. It is possible to provide a polymer for a liquid crystal aligning agent that exhibits excellent coating properties within such a range and excellent in process characteristics and can realize a high imidation ratio.
  • the polymer for a liquid crystal aligning agent of the embodiment is at least one type selected from the group consisting of a repeating unit represented by the following formula 11, a repeating unit represented by the following formula 12 and a repeating unit represented by the following formula It may further include a unit.
  • At least one of R 3 and R 4 is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen,
  • X 4 to X 6 are each independently a tetravalent organic group
  • X 4 to X 6 are each independently a divalent organic group represented by the following formula (14),
  • R 5 and R 6 are each independently hydrogen, halogen, cyano, alkyl, C 2 - 10 alkenyl, alkoxy, Cwo alkoxy, alkyl, d- or 10-fluoro- ⁇ d) fluoro, p and q are each independently Is an integer of 0 to 4,
  • L 1 is a single bond, -E, -CO-, -S-, -S0 2- , -C (C3 ⁇ 4) 2 — , — C (CF 3 ) 2 — , -CONH-,
  • z is an integer from 1 to 10,
  • k and m are each independently an integer of 0-3, or 1-3, and n is an integer of 0-3.
  • Hydrogen may be bonded to carbon which is not substituted with R 5 or R 6 in Formula 14, and P and q are each independently 0 to 4, or.
  • P and q are each independently 0 to 4, or.
  • p or q is an integer of 2 to 4
  • a plurality of R 5 or R 6 may be the same or different substituents.
  • k and m may be each independently an integer of 0 to 3, or 1 to 3
  • n may be an integer of 0 to 3, or 1 to 3.
  • Formula 14 may be Formula 15 or Formula 16 below.
  • D is a direct bond, -0-, -S0 2 -or -C (R 7 ) (R 8 ) one, wherein R 7 and 3 ⁇ 4 are each independently hydrogen, or of 1 to 10 carbon atoms Alkyl group.
  • Formula 15 may be the following Formula 17. [Formula 17]
  • Chemical Formula 16 may be Chemical Formula 18.
  • R 9 to R 14 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms
  • L 2 is a direct bond, -0-, -CO-, -S-, -S0-, -S0 2 -, -CR 15 R 16 _, -C0NH-, -C00-,-(CH 2 ) b- , -0 (CH 2 ) b 0-, -C00- (CH 2 ) b -0C0-, phenylene or It is any one selected from the group consisting of these, R ⁇ 15> and R ⁇ 16> is respectively independently hydrogen, a C1-C10 alkyl group, or a C1-C10 fluoroalkyl group, b is an integer of 1-10.
  • the repeating unit represented by the formula (1) at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) and the repeating unit represented by the formula (11)
  • the molar ratio between one or more repeating units selected from the group consisting of a repeating unit represented by 12 and a repeating unit represented by Formula 13 may be 1: 100 to 100: 1.
  • the polymer for a liquid crystal aligning agent of the embodiment further comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula 21, a repeating unit represented by the following formula 22 and a repeating unit represented by the following formula 23 can do.
  • R 21 and R 22 are each alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X 21 to 3 ⁇ 4 3 is different from X 1 to X 3 of the formula 1 to 3, Different from X 4 to X 6 of Formulas 11 to 13, or different from X 1 to X 3 of Formulas 1 to 3 and X 4 to X 6 of Formulas 11 to 13, each independently represented by Formula 5 It is a tetravalent organic group to be, Y 21 to 3 ⁇ 4 are each independently a divalent organic group represented by the formula (4) or a divalent organic group represented by the formula (14).
  • the weight average molecular weight of the polymer for liquid crystal aligning agent may be 1000 g / mol to 200, 000 g / nrol.
  • a weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method.
  • a detector and an analytical column such as a commonly known analytical device and a differential refractive index detector (Refractive Index Detector), may be used.
  • Temperature conditions, solvents, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C, a chloroform solvent (Chloroform) and f low rate of 1 mL / min.
  • Such a polymer may be used as a liquid crystal aligning agent to provide a liquid crystal alignment layer that realizes excellent stability and reliability.
  • Examples of the method for producing the polymer for liquid crystal aligning agent are greatly limited For example, the step of preparing a compound of formula 8 by reacting a heteroaromatic compound of formula 6 with an aromatic compound of formula 7; Reducing the compound of Formula 8 to prepare a diamine of Formula 9; Reacting the diamine of Formula 9 with tetracarboxylic acid or its anhydride; And a method for producing a polymer for a liquid crystal aligning agent comprising the step of imidizing a reaction product of the following tetracarboxylic acid or an anhydride thereof.
  • At least one of ⁇ to Z 4 is nitrogen, the rest is carbon,
  • A is a group 15 element
  • R 3 is hydrogen, an alkyl group having 1 to 10 carbon atoms
  • q is an integer of 2 to 4
  • R 23 is an amino group or a nitrogen oxide functional group
  • R 21 is a chlorine element
  • R 22 is a nitro group
  • A is a nitrogen element
  • 3 ⁇ 4 is hydrogen
  • q is 2
  • R 23 may be an amino group.
  • examples of the formula (7) include paraphenylenediamine metaphenylenediamine and the like.
  • the compound of Formula 8 may be prepared by reacting the heteroaromatic compound of Formula 6 with the aromatic compound of Formula 7.
  • a reaction in which the halogen element of R 21 included in the heteroaromatic compound of Formula 6 is substituted with a group 15 element of A included in the aromatic compound of Formula 7 may be performed.
  • the reaction can be carried out in a high yield of 50% or more under mild conditions that proceed for 6 to 15 hours at room temperature by the tertiary amine catalyst.
  • the reaction can be carried out in the presence of various conventionally known organic solvents, specific examples of the organic solvents include ethyl acetate, tetrahydrofuran, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methyl-2- Pyridone, ⁇ -methylcaprolactam, 2 ⁇ pyridone, ⁇ -ethylpyrrolidone, ⁇ -vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, butyrolactone , 3-Methoxy- ⁇ , ⁇ -dimethylpropanamide , 3-Ethoxy- ⁇ , ⁇ -dimethylpropanamide , 3-Butoxy- ⁇ , ⁇ ⁇ dimethylpropanamide , 1, 3-dimethyl ⁇ imidazolidinone , Ethyl amyl ketone, methyl nonyl ketone
  • R 21 is a halogen element
  • R 22 is a nitrogen oxide functional group
  • at least one of Zi to Z 4 may be nitrogen
  • the rest may be carbon.
  • one of 1 ⁇ to ⁇ 4 may be nitrogen
  • the rest may be carbon.
  • one of ⁇ ⁇ or 3 ⁇ 4 is nitrogen and the others are carbon, 3 ⁇ 4 and ⁇ 4 May be carbon.
  • R 21 may be chlorine
  • R 22 may be a nitro group.
  • A is a group 15 element
  • 3 ⁇ 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • q is an integer of 2 to 4
  • R 23 may be an amino group or a nitrogen oxide functional group.
  • A is nitrogen
  • R 3 is hydrogen
  • q is 2
  • R 23 may be an amino group.
  • nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded
  • the nitrogen oxide functional group means a functional group including nitrogen oxide in the functional group.
  • examples of the nitrogen oxide functional group can be used nitro group (-N02) and the like.
  • the group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sb) or bismuth (Bi).
  • 3 ⁇ 4 is a functional group that binds to A, and may bind to element A as many as the number represented by q.
  • the compound of Formula 8 thus prepared may prepare a diamine compound of Formula 9 through reduction reaction.
  • the diamine compound may be synthesized as the nitrogen oxide functional group of R 22 included in the compound of Formula 8 is reduced under reduced conditions to be reduced to a primary amino group.
  • the reduction reaction may be carried out in a high yield of 80% or more under mild conditions that proceed for 10 to 15 hours at room temperature by a palladium / carbon catalyst.
  • the reaction may be carried out in the presence of various conventionally known organic solvents, and specific examples of the organic solvent include ethyl acetate, tetrahydrofuran, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methyl-2- Pyrlidone, ⁇ -methylcaprolactam, 2-pyridone, ⁇ -ethylpyridone, ⁇ -vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, ⁇ - Butyrolactone, 3—Methoxy- ⁇ , ⁇ -dimethylpropanamide, 3-Especial - ⁇ , ⁇ -dimethylpropanamide, 3-Buroxy- ⁇ , ⁇ -d
  • the content of 3 ⁇ 4 3 includes the content described above in Chemical Formulas 6 and 7.
  • the diamine of Formula 9 prepared through the above steps may be used for the tetracarboxylic acid or anhydride thereof, for example, pyromel l di anhydride (PMDA), 3,3 ', which is commonly used for preparing polyamic acid.
  • PMDA pyromel l di anhydride
  • diamine of the general formula (9) prepared through the above steps various kinds of diamine compounds well known in the art of liquid crystal aligning agents, for example, ⁇ -phenylenediamine ⁇ 4,4-oxydianiline, 4,4'-methylenedianiline etc. can be mixed, and amic acid, amic acid ester, or its mixture can be manufactured.
  • diamine compounds well known in the art of liquid crystal aligning agents for example, ⁇ -phenylenediamine ⁇ 4,4-oxydianiline, 4,4'-methylenedianiline etc. can be mixed, and amic acid, amic acid ester, or its mixture can be manufactured.
  • reaction conditions may be appropriately adjusted with reference to the preparation conditions of the polyamic acid known in the art. Then, the obtained amic acid, amic acid ester, or a mixture thereof can be imidized to prepare a polymer having the above-described repeating units of the formulas (1) to (3).
  • a liquid crystal aligning agent comprising the polymer.
  • the liquid crystal aligning agent includes the polymer described above, the liquid crystal aligning agent effectively suppresses deterioration in stability and reliability due to polymer degradation reaction during the firing process and storage, and exhibits excellent coating properties and at the same time excellent imide conversion rate. Can be represented.
  • Such liquid crystal aligning agent may be provided through various methods known in the art to which the present invention pertains, except for including the polymer described above.
  • the above-described polymer may be dissolved or dispersed in an organic solvent to provide a liquid crystal aligning agent.
  • organic solvent examples include ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methyl-2-pyrrolidone, ⁇ -methylcaprolactam, 2-pyridone and ⁇ -ethylpyrroli Money, ⁇ -vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, butyrolactone, 3-methoxy- ⁇ , ⁇ - dimethylpropanamide, 3-especially- ⁇ , ⁇ -dimethylpropanamide, 3-Buroxy- ⁇ , ⁇ -dimethylpropanamide, 1, 3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Isopropyl ketone, cyclonucleanone, ethylene carbonate,
  • the liquid crystal aligning agent may further include other components in addition to the polymer and the organic solvent.
  • a liquid crystal aligning agent when applied, it improves the uniformity and surface smoothness of a film thickness, improves the adhesiveness of a liquid crystal aligning film and a board
  • a liquid crystal aligning film including the liquid crystal aligning agent described above is provided.
  • the fact that the liquid crystal aligning film includes a liquid crystal aligning agent means that the liquid crystal aligning film includes the liquid crystal aligning agent itself or the black liquid crystal aligning film includes a product (for example, a cured product) obtained through chemical reaction of the liquid crystal aligning agent. it means.
  • the said liquid crystal aligning film uses the liquid crystal aligning agent mentioned above It can be formed through various methods known in the art.
  • step (step 1) which forms the coating film by apply
  • Step 1 is a step of coating the liquid crystal aligning agent on the substrate to form a coating film.
  • the method of applying the liquid crystal aligning agent to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, inkjet, or the like may be used.
  • the liquid crystal aligning agent may be dissolved or dispersed in an organic solvent.
  • organic solvent include ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methyl-2-pyridone, ⁇ -methylcaprolactam, 2-pyridone, and ⁇ -ethylpyri.
  • the liquid crystal aligning agent may further contain other components in addition to the organic solvent. It may include. As a non-limiting example, when the liquid crystal aligning agent is applied, it improves the uniformity and surface smoothness of the film thickness, improves the adhesion between the liquid crystal aligning film and the substrate, or changes the dielectric constant or conductivity of the liquid crystal aligning film, Alternatively, an additive that may increase the compactness of the liquid crystal alignment layer may be further included. Such additives may be exemplified by various solvents, surfactant 1, silane-based compounds, dielectric or crosslinkable compounds.
  • the said step 2 is a step of drying the coating film formed by apply
  • Drying the coating film may be a method such as heating, vacuum evaporation of the coating film, it is preferably carried out at 50 ° C to 150 ° C, or 60 ° C to 140 ° C.
  • Step 3 is a step of performing alignment treatment by irradiating light or rubbing the coating film immediately after the drying step.
  • the "coating film immediately after the drying step” means immediately irradiating the light without proceeding the heat treatment step at a temperature higher than the drying step after the drying step, and other steps other than the heat treatment may be added.
  • the step of irradiating light after performing a high temperature heat treatment essentially for the imidization of the polyamic acid when the liquid crystal aligning film is manufactured by using the liquid crystal aligning agent of the above-described embodiment, the alignment film is not formed by directly irradiating the light without the heat treatment step, and then curing the alignment film by heat-treating the alignment-treated coating film. It can manufacture.
  • the light irradiation in the alignment treatment may be to irradiate polarized ultraviolet rays having a wavelength of 150 ran to 450 ran.
  • the intensity of exposure depends on the type of polymer for the liquid crystal aligning agent, and energy of 10 mJ / cm 2 to 10 J / crf, preferably 30 mJ / ciii 2 to 2 J / cuf, can be irradiated. .
  • a polarizer 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, a polarizing plate on which fine aluminum or metal wire is deposited or
  • An alignment treatment is performed by irradiating polarized ultraviolet rays selected from polarized ultraviolet rays by a method of passing or reflecting through a Brewster polarizer or the like by reflection of quartz glass.
  • the polarized ultraviolet rays may be irradiated perpendicularly to the substrate surface, or may be irradiated at an inclined angle at a specific angle. In this way, 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 with the cloth of rubbing cloth attached to the metal ruler.
  • Step 4 is a step of curing the alignment-treated coating film by heat treatment.
  • the curing of the alignment-treated coating film may be performed after irradiation with light even in a method of manufacturing a liquid crystal alignment film using a polymer for liquid crystal aligning agent including polyamic acid or polyamic acid ester. It is distinguished from the heat treatment step applied to the substrate and carried out to imidize the liquid crystal aligning agent before irradiating light or while irradiating light.
  • the heat treatment may be carried out by a heating means such as a hot plate, hot air circulation furnace, infrared furnace, it is preferable to be carried out at 150 ° C to 300 ° C, or 180 ° C to 250 ° C.
  • a heating means such as a hot plate, hot air circulation furnace, infrared furnace, it is preferable to be carried out at 150 ° C to 300 ° C, or 180 ° C to 250 ° C.
  • the coating film immediately after the drying step may further comprise the step of heat treatment at a temperature above the drying step.
  • the heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and is preferably performed at 150 ° C to 250 ° C.
  • the liquid crystal aligning agent can be imidated.
  • the manufacturing method of the liquid crystal aligning film includes the steps of applying the above-mentioned liquid crystal aligning 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 to a temperature above the drying step (step 3); Irradiating or rubbing the light to the heat-treated coating film (step 4) and curing the heat-treated coating film by heat treatment. Step (step 5).
  • a liquid crystal display device comprising the liquid crystal alignment film described above.
  • the liquid crystal alignment layer may be introduced into the liquid crystal sal by a known method, and the liquid crystal cell may likewise be introduced into the liquid crystal display device by a known method.
  • the liquid crystal alignment layer may be prepared from a polymer including the repeating units of Chemical Formulas 1 to 3 to implement excellent stability with excellent physical properties. Accordingly, a liquid crystal display device capable of exhibiting high reliability is provided.
  • a polymer for a liquid crystal aligning agent excellent in liquid crystal alignment and electrical properties and a method of manufacturing the same can be provided.
  • the diamine of Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that metaphenylenediamine (m-PDA) was used instead of the paraphenylenediamine (p—PDA, Compound 2).
  • m-PDA metaphenylenediamine
  • p—PDA paraphenylenediamine
  • Polymer R-5 was prepared in the same manner as in Synthesis Example 1, except that 4,4'-diaminodiphenylamine [4,4'-diaminodiphenylamine] was used.
  • Polymer R-6 was prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following Formula C was used instead of the diamine prepared in Preparation Example 1.
  • Example 2 19.95 g and 2-butoxyethane were dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-1.
  • Example 2 19.95 g and 2-butoxyethane were dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-1.
  • a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-1.
  • liquid crystal aligning agent polymer (R-6) of Comparative Synthesis Example 6 20 g was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (im / im) of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent R'-6.
  • the ITO electrode having a thickness of 60 nm and an area of 1 cm X 1 cm on a rectangular glass substrate having a size of 2.5 cm X 2.7 cm is spin-coated on each of the upper and lower substrates for the voltage holding ratio (VHR) patterned.
  • the liquid crystal aligning agent obtained by the said Example and the comparative example was apply
  • the substrate to which the liquid crystal aligning agent was applied was placed on a hot plate of about 80 ° C., dried for 2 minutes to evaporate the solvent.
  • the orientation-treated upper and lower plates were baked (cured) for 15 minutes in an Aubon at about 230 ° C. to obtain a coating film having a film thickness of 0.1.
  • a sealing agent impregnated with a 4.5 urn ball spacer was applied to the edges of the upper plate except for the liquid crystal injection hole.
  • the alignment films formed on the upper and lower plates face each other and are aligned so that the alignment directions are parallel to each other.
  • the upper and lower plates are bonded to each other, and an empty cell is prepared by UV and thermal curing the sealing agent.
  • a 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.
  • VHR Voltage holding ratio
  • the polarizing plates were attached to the upper and lower plates of the liquid crystal cell so as to be perpendicular to each other.
  • the liquid crystal cell to which the polarizing plate was attached was attached to a backlight of 7,000 cd / ri, and the luminance of the black state was measured using the PR-880 equipment, which is a luminance brightness measuring instrument. Then, the liquid crystal cell was driven for 24 hours at 5V at room temperature. Then, the brightness of the black state was measured in the same manner as described above with the voltage of the liquid crystal cell turned off.
  • the difference between the initial luminance L0 measured before driving the liquid crystal cell and the later luminance L1 measured after driving was divided by the initial luminance L0 value and multiplied by 100 to calculate the luminance variation rate.
  • the calculated luminance fluctuation rate means that the closer to TO, the better the orientation stability.
  • the afterimage level was evaluated based on the following criteria through the measurement results of the luminance change rate.
  • Luminance variation rate is 10% to 20%
  • the FT-IR spectrum was measured by the ATR method, and the imide structure ratio in the polymer molecule contained was measured.
  • Comparative Example 6 R-6 Formula C PMDA 53 Defect 73
  • the liquid crystal aligning agent of the example included a polymer prepared from a semi-ungmul containing a diamine having an asymmetric structure as in Preparation Examples 1 to 3, It was confirmed that the voltage retention (VHR) was improved to 80% or higher, and that the AC afterimage can be maintained at an equivalent level or higher.
  • VHR voltage retention
  • the luminance variation was measured to be less than 10% with the improvement of the voltage retention (VHR), and it was confirmed that the AC afterimage characteristic was improved very well.
  • liquid crystal aligning agent of the comparative example is prepared in Preparation Example 1 to the reactants in the polymer preparation

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Abstract

The present invention relates to a polymer suitable for use in a liquid crystal aligning agent thanks to excellent liquid crystal alignment and electrical properties thereof, a liquid crystal aligning agent comprising the same, a liquid crystal alignment film formed from the liquid crystal aligning agent, and a liquid crystal display device comprising the liquid crystal alignment film.

Description

【발명의 명칭】  [Name of invention]
액정 배향제용 중합체， 이를 포함하는 액정 배향제， 그리고 이를 이용한 액정배향막 및 액정표시소자 【기술분야】  Polymer for liquid crystal aligning agent, liquid crystal aligning agent comprising the same, and liquid crystal aligning film and liquid crystal display element using same
관련 출원 (들)과의 상호 인용 Cross Citation with Related Application (s)
본 출원은 2017년 5월 22일자 한국 특허 출원 제 10-2017-0063088호 및 2017년 11월 13일자 한국 특허 출원 제 10-2017— 0150898호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0063088 filed May 22, 2017 and Korean Patent Application No. 10-2017-0150898 filed November 13, 2017. All content disclosed in the literature is included as part of this specification.
본 발명은 액정 배향성 및 전기적 특성이 우수하여 액정 배향제에 이용되기에 적합한 중합체, 이를 포함하는 액정 배향제, 상기 액정 배향제로부터 형성된 액정 배향막 및 상기 액정 배향막을 포함하는 액정표시소자에 관한 것이다.  The present invention relates to a polymer suitable for use in a liquid crystal aligning agent having excellent liquid crystal alignment property and electrical properties, a liquid crystal aligning agent comprising the same, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display device comprising the liquid crystal aligning film.
【발명의 배경이 되는 기술】  [Technique to become background of invention]
액정 표시소자에서 균일한 휘도 (br ightness)와 높은 명암비 (contrast rat io)를 얻기 위해서는 액정을 균일하게 배향하는 것이 필수적이다. 액정 배향제는 액정 분자의 배열에 방향자 (director) 역할을 하여 전기장 (electr ic f ield)에 의해 액정이 움직여서 화상을 형성할 때， 적당한 방향을 잡도록 해준다.  In the liquid crystal display device, in order to obtain uniform brightness and high contrast rat io, it is essential to orient the liquid crystal uniformly. The liquid crystal aligning agent 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 appropriate direction when the image is formed.
종래 액정 배향제로는 폴리이미드， 폴리아미드， 또는 폴리에스테르 등이 널리 알려져 있고, 이중에서도 특히 폴리이미드는 내열성, 액정과의 친화성， 기계적 강도 등이 우수하기 때문에 많은 액정표시소자에서 사용되고 있다.  Conventionally, as the liquid crystal aligning agent, polyimide, polyamide, polyester, and the like are widely known. Among them, polyimide is particularly used in many liquid crystal display devices because of its excellent heat resistance, affinity with liquid crystal, mechanical strength, and the like.
그러나， 최근에는 저전력 디스플레이에 대한 요구가 증가함에 따라， 액정배향제는 액정의 배향성이라는 기본 특성뿐 아니라， 직류 /교류전압에 의해 발생하는 잔상, 전압유지율과 같은 전기적인 특성에도 영향을 미칠 수 있음을 발견하게 되었고， 이에 우수한 액정 배향성과 전기적 특성을 동시에 구현할 수 있는 액정 배향재료에 대한 개발의 필요성이 커지고 있다.  However, in recent years, as the demand for low-power displays increases, liquid crystal alignment agents can affect not only the basic characteristics of liquid crystal alignment, but also electrical characteristics such as afterimage and voltage retention caused by DC / AC voltage. It has been found that the need for the development of a liquid crystal alignment material that can simultaneously realize excellent liquid crystal alignment and electrical properties is increasing.
이를 위해 액정배향제 제조에 사용되는 모노머를 변경하거나 서로 다른 복수의 모노머를 조합하는 방법 등을 통해， 액정배향제의 구조 자체를 변경하여， 물리적 /화학적 물성의 개선을 이루려는 다양한 시도가 있었지만, 아직까지 획기적인 물성 개선에 미치지 못하고 있는 실정이다. To this end, the monomers used to prepare the liquid crystal alignment agent may be changed or Although various attempts have been made to improve the physical and chemical properties by changing the structure of the liquid crystal aligning agent through a method of combining a plurality of other monomers, the situation has not yet reached a breakthrough in physical properties.
이에, 우 액정 배향성 및 전기적 특성을 갖는 새로운 액정배향제에 대한 개발이 요구되고 있다. ' Accordingly, there is a demand for development of a new liquid crystal aligning agent having right liquid crystal alignment and electrical characteristics. '
【발명의 내용】  [Content of invention]
【해결하고자 하는 과제】  Problem to be solved
본 발명은 액정 배향성 및 전기적 특성이 우수하여 액정 배향제에 이용되기에 적합한 중합체를 제공하기 위한 것이다.  The present invention is to provide a polymer suitable for use in a liquid crystal aligning agent because of excellent liquid crystal alignment and electrical properties.
또한， 본 발명은 상기 액정 배향제용 중합체를 이용한 액정 배향제，. 액정배향막 및 액정표시소자를 제공하기 위한 것이다. In addition, the present invention liquid crystal aligning agent, with the liquid crystal alignment jeyong polymer. An object of the present invention is to provide a liquid crystal alignment film and a liquid crystal display device.
【과제의 해결 수단】  [Measures of problem]
본 명세서에서는， 하기 화학식 1로 표시되는 반복.단위， 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는， 액정 배향제용 증합체가 제공된다.  In the present specification, a repeater represented by the following Chemical Formula 1. A unit, a repeating unit represented by the following Chemical Formula 2 and a repeating unit selected from the group consisting of a repeating unit represented by the following Chemical Formula 3, a polymerizer for a liquid crystal aligning agent Is provided.
[화학식 1]  [Formula 1]
Figure imgf000003_0001
Figure imgf000003_0001
[화학식 2] [Formula 2]
Figure imgf000003_0002
Figure imgf000003_0002
[화학식 3]
Figure imgf000004_0001
[Formula 3]
Figure imgf000004_0001
상기 화학식 1 내지 3에서， R1 및 R2 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고， 나머지는 수소이며， X1 내지 X3는 각각 독립적으로 4가의 유기기이고， Y1 내지 Y3은 각각 독립적으로 하기 화학식 4로 표시되는 2가의 유기기이고， In Formulas 1 to 3, at least one of R 1 and R 2 is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X 1 to X 3 are each independently a tetravalent organic group, Y 1 to Y 3 is Each independently represent a divalent organic group represented by Formula 4,
[화학식 4]  [Formula 4]
Figure imgf000004_0002
상기 화학식 4에서， A는 15족 원소이고， ¾는 수소， 또는 탄소수 1 내지 10의 알킬기이며, a는 1 내지 3의 정수이고， 내지 Z4 중 적어도 하나는 질소이고, 나머지는 탄소이다.
Figure imgf000004_0002
In Formula 4, A is a group 15 element, ¾ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 1 to 3, at least one of Z 4 is nitrogen, the rest is carbon.
이하 발명의 구체적인 구현예에 따른 액정 배향제용 중합체， 및 이의 제조방법에 대하여 보다 상세하게 설명하기로 한다. 본 명세서에서， 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.  Hereinafter, a polymer for a liquid crystal aligning agent according to a specific embodiment of the present invention, and a manufacturing method thereof will be described in more detail. In the present specification, when a part "contains" a certain component, it means that it may further include other components, without excluding other components, unless specifically stated otherwise.
본 명세서에서， "치환 "이라는 용어는 화합물 내의 수소 원자 대신 다른 작용기가 결합하는 것을 의미하며， 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정되지 않으며， 2 이상 치환되는 경우， 2 이상의 치환기는 서로 동일하거나상이할 수 있다. 본 명세서에서 "치환 또는 비치환된'' 이라는 용어는' 증수소; 할로겐기; 시아노기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 아미노기; 카르복시기; 술폰산기; 술폰아미드기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 시클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 아릴포스핀기; 또는 N, 0 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나， 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대， "2 이상의 치환기가 연결된 치환기 "는 바이페닐기일 수 있다. 즉， 바이페닐기는 아릴기일 수도 있고， 2개의 페닐기가 연결된 치환기로 해석될 수도 있다. In the present specification, the term "substitution" means that another functional group is bonded to the 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 a substituent may be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other. As used herein, the term " substituted or unsubstituted " means ' hydrogen hydrogen; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group ; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, 0 and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "the substituent to which two or more substituents are linked" 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 linked.
본 명세서에서， +， 또는 ᅳ 는 다른 치환기에 연결되는 결합을 의미하고， 직접결합은 L 로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다.  In the present specification, +, or 의미 means a bond connected to another substituent, a direct bond means a case where no separate atom is present in the portion represented by L.
본 명세서에서， 알킬기는 직쇄 또는 분지쇄일 수 있고， 탄소수는 특별히 한정되지 않으나 1 내지 10인 것이 바람직하다. 또 하나의 실시상태에 따르면 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸， 프로필， n-프로필, 이소프로필, 부틸， n-부틸 이소부틸， tert-부틸， sec-부틸， 1-메틸-부틸， 1-에틸-부틸, 펜틸, n-펜틸， 이소펜틸， 네오펜틸, tert-펜틸， 핵실, n-핵실， 1—메틸펜틸， 2-메틸펜틸， 4-메틸 -2-펜틸， 3，3-디메틸부틸， 2—에틸부틸， 헵틸， n-헵틸, 1-메틸핵실， 시클로펜틸메틸， 시클로헥틸메틸， 옥틸, n-옥틸， tert-옥틸, 1_메틸헵틸, 2-에틸핵실， 2-프로필펜틸， n-노닐, 2 , 2-디메틸헵틸， 1-에틸-프로필， 1 , 1- 디메틸-프로필， 이소핵실， 2-메틸펜틸， 4ᅳ메틸핵실，. 5-메틸핵실 등이 있으나， 이들에 、한정되지 않는다.  In the present specification, the alkyl group may be straight or branched chain, 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 include 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, nuclear chamber, n-nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylnuclear, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1_methylheptyl, 2-ethylnuclear, 2-propylpentyl, n-nonyl, 2, 2- Dimethylheptyl, 1-ethyl-propyl, 1, 1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl, 4 ᅳ methylnuclear chamber ,. 5-methyl nucleus, etc., but not limited thereto.
탄소수 1 내지 10의 플루오로알킬기는 상기 탄소수 1 내지 10의 알킬기의 하나 이상의 수소가 불소로 치환된 것일 수 있고， 탄소수 1 내지 10의 플루오로알콕시기는 상기 탄소수 1 내지 10의 알콕시기의 하나 이상의 수소가불소로 치환된 것일 수 있다.  The fluoroalkyl group having 1 to 10 carbon atoms may have one or more hydrogens of the alkyl group having 1 to 10 carbon atoms substituted with fluorine, and the fluoroalkoxy group having 1 to 10 carbon atoms may have at least one hydrogen of the alkoxy group having 1 to 10 carbon atoms. It may be substituted with fluorine.
할로겐 (halogen)은 불소 (F) , 염소 (C1 ) , 브롬 (Br ) 또는 요오드 ( I )일 수 있다.  Halogen may be fluorine (F), chlorine (C1), bromine (Br) or iodine (I).
15족 원소는 질소 (N) , 인 (P) , 비소 (As) , 주석 (Sb) 또는 비스무트 (Bi )일 수 있다. Group 15 elements are nitrogen (N), phosphorus (P), arsenic (As), tin (Sb) or Bismuth (Bi).
질소 산화물은 질소 원자와 산소 원자가 결합한 화합물로서， 질소 산화물 작용기는 작용기 내에 질소 산화물을 포함한 작용기를 의미한다. 상기 질소 산화물 작용기의 예를 들면 , 니트로기 (-N02) 등을 사용할 수 있다. 이에 본 발명자들은 실험을 통해， 질소원자를 함유한 특정 구조의 디아민 화합물을 포함한 반웅물로부터 제조된 상기 화학식 1 내지 3의 반복 단위를 포함하는 액정 배향제용 중합체를 이용하면， 고온에서 높은 전압유지을을 가질 수 있고， 콘트라스트 비율의 저하나 잔상 현상을 개선할 수 있음을 확인하고 발명을 완성하였다. Nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and a nitrogen oxide functional group means a functional group including nitrogen oxide in a functional group. Examples of the oxides of nitrogen functional groups, may be used a nitro group (-N0 2) or the like. Accordingly, the present inventors, through experiments, using a polymer for a liquid crystal aligning agent comprising the repeating units of the above formulas 1 to 3 prepared from the semi-ungmul containing a diamine compound having a specific structure containing a nitrogen atom, to maintain a high voltage at a high temperature The present invention was completed after confirming that it can have a decrease in contrast ratio and an afterimage phenomenon.
구체적으로， 발명의 일 구현예에 따르면 상기 화학식 1로 표시되는 반복 단위 , 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는 액정 배향제용 중합체가 제공될 수 있다.  Specifically, according to one embodiment of the invention liquid crystal comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 Polymers for the alignment agent may be provided.
구체적으로， 일 구현예에 따른 중합체는 상기 화학식 1 내지 3의 반복 단위를 포함한다. 상기 화학식 1 내지 3의 반복 단위에서 X1 내지 X3은 상술한 바와 같이 다양한 4가의 유기기일 수 있고, Y1 내지 Y3은 상술한 바와 같이 다양한 2가의 유기기일 수 있다. Specifically, the polymer according to one embodiment includes the repeating unit of Formula 1 to 3 above. In the repeating units of Chemical Formulas 1 to 3, X 1 to X 3 may be various tetravalent organic groups as described above, and Y 1 to Y 3 may be various divalent organic groups as described above.
상기 Y1 내지 Y3은 상기 화학식 4로 표시되는 2가의 유기기로 정의되어 상술한 효과를 발현할 수 있는 다양한 구조의 액정 배향제용 중합체를 제공할 수 있다. Y 1 to Y 3 may be defined as a divalent organic group represented by Formula 4 to provide a polymer for a liquid crystal aligning agent having a variety of structures that can express the above-described effect.
[화학식 4]  [Formula 4]
Figure imgf000006_0001
상기 화학식 4에서， A는 15족 원소이고， ¾는 수소， 또는 탄소수 1 내지, 10의 알킬기이며， a는 1 내지 3의 정수이고， 1 내지 Ζ4 중 적어도 하나， 즉 하나 이상이 질소이고， 나머지는 탄소이다.
Figure imgf000006_0001
In Formula 4, A is a group 15 element, ¾ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 1 to 3, at least one of 1 to Ζ 4 , that is, at least one is nitrogen, The rest is carbon.
상기 15족 원소는 질소 (Ν) , 인 (Ρ) , 비소 (As) , 주석 (Sb) 또는 비스무트 (Bi )일 수 있다. 상기 R3는 상기 A에 결합하는 작용기로서， a로 표시되는 숫자의 개수만큼 A원소에 결합할 수 있다. 바람직하게는 상기 화학식 4에서， A는 질소이고， ¾은 수소이며， a는 1 일 수 있다. The group 15 element may be nitrogen (Ν), phosphorus (Ρ), arsenic (As), tin (Sb) or bismuth (Bi). R 3 is a functional group bonded to A, wherein The number of displayed numbers can be combined with element A. Preferably, in Formula 4, A is nitrogen, ¾ is hydrogen, a may be 1.
한편， 상기 화학식 4에서， 내지 Ζ4 중 적어도 하나는 질소이고， 나머지는 탄소를 만족함에 따라, 상기 질소원자에 의해 상기 화학식 4는 중심점 또는 중심선을 기준으로 대칭을 이루지 않는 비대칭 구조를 이를 수 있다. 상기 화학식 4는 액정 배향제용 중합체 형성에 사용되는 전구체인 디아민으로부터 유래한 반복단위로서， 후술하는 바와 같이 비대칭 디아민을 사용함에 따른 것으로 보인다. On the other hand, in the general formula (4), to Ζ 4 at least one of which is nitrogen, and the other is along the carbon satisfied, the formula (4) by the nitrogen atom may be this asymmetric structure do not form a symmetric relative to the center point or center line . Formula 4 is a repeating unit derived from diamine which is a precursor used to form a polymer for a liquid crystal aligning agent, and may be due to the use of an asymmetric diamine as described below.
기존에 알려진 액정 배향제용 중합체 분야에서 비대칭 디아민 또는 이로부터 유래한 반복단위에 대한 구성 및 그에 따른 효과를 전혀 인지하지 못하고 있다는 점에서 상기 화학식 4의 반복단위와 이의 전구체인 디아민 화합물은 신규한 것이라고 보인다.  In the known polymer for liquid crystal aligning agent, since the structure and effects thereof are not recognized at all in the asymmetric diamine or the repeating unit derived therefrom, the repeating unit of Formula 4 and the diamine compound as a precursor thereof are novel. .
보다 구체적으로， 상기 화학식 4에서， τγ 내지 ζ4 중 하나가 질소이고 나머지는 탄소일 수 있고， 상기 화학식 4에서， ^ 또는 ¾ 중 하나가 질소이고 나머지는 탄소이며， Ζ2 및 Ζ4 는 탄소일 수 있다. 즉, 상기 화학식 4에서 Λ 내지 Ζ4가 포함된 방향족 고리는 피리딘 (pyr i dine ) 구조를 가질 수 있다. 이에 따라， 상기 일 구현예의 액정 배향제용 중합체가 적용된 액정디스플레이 소자가 높은 전압유지율 및 액정배향성을 구현할 수 있다. More specifically, in Formula 4, one of τ γ to ζ 4 may be nitrogen and the rest may be carbon, in Formula 4, one of ^ or ¾ is nitrogen and the rest is carbon, Ζ 2 and Ζ 4 are Carbon. That is, the ring comprising a Λ Ζ to 4 in the general formula (4) may have a pyridine (pyr dine i) structure. Accordingly, the liquid crystal display device to which the polymer for liquid crystal aligning agent of the above embodiment is applied may implement high voltage retention and liquid crystal alignment.
반면， 2개의 방향족 고리화합물이 2차 아민기 또는 3차 아민기 없이 단일결합으로 결합하는 경우, 액정배향제의 휘도변동를이 증가하여 잔상특성이 불량하고， 전압보유율이 현저히 감소하는 기술적 문제가 발생할 수 있다.  On the other hand, when two aromatic cyclic compounds are combined in a single bond without a secondary amine group or a tertiary amine group, there is a technical problem that the afterimage property is poor due to an increase in the luminance variation of the liquid crystal aligning agent, and the voltage retention is significantly reduced. Can be.
또한， 2차 아민기 또는 3차 아민기를 통해 결합하는 2개의 방향족 고리화합물 각각이 질소원자를 포함하지 않는 경우， 아민과 산무수물의 반웅으로 형성되는 폴리아믹산 또는 폴리아믹산 에스터에 대해 이미드화 반웅을 진행하더라도， (예를들어， 230 °C 열처리를 통해) 층분한 이미드화반웅을 진행하지 못함에 따라， 최종 액정배향막 내에서 이미드화율이 감소하는 한계가 있다.  In addition, when each of the two aromatic cyclic compounds bonded through the secondary amine group or the tertiary amine group does not contain a nitrogen atom, an imidization reaction is applied to the polyamic acid or polyamic acid ester formed by reaction of the amine and the acid anhydride. Even if it proceeds, there is a limit that the imidization rate decreases in the final liquid crystal alignment film as the layered imidization reaction cannot be progressed (for example, through 230 ° C. heat treatment).
또한， 상기 화학식 4로 표시되는 작용기는 2개의 방향족 고리 화합물 바람직하게는 헤테로 방향족 고리 화합물 및 방향족 고리 화합물 각각에 아민기 및 수소만이 결합하고 있을 뿐， 이외의 다른 치환기가 도입되지 않는 것을 특징으로 하며， 헤테로 방향족 고리 화합물 또는 방향족 고리 화합물에 치환기， 예를 들어 플루오로알킬기가 도입될 경우， 휘도변동를이 증가하여 잔상특성이 불량하고， 전압보유율이 현저히 감소하는 기술적 문제가 발생할 수 있다. In addition, the functional group represented by Formula 4 is two aromatic ring compounds Preferably, only the amine group and hydrogen are bonded to each of the heteroaromatic ring compound and the aromatic ring compound, and other substituents are not introduced. Substituents to the heteroaromatic ring compound or the aromatic ring compound, for example, For example, when a fluoroalkyl group is introduced, there is a technical problem that the brightness fluctuation is increased and the afterimage property is poor and the voltage retention rate is significantly reduced.
또한， 상기 화학식 4는 하기 화학식 4-1， 화학식 4-2 및 화학식 4-3으로 이루어진 군에서 선택된 1종 이상의 작용기를 포함할 수 있다.  In addition, Chemical Formula 4 may include one or more functional groups selected from the group consisting of Chemical Formulas 4-1, 4-2, and 4-3.
[화학식 4-1] [Formula 4-1]
Figure imgf000008_0001
Figure imgf000008_0001
상기 화학식 4-1， 화학식 4-2 및 화학식 4-3에 기재된 A , R3 , a , Ζχ , Ζ2 , ， Ζ4 ) 에 대한 내용은 상기 화학식 4에서 상술한 내용을 포함한다. The contents of A, R 3 , a, Ζχ, 2 , and Ζ 4) described in Chemical Formulas 4-1, 4-2, and 4-3 include those described in Chemical Formula 4 above.
이와 같이， 상기 화학식 4 반복단위가 화학식 4-1， 화학식 4-2 및 화학식 4-3으로 이루어진 군에서 선택된 1종 이상의 작용기를 포함함에 따라 보다 우수한 액정 배향성을 구현할 수 있다.  As such, the repeating unit of Formula 4 includes at least one functional group selected from the group consisting of Formulas 4-1, 4-2, and 4-3, thereby achieving better liquid crystal alignment.
한편， 상기 X1 '내지 X3은 각각 독립적으로 하기 화학식 5에 기재된 4가의 유기기를 포함할 수 있다. 즉， 상기 X1 내지 X3은 각각 독립적으로 하기 화학식 5에 기재된 4가의 유기기 중 어느 하나에 해당할 수 있다. On the other hand, X 1 ' to X 3 are each independently represented by the formula (5) It may include a tetravalent organic group. That is, X 1 to X 3 may each independently correspond to any one of the tetravalent organic groups described in the following Formula 5.
[화학식 5]  [Formula 5]
Figure imgf000009_0001
Figure imgf000009_0001
상기 화학식 5에서， 내지 ¾는 각각 독립적으로 수소， 또는 탄소수 1 내지 10의 알킬기이고， L2는 직접 결합, -0-， -CO—, -S- , -S0-, - S02— , -CRioRn-, -C0NH-, -C00- , -(CH2)b-, -0(CH2)b0-, -C00-(CH2)b-0C0-, 페닐렌 또는 이들의 조합으로 이루어진 군에서 선택된 어느 하나이며， R10 및 Ru는 각각 독립적으로 수소， 탄소수 1 내지 10의 알킬기, 또는 탄소수 1 내지 10의 플루오로알킬기이고， b는 1 내지 10의 정수이다. In Formula 5, To ¾ is each independently hydrogen, or an alkyl group having 1 to 10 carbon atoms, L 2 is a direct bond, -0-, -CO—, -S-, -S0-, -S0 2 —,- CRioRn-, -C0NH-, -C00-,-(CH 2 ) b- , -0 (CH 2 ) b 0-, -C00- (CH 2 ) b -0C0-, phenylene or a combination thereof Is any one selected from, R 10 and R u are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, b is an integer of 1 to 10.
보다 바람직하게는 상기 χΐ 내지 X3은 각각 독립적으로 피로멜리틱산 디무수물 (pyromel l i t ic di anhydride, PMDA)로부터 유래한 하기 화학식 5- 1의 유기기; 3，3 '，4，4' -바이페닐테트라카복실산 디무수물 (3，3 '，4，4' - Bi phenyl Tetracarboxyl ic Acid Di anhydr ide, BPDA)로부터 유래한 하기 화학식 5-2의 유기기; 1,2, 4,5-시클로핵산테트라카복실산 디무수물 (1，2，4，5ᅳ Cyclohexanetetracarboxylic Di anhydride, HPMDA)로부터 유래한 하기 화학식 5-3의 유기기; 또는 1，3-디메틸-사이클로부탄 _1，2，3，4- 테트라카복실산 디무수물 (DMCBDA)로부터 유래한 하기 화학식 ' 5-4의 유기기일 수 있다. More preferably, the χ ΐ to X 3 are each independently an organic group represented by the following Chemical Formula 5-1 derived from pyromel lit ic di anhydride (PMDA); The following derived from 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-biphenylphenyltracarboxylic acid dianhydride, BPDA) An organic group of Formula 5-2; An organic group represented by the following Chemical Formula 5-3 derived from 1,2,4,5-cyclotetracarboxylic acid tetraanhydride (1,2,4,5 ′ Cyclohexanetetracarboxylic Dihydride, HPMDA); Or an organic group of formula ' 5-4 ' derived from 1,3-dimethyl-cyclobutane _1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA).
[화학식 5-1]
Figure imgf000010_0001
-2] [Formula 5-1]
Figure imgf000010_0001
-2]
Figure imgf000010_0002
Figure imgf000010_0002
[화학식 5-3]
Figure imgf000010_0003
[Formula 5-3]
Figure imgf000010_0003
[화학식 5-4] [Formula 5-4]
Figure imgf000010_0004
Figure imgf000010_0004
상기 중합체는 상기 화학식 1， 화학식 2 및 화학식 3으로 표시되는 반복 단위 중에서， 이미드 반복 단위인 화학식 1로 표시되는 반복 단위를 전체 반복 단위에 대하여 0몰% 내지 80몰%， 바람직하게는 0.1몰% 내지 65몰% 포함할 수 있다.  The polymer is 0 mol% to 80 mol%, preferably 0.1 mol of the repeating units represented by Formula 1, which is an imide repeating unit, among the repeating units represented by Formulas 1, 2, and 3 % To 65 mol% may be included.
상술한 바와 같이， 상기 화학식 1로 표시되는 이미드 반복 단위를 특정 함량 포함하는 중합체를 이용하면， 상기 중합체가 이미 이미드화된 이미드 반복 단위를 일정 함량 포함하므로， 고온의 열처리 공정을 생략하고， 바로 광을 조사하여도 배향성과 안정성이 우수한 액정 배향막을 제조할 수 있다. As described above, when using a polymer containing a specific content of the imide repeating unit represented by Formula 1, since the polymer contains a predetermined amount of imide repeating units already imidized, a high temperature heat treatment step is omitted, Even if light is irradiated immediately, the liquid crystal aligning film excellent in the orientation and stability can be manufactured.
만일 화학식 1로 표시되는 반복 단위가 상기 함량 범위보다 적게 포함되면 층분한 배향 특성을 나타내지 못하고， 배향 안정성이 저하될 수 있으며， 상기 화학식 1로 표시되는 반복 단위의 함량이 상기 범위를 초과하면 용해도가 낮아져 코팅 가능한 안정적인 배향액을 제조하기 어려운 문제가 나타날 수 있다. 이에 따라， 상기 화학식 1로 표시되는 반복 단위를 상술한 함량 범위로 포함하는 것이 보관 안정성， 전기적 특성, 배향 특성 및 배향 안정성아 모두 우수한 액정 배향제용 중합체를 제공할 수 있어 바람직하다.  If the repeating unit represented by the formula (1) is included less than the content range does not exhibit a sufficient orientation characteristics, the orientation stability may be lowered, and if the content of the repeating unit represented by the formula (1) exceeds the range solubility Problems may appear that are difficult to produce a stable alignment liquid coatable. Accordingly, it is preferable to include the repeating unit represented by the formula (1) in the above-described content range because it can provide a polymer for liquid crystal aligning agent excellent in all of storage stability, electrical properties, orientation characteristics and orientation stability.
또한， 상기 화학식 2로 표시되는 반복 단위 또는 화학식 3으로 표시되는 반복 단위는 목적하는 특성에 따라 적절한 함량으로 포함될 수 있다.  In addition, the repeating unit represented by Formula 2 or the repeating unit represented by Formula 3 may be included in an appropriate content according to the desired properties.
구체적으로, 상기 화학식 2로 표시되는 반복 단위는 상기 화학식 1 내지 3으로 표시되는 전체 반복 단위에 대하여 0몰% 내지 50몰%， 바람직하게는 0. 1몰% 내지 30몰% 포함될 수 있다. 상기 화학식 2으로 표시되는 반복 단위는 광 조사 후 고온 열처리 공정 중 이미드로 전환되는 비율이 낮기 때문에， 상기 범위를 넘어서는 경우 전체적인 이미드화율이 부족하여 배향 안정성이 저하될 수 있다. 따라서， 상기 화학식 2로 표시되는 반복 단위는 상술한 범위 내에서 적절한 용해도를 나타내어 공정 특성이 우수하면서도 높은 이미드화율을 구현할 수 있는 액정 배향제용 중합체를 제공할 수 있다.  Specifically, the repeating unit represented by Chemical Formula 2 may include 0 mol% to 50 mol%, preferably 0.01 mol% to 30 mol% with respect to all the repeating units represented by Chemical Formulas 1 to 3. Since the repeating unit represented by the formula (2) has a low rate of conversion to imide during the high temperature heat treatment process after light irradiation, when it exceeds the above range, the overall imidation ratio may be insufficient and the orientation stability may be lowered. Accordingly, the repeating unit represented by Formula 2 may provide a polymer for a liquid crystal aligning agent that exhibits proper solubility within the above-described range and may realize excellent imidation ratio while having excellent process characteristics.
그리고， 상기 화학식 3으로 표시되는 반복 단위는 상기 화학식 1 내지 3으로 표시되는 전체 반복 단위에 대하여 10몰% 내지 100몰 바람직하게는 30몰% 내지 99.8몰% 포함될 수 있다. 이러한 범위 내에서 우수한 코팅성을 나타내 공정 특성이 우수하면서도 높은 이미드화율을 구현할 수 있는 액정 배향제용 중합체를 제공할 수 있다.  In addition, the repeating unit represented by Chemical Formula 3 may include 10 mol% to 100 mol, preferably 30 mol% to 99.8 mol%, based on the total repeating units represented by Chemical Formulas 1 to 3. It is possible to provide a polymer for a liquid crystal aligning agent that exhibits excellent coating properties within such a range and excellent in process characteristics and can realize a high imidation ratio.
한편， 상기 일 구현예의 액정 배향제용 중합체는 하기 화학식 11로 표시되는 반복 단위， 하기 화학식 12로 표시되는 반복 단위 및 하기 화학식 13으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함할 수 있다. On the other hand, the polymer for a liquid crystal aligning agent of the embodiment is at least one type selected from the group consisting of a repeating unit represented by the following formula 11, a repeating unit represented by the following formula 12 and a repeating unit represented by the following formula It may further include a unit.
[화학식 11]  [Formula 11]
Figure imgf000012_0001
Figure imgf000012_0001
[화학식 12] [Formula 12]
Figure imgf000012_0002
Figure imgf000012_0002
[화학식 13]  [Formula 13]
Figure imgf000012_0003
Figure imgf000012_0003
상기 화학식 11 내지 13에서，  In Chemical Formulas 11 to 13,
R3 및 R4 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고， 나머지는 수소이며, At least one of R 3 and R 4 is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen,
X4내지 X6는 각각 독립적으로 4가의 유기기이고， ,X 4 to X 6 are each independently a tetravalent organic group,
Υ4 내지 Υ6은 각각 독립적으로 하기 화학식 14 로 표시되는 2가의 유기기이고, X 4 to X 6 are each independently a divalent organic group represented by the following formula (14),
[화학식 14]  [Formula 14]
Figure imgf000012_0004
상기 화학식 14에서，
Figure imgf000012_0004
In Chemical Formula 14,
5 및 R6는 각각 독립적으로 수소, 할로겐， 시아노， 알킬， C2-10 알케닐， Cwo 알콕시， d-κ)플루오로알킬， 또는 d-10 플루오로알콕시이고， p 및 q는 각각 독립적으로 0 내지 4의 정수이고, 5 and R 6 are each independently hydrogen, halogen, cyano, alkyl, C 2 - 10 alkenyl, alkoxy, Cwo alkoxy, alkyl, d- or 10-fluoro-κ d) fluoro, p and q are each independently Is an integer of 0 to 4,
L1은 단일결합， -으, -CO- , -S- , -S02- , -C(C¾)2—， — C(CF3)2—， -CONH- ,L 1 is a single bond, -E, -CO-, -S-, -S0 2- , -C (C¾) 2 — ， — C (CF 3 ) 2 — ， -CONH-,
-C00- , -(CH2)Z- , -0(CH2)z0- , -0(CH2)z- , -NH -， -NH(CH2)Z-NH- , -NH(CH2)z0- , -0CH2-C(CH3)2ᅳ CH20- , -C00-(CH2)z-0C0- , 또는 -0C0-(CH2)z— C0()-이며， -C00-,-(CH 2 ) Z- , -0 (CH 2 ) z 0-, -0 (CH 2 ) z- , -NH-, -NH (CH 2 ) Z -NH-, -NH (CH 2 ) z 0-, -0CH 2 -C (CH 3 ) 2 ᅳ CH 2 0-, -C00- (CH 2 ) z -0C0-, or -0C0- (CH 2 ) z —C0 ()-,
z는 1 내지 10의 정수이고，  z is an integer from 1 to 10,
k 및 m은 각각 독립적으로 0 내지 3， 또는 1 내지 3의 정수이고， n은 0 내지 3의 정수이다.  k and m are each independently an integer of 0-3, or 1-3, and n is an integer of 0-3.
상기 화학식 14에서 R5 또는 R6로 치환되지 않은 탄소에는 수소가 결합될 수 있으며， P 및 q는 각각 독립적으로 0 내지 4， 또는. 1 내지 4， 또는 2 내지 4의 정수이고， p 또는 q가 2 내지 4의 정수일 때 복수의 R5 또는 R6는 동일하거나서로 상이한 치환기일 수 있다. Hydrogen may be bonded to carbon which is not substituted with R 5 or R 6 in Formula 14, and P and q are each independently 0 to 4, or. When an integer of 1 to 4, or 2 to 4, and p or q is an integer of 2 to 4, a plurality of R 5 or R 6 may be the same or different substituents.
그리고, 상기 화학식 4에서 k 및 m은 각각 독립적으로 0 내지 3， 또는 1 내지 3의 정수일 수 있고， n은 0 내지 3， 또는 1 내지 3의 정수일 수 있다.  In Formula 4, k and m may be each independently an integer of 0 to 3, or 1 to 3, n may be an integer of 0 to 3, or 1 to 3.
보다 구체적으로， 상기 화학식 14는 하기 화학식 15또는 화학식 16일 수 있다.  More specifically, Formula 14 may be Formula 15 or Formula 16 below.
[화학식 15]  [Formula 15]
Figure imgf000013_0001
상기 화학식 16에서， D는 직접결합, -0-， -S02- 또는 -C(R7) (R8)一 이고， 여기서, R7 및 ¾는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다. 바람직하게는， 상기 화학식 15는 하기 화학식 17일 수 있다. [화학식 17]
Figure imgf000013_0001
In Formula 16, D is a direct bond, -0-, -S0 2 -or -C (R 7 ) (R 8 ) one, wherein R 7 and ¾ are each independently hydrogen, or of 1 to 10 carbon atoms Alkyl group. Preferably, Formula 15 may be the following Formula 17. [Formula 17]
Figure imgf000014_0001
또한， 상기 화학식 16는 하기 화학식 18일 수 있다.
Figure imgf000014_0001
In addition, Chemical Formula 16 may be Chemical Formula 18.
[화학식 18]  [Formula 18]
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000014_0002
Figure imgf000015_0001
상기 화학식 5에서， R9 내지 R14는 각각 독립적으로 수소， 또는 탄소수 1 내지 10의 알킬기이고， L2는 직접 결합， -0-， -CO- , -S- , -S0- , - S02- , -CR15R16_ , -C0NH- , -C00- , -(CH2)b -， -0(CH2)b0- , -C00-(CH2)b-0C0-, 페닐렌 또는 이들의 조합으로 이루어진 군에서 선택된 어느 하나이며， R15 및 R16는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬기， 또는 탄소수 1 내지 10의 플루오로알킬기이고， b는 1 내지 10의 정수이다. In Formula 5, R 9 to R 14 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, L 2 is a direct bond, -0-, -CO-, -S-, -S0-, -S0 2 -, -CR 15 R 16 _, -C0NH-, -C00-,-(CH 2 ) b- , -0 (CH 2 ) b 0-, -C00- (CH 2 ) b -0C0-, phenylene or It is any one selected from the group consisting of these, R <15> and R <16> is respectively independently hydrogen, a C1-C10 alkyl group, or a C1-C10 fluoroalkyl group, b is an integer of 1-10.
이때, 상기 화학식 1로 표시되는 반복 단위， 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위와 상기 화학식 11로 표시되는 반복 단위， 상기 화학식 12로 표시되는 반복 단위 및 상기 화학식 13으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위간의 몰비율은 1 : 100 내지 100 : 1일 수 있다. . 또한， 상기 일 구현예의 액정 배향제용 중합체는 하기 화학식 21로 표시되는 반복 단위, 하기 화학식 22로 표시되는 반복 단위 및 하기 화학식 23으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함할 수 있다.  At this time, the repeating unit represented by the formula (1), at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) and the repeating unit represented by the formula (11), The molar ratio between one or more repeating units selected from the group consisting of a repeating unit represented by 12 and a repeating unit represented by Formula 13 may be 1: 100 to 100: 1. . In addition, the polymer for a liquid crystal aligning agent of the embodiment further comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula 21, a repeating unit represented by the following formula 22 and a repeating unit represented by the following formula 23 can do.
[화학식 21]  [Formula 21]
Figure imgf000015_0002
Figure imgf000015_0002
[화학식 22] [Formula 22]
Figure imgf000016_0001
Figure imgf000016_0001
[화학식 23] [Formula 23]
Figure imgf000016_0002
Figure imgf000016_0002
상기 화학식 21 내지 23에서， R21 및 R22 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고, 나머지는 수소이며， X21 내지 ¾3는 상기 화학식 1 내지 3의 X1내지 X3과 상이하거나， 상기 화학식 11 내지 13의 X4내지 X6과 상이하거나, 상기 화학식 1 내지 3의 X1내지 X3 및 상기 화학식 11 내지 13의 X4 내지 X6과 상이하며 , 각각 독립적으로 상기 화학식 5로 표시되는 4가의 유기기이고， Y21 내지 ¾은 각각 독립적으로 상기 화학식 4로 표시되는 2가의 유기기 또는 상기 화학식 14 로 표시되는 2가의 유기기이다. 상기 액정 배향제용 중합체의 중량평균 분자량이 1000 g/mol 내지 200 , 000 g/nrol일 수 있다. 중량 평균 분자량은 GPC법에 의해 측정한 폴리스티렌 환산의ᅳ 중량 평균 분자량을 의미한다. 상기 GPC법에 의해 측정한 폴리스티렌 환산의 중량 평균 분자량을 측정하는 과정에서는， 통상적으로 알려진 분석 장치와 시차 굴절 검출기 (Refract ive Index Detector ) 등의 검출기 및 분석용 컬럼을 사용할 수 있으며， 통상적으로 적용되는 온도 조건, 용매， f low rate를 적용할 수 있다. 상기 측정 조건의 구체적인 예로， 30 °C의 온도， 클로로포름 용매 (Chloroform) 및 1 mL/min의 f low rate를 들 수 있다. In Formulas 21 to 23, at least one of R 21 and R 22 is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X 21 to ¾ 3 is different from X 1 to X 3 of the formula 1 to 3, Different from X 4 to X 6 of Formulas 11 to 13, or different from X 1 to X 3 of Formulas 1 to 3 and X 4 to X 6 of Formulas 11 to 13, each independently represented by Formula 5 It is a tetravalent organic group to be, Y 21 to ¾ are each independently a divalent organic group represented by the formula (4) or a divalent organic group represented by the formula (14). The weight average molecular weight of the polymer for liquid crystal aligning agent may be 1000 g / mol to 200, 000 g / nrol. A weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, a detector and an analytical column, such as a commonly known analytical device and a differential refractive index detector (Refractive Index Detector), may be used. Temperature conditions, solvents, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C, a chloroform solvent (Chloroform) and f low rate of 1 mL / min.
이러한 중합체는 액정 배향제로 사용되어 우수한 안정성 및 신뢰성을 구현하는 액정 배향막을 제공할 수 있다.  Such a polymer may be used as a liquid crystal aligning agent to provide a liquid crystal alignment layer that realizes excellent stability and reliability.
상기 액정배향제용 중합체를 제조하는 방법의 예가 크게 한정되는 것은 아니며， 예를 들어， 하기 화학식 6의 헤테로 방향족 화합물을 하기 화학식 7의 방향족 화합물과 반응시켜 하기 화학식 8의 화합물을 제조하는 단계; 상기 화학식 8의 화합물을 환원시켜 하기 화학식 9의 디아민을 제조하는 단계; 상기 화학식 9의 디아민을 테트라카복실산 흑은 이의 무수물과 반웅시키는 단계; 및 하기 테트라카복실산 혹은 이의 무수물과의 반웅 결과물을 이미드화하는 단계를 포함하는 액정 배향제용 중합체의 제조 방법을 사용할 수 있다. Examples of the method for producing the polymer for liquid crystal aligning agent are greatly limited For example, the step of preparing a compound of formula 8 by reacting a heteroaromatic compound of formula 6 with an aromatic compound of formula 7; Reducing the compound of Formula 8 to prepare a diamine of Formula 9; Reacting the diamine of Formula 9 with tetracarboxylic acid or its anhydride; And a method for producing a polymer for a liquid crystal aligning agent comprising the step of imidizing a reaction product of the following tetracarboxylic acid or an anhydride thereof.
[화학식 6]
Figure imgf000017_0001
상기 화학식. 6에서， R21은 할로겐 원소이고， R22는 질소 작용기이며， [Formula 6]
Figure imgf000017_0001
The above formula . At 6, R 21 is a halogen element, R 22 is a nitrogen functional group,
Ζι 내지 Z4중 적어도 하나는 질소이고， 나머지는 탄소이고, At least one of Ζι to Z 4 is nitrogen, the rest is carbon,
[ 7] [7]
Figure imgf000017_0002
Figure imgf000017_0002
상기 화학식 7에서， A는 15족 원소이고， R3은 수소， 또는 탄소수 1 내지 10의 알킬기이며, q는 2 내지 4의 정수이고, R23은 아미노기 또는 질소 산화물 작용기이며， In Formula 7, A is a group 15 element, R 3 is hydrogen, an alkyl group having 1 to 10 carbon atoms, q is an integer of 2 to 4, R 23 is an amino group or a nitrogen oxide functional group,
[화학식 8]
Figure imgf000017_0003
[Formula 8]
Figure imgf000017_0003
[화학식 9]
Figure imgf000018_0001
바람직하게는 상기 화학식 6에서， R21은 염소 원소이고， R22는 니트로기이며, [Formula 9]
Figure imgf000018_0001
Preferably, in Chemical Formula 6, R 21 is a chlorine element, R 22 is a nitro group,
또는 ¾ 중 하나는 질소이고， 나머지는 탄소이고，. 및 Z4 는 탄소일 수 있다. 즉， 상기 화학식 6의 바람직한 예로는 2-클로로 -5- 니트로피리딘， 2-클로로 -4-니트로피리딘 등을 들 수 있다. Or wherein one of ¾ is nitrogen, and the others are carbon. And Z 4 may be carbon. That is, preferred examples of the formula (6) include 2-chloro-5-nitropyridine, 2-chloro-4-nitropyridine and the like.
또한 바람직하게는, 상기 화학식 7에서， A는 질소 원소이고, ¾은 수소이며， q는 2이고， R23은 아미노기일 수 있다. 즉， 상기 화학식 7의 바람직한 예로는 파라페닐렌디아민 메타페닐렌디아민 등을 들 수 있다. 구체적으로， 상기 화학식 8의 화합물을 제조하는 단계에서는 상기 화학식 6의 헤테로 방향족 화합물을 상기 화학식 7의 방향족 화합물과 반웅을 통해 상기 화학식 8의 화합물을 제조할 수 있다. 구체적으로 상기 화학식 6의 헤테로 방향족 화합물에 포함된 R21의 할로겐 원소가 화학식 7의 방향족 화합물에 포함된 A의 15족 원소로 치환되는 반웅이 진행될 수 있다. 상기 반웅은 3차아민 촉매에 의해 상온에서 6시간 내지 15시간동안 진행되는 온화한 조건에서 50%이상의 높은 수율로 진행될 수 있다. 상기 반웅은 종래 알려진 다양한 유기 용매 존재하에서 진행될 수 있으며， 상기 유기 용매의 구체적인 예로는 에틸 아세테이트， 테트라하이드로퓨란， Ν , Ν- 디메틸포름아미드， Ν ,Ν-디메틸아세트아미드， Ν-메틸 -2-피를리돈， Ν- 메틸카프로락탐， 2ᅳ피를리돈， Ν-에틸피롤리돈， Ν-비닐피롤리돈， 디메틸술폭사이드， 테트라메틸우레아， 피리딘， 디메틸술폰， 핵사메틸술폭사이드， 부티로락톤， 3-메특시 -Ν, Ν-디메틸프로판아미드， 3- 에록시 -Ν , Ν-디메틸프로판아미드， 3-부톡시—Ν , Νᅳ디메틸프로판아미드， 1 , 3- 디메틸ᅳ이미다졸리디논， 에틸아밀케톤, 메틸노닐케톤， 메틸에틸케톤， 메틸이소아밀케톤， 메틸이소프로필케톤， 사이클로핵사논， 에틸렌카보네이트, 프로필렌카보네이트, 디글라임 또는 4-하이드록시 -4-메틸 -2-펜타논 등을 들 수 있다. 이들은 단독으로 사용될 수도 있고, 흔합하여 사용될 수도 있다. 상기 화학식 6에서， R21은 할로겐 원소이고, R22는 질소 산화물 작용기이며， Zi 내지 Z4 중 적어도 하나는 질소이고， 나머지는 탄소일 수 있다. 보다 구체적으로, 상기 화학식 4에서， 1λ 내지 Ζ4 중 하나가 질소이고， 나머지는 탄소일 수 있고, 상기 화학식 4에서， τγ 또는 ¾ 중 하나가 질소이고 나머지는 탄소이며， ¾ 및 Ζ4 는 탄소일 수 있다. 또한 바람직하게는 상기 화학식 6에서， R21은 염소이고, R22는 니트로기일 수 있다. 상기 화학식 7에세 A는 15족 원소이고, ¾은 수소， 또는 탄소수 1 내지 10의 알킬기이며， q는 2 내지 4의 정수이고, R23은 아미노기 또는 질소 산화물 작용기일 수 있다. 바람직하게는 상기 화학식 7에서， A는 질소이고， R3은 수소， q는 2， R23은 아미노기일 수 있다. Also preferably, in Chemical Formula 7, A is a nitrogen element, ¾ is hydrogen, q is 2, and R 23 may be an amino group. That is, examples of the formula (7) include paraphenylenediamine metaphenylenediamine and the like. Specifically, in the preparing of the compound of Formula 8, the compound of Formula 8 may be prepared by reacting the heteroaromatic compound of Formula 6 with the aromatic compound of Formula 7. Specifically, a reaction in which the halogen element of R 21 included in the heteroaromatic compound of Formula 6 is substituted with a group 15 element of A included in the aromatic compound of Formula 7 may be performed. The reaction can be carried out in a high yield of 50% or more under mild conditions that proceed for 6 to 15 hours at room temperature by the tertiary amine catalyst. The reaction can be carried out in the presence of various conventionally known organic solvents, specific examples of the organic solvents include ethyl acetate, tetrahydrofuran, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2- Pyridone, Ν-methylcaprolactam, 2 ᅳ pyridone, Ν-ethylpyrrolidone, Ν-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, butyrolactone ， 3-Methoxy-Ν, Ν-dimethylpropanamide ， 3-Ethoxy-Ν, Ν-dimethylpropanamide ， 3-Butoxy-Ν, Ν ᅳ dimethylpropanamide ， 1, 3-dimethyl ᅳ imidazolidinone , Ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme or 4-hydroxy-4-methyl 2-pentanone etc. are mentioned. These may be used alone or in combination. In Formula 6, R 21 is a halogen element, R 22 is a nitrogen oxide functional group, at least one of Zi to Z 4 may be nitrogen, the rest may be carbon. More specifically, in Formula 4, one of 1 λ to Ζ 4 may be nitrogen, and the rest may be carbon. In Formula 4, one of τ γ or ¾ is nitrogen and the others are carbon, ¾ and Ζ 4 May be carbon. Also preferably, in Chemical Formula 6, R 21 may be chlorine, and R 22 may be a nitro group. In Formula 7, A is a group 15 element, ¾ is hydrogen or an alkyl group having 1 to 10 carbon atoms, q is an integer of 2 to 4, and R 23 may be an amino group or a nitrogen oxide functional group. Preferably, in Formula 7, A is nitrogen, R 3 is hydrogen, q is 2, R 23 may be an amino group.
상기 질소 산화물 작용기에서 질소 산화물은 질소 원자와 산소 원자가 결합한 화합물로서， 질소 산화물 작용기는 작용기 내에 질소 산화물을 포함한 작용기를 의미한다. 상기 질소 산화물 작용기의 예를 들면 니트로기 (-N02) 등을 사용할 수 있다.  In the nitrogen oxide functional group, nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and the nitrogen oxide functional group means a functional group including nitrogen oxide in the functional group. Examples of the nitrogen oxide functional group can be used nitro group (-N02) and the like.
상기 15족 원소는 질소 (N) , 인 (P) , 비소 (As ) , 주석 (Sb) 또는 비스무트 (Bi )일 수 있다. 상기 ¾는 상기 A에 결합하는 작용기로서， q로 표시되는 숫자의 개수만큼 A원소에 결합할 수 있다  The group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sb) or bismuth (Bi). ¾ is a functional group that binds to A, and may bind to element A as many as the number represented by q.
이렇게 제조된 상기 화학식 8의 화합물은 환원반웅을 통해 화학식 9의 디아민 화합물을 제조할 수 있다. 구체적으로， 상기 화학식 8의 화합물에 포함된 R22의 질소 산화물 작용기가 환원 조건에서 환원되어 1차 아미노기로 환원됨에 따라， 디아민 화합물이 합성될 수 있다. The compound of Formula 8 thus prepared may prepare a diamine compound of Formula 9 through reduction reaction. Specifically, the diamine compound may be synthesized as the nitrogen oxide functional group of R 22 included in the compound of Formula 8 is reduced under reduced conditions to be reduced to a primary amino group.
상기 환원반웅은 팔라듐 /탄소 촉매에 의해 상온에서 10 내지 15시간동안 진행되는 온화한 조건에서 80%이상의 높은 수율로 진행될 수 있다. 상기 반웅은 종래 알려진 다양한 유기 용매 존재하에서 진행될 수 있으며， 상기 유기 용매의 구체적인 예로는 에틸 아세테이트， 테트라하이드로퓨란， Ν , Ν-디메틸포름아미드, Ν , Ν-디메틸아세트아미드, Ν- 메틸 -2-피를리돈， Ν-메틸카프로락탐， 2-피를리돈, Ν-에틸피를리돈， Ν- 비닐피를리돈， 디메틸술폭사이드， 테트라메틸우레아， 피리딘, 디메틸술폰， 핵사메틸술폭사이드, Υ -부티로락톤， 3—메록시 -Ν , Ν-디메틸프로판아미드， 3- 에특시 -Ν , Ν-디메틸프로판아미드， 3-부록시 -Ν , Ν-디메틸프로판아미드， 1 , 3- 디메틸 -이미다졸리디논， 에틸아밀케톤， 메틸노닐케톤， 메틸에틸케톤， 메틸이소아밀케톤， 메틸이소프로필케톤， 사이클로핵사논， ,에틸렌카보네이트 프로필렌카보네이트， 디글라임 또는 4-하이드록시 -4ᅳ메틸 -2-펜타논 등을 들 수 있다. 이들은 단독으로 사용될 수도 있고, 흔합하여 사용될 수도 있다. 상기 화학식 8, 화학식 9에 기재된 A, R3, q, Zi, Z2, Z3 > Z4, R22,The reduction reaction may be carried out in a high yield of 80% or more under mild conditions that proceed for 10 to 15 hours at room temperature by a palladium / carbon catalyst. The reaction may be carried out in the presence of various conventionally known organic solvents, and specific examples of the organic solvent include ethyl acetate, tetrahydrofuran, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2- Pyrlidone, Ν-methylcaprolactam, 2-pyridone, Ν-ethylpyridone, Ν-vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, Υ- Butyrolactone, 3—Methoxy-Ν, Ν-dimethylpropanamide, 3-Especial -Ν, Ν-dimethylpropanamide, 3-Buroxy-Ν, Ν-dimethylpropanamide, 1, 3- Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, cyclonucleanone, ethylene carbonate propylene carbonate, diglyme or 4-hydroxy-4 Methyl-2-pentanone etc. are mentioned. These may be used alone or in combination. A, R 3 , q, Zi, Z 2 , Z 3> Z 4 , R 22 , in Formulas 8 and 9,
¾3에 대한 내용은 상기 화학식 6 및 7에서 상술한 내용을 포함한다. The content of ¾ 3 includes the content described above in Chemical Formulas 6 and 7.
상기 단계들을 통해 제조된 화학식 9의 디아민을 폴리아믹산의 제조에 통상적으로 사용되는 테트라카복실산 혹은 이의 무수물， 예를 들어, 피로멜리틱산 디무수물 (pyromel l ic di anhydride, PMDA) , 3，3 '，4，4'ᅳ 바이페닐테트라카복실산 디무수물 (3，3 ' ,4,4' -Biphenyl Tetracarboxyl ic Acid Di anhydride, BPDA) , 1，2，4，5-시클로핵산테트라카복실산 디무수물( 1，2 , 4，5 01 3] 6^^31 « 1 ^： Di anhydride , HPMDA) , 1 , 3- 디메틸-사이클로부탄 -1，2，3，4-테트라카복실산 디무수물 (DMCBDA) 또는 이들의 2종 이상의 흔합물 등과 반웅시켜 아믹산， 아믹산 에스테르， 또는 이의 혼합물로 이루어진 중합체를 제조할 수 있다.  The diamine of Formula 9 prepared through the above steps may be used for the tetracarboxylic acid or anhydride thereof, for example, pyromel l di anhydride (PMDA), 3,3 ', which is commonly used for preparing polyamic acid. 4,4 'ᅳ Biphenyltetracarboxylic acid dianhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Dihydride, BPDA), 1,2,4,5-cyclonucleic acid tetracarboxylic acid anhydride (1,2 , 4,5 01 3] 6 ^^ 31 «1 ^ ： Di anhydride, HPMDA), 1, 3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) or two of them By reacting with the above mixture and the like, a polymer made of amic acid, amic acid ester, or a mixture thereof can be prepared.
또는 필요에 따라, 상기 단계들을 통해 제조된 화학식 9의 디아민 외에 일반적으로 액정배향제 관련 분야에 널리 알려진 다양한 종류의 디아민 화합물， 예를 들어， Ρ-페닐렌디아민ᅳ 4,4-옥시디아닐린， 4,4' - 메틸렌디아닐린 등을 흔합하여 아믹산， 아믹산 에스테르， 또는 이의 흔합물을 제조할 수 있다.  Or if necessary, in addition to the diamine of the general formula (9) prepared through the above steps, various kinds of diamine compounds well known in the art of liquid crystal aligning agents, for example, Ρ-phenylenediamine ᅳ 4,4-oxydianiline, 4,4'-methylenedianiline etc. can be mixed, and amic acid, amic acid ester, or its mixture can be manufactured.
상기 반웅 조건은 본 발명이 속한 기술분야에 알려진 폴리아믹산의 제조 조건을 참고하여 적절히 조절할 수 있다. 그리고， 얻어진 아믹산， 아믹산 에스테르， 또는 이의 흔합물을 이미드화하여 상술한 화학식 1 내지 3의 반복 단위를 갖는 중합체를 제조할 수 있다. 한편， 발명의 또 다른 구현예에 따르면， 상기 중합체를 포함하는 액정 배향제가 제공된다.  The reaction conditions may be appropriately adjusted with reference to the preparation conditions of the polyamic acid known in the art. Then, the obtained amic acid, amic acid ester, or a mixture thereof can be imidized to prepare a polymer having the above-described repeating units of the formulas (1) to (3). On the other hand, according to another embodiment of the invention, there is provided a liquid crystal aligning agent comprising the polymer.
상기 액정 배향제는 상술한 중합체를 포함함으로 인해, 소성 공정 및 보관 중에 고분자 분해 반웅으로 인한 안정성 및 신뢰성 저하를 효과적으로 억제하며， 뛰어난 코팅성을 나타내고 동시에 우수한 이미드 전환율을 나타낼 수 있다. Since the liquid crystal aligning agent includes the polymer described above, the liquid crystal aligning agent effectively suppresses deterioration in stability and reliability due to polymer degradation reaction during the firing process and storage, and exhibits excellent coating properties and at the same time excellent imide conversion rate. Can be represented.
이러한 액정 배향제는 상술한 중합체를 포함하는 것을 제외하면 본 발명이 속한 기술분야에 알려져 있는 다양한 방법을 통해 제공될 수 있다. 비제한적인 예로， 상술한 중합체를 유기 용매에 용해 또는 분산시켜 액정 배향제를 제공할 수 있다.  Such liquid crystal aligning agent may be provided through various methods known in the art to which the present invention pertains, except for including the polymer described above. As a non-limiting example, the above-described polymer may be dissolved or dispersed in an organic solvent to provide a liquid crystal aligning agent.
상기 유기 용매의 구체적인 예로는 Ν , Ν-디메틸포름아미드， Ν , Ν- 디메틸아세트아미드， Ν-메틸 -2-피롤리돈， Ν-메틸카프로락탐， 2-피를리돈， Ν-에틸피롤리돈， Ν-비닐피를리돈， 디메틸술폭사이드， 테트라메틸우레아， 피리딘， 디메틸술폰， 핵사메틸술폭사이드， 부티로락톤， 3-메록시 -Ν , Ν- 디메틸프로판아미드， 3-에특시 -Ν , Ν-디메틸프로판아미드， 3-부록시 -Ν ,Ν- 디메틸프로판아미드， 1， 3-디메틸 -이미다졸리디논， 에틸아밀케톤, 메틸노닐케톤, 메틸에틸케톤， 메틸이소아밀케톤， 메틸이소프로필케톤， 사이클로핵사논， 에틸렌카보네이트, 프로필렌카보네이트， 디글라임 및 4— 하이드록시 -4-메틸 -2-펜타논 등을 들 수 있다. 이들은 단독으로 사용될 수도 있고， 흔합하여 사용될 수도 있다.  Specific examples of the organic solvent include Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone, Ν-methylcaprolactam, 2-pyridone and Ν-ethylpyrroli Money, Ν-vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, butyrolactone, 3-methoxy-Ν, Ν- dimethylpropanamide, 3-especially-Ν , Ν-dimethylpropanamide, 3-Buroxy-Ν, Ν-dimethylpropanamide, 1, 3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme, and 4—hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.
또한， 상기 액정 배향제는 중합체 및 유기 용매 외에 다른 성분을 추가로 포함할 수 있다. 비제한적인 예로， 액정 배향제가 도포되었을 때， 막 두께의 균일성이나 표면 평활성을 향상시키거나， 흑은 액정 배향막과 기판의 밀착성을 향상시키거나， 혹은 액정 배향막의 유전율이나 도전성을 변화시키거나， 흑은 액정 배향막의 치밀성을 증가시킬 수 있는 첨가제가 추가로 포함될 수 있다. 이러한 첨가제로는 각종 용매， 계면 활성거 I， 실란계 화합물， 유전체 또는 가교성 화합물 등이 예시될 수 있다. 한편， 발명의 또 다른 구현예에 따르면， 상술한 액정 배향제를 포함하는 액정 배향막이 제공된다.  In addition, the liquid crystal aligning agent may further include other components in addition to the polymer and the organic solvent. As a non-limiting example, when a liquid crystal aligning agent is applied, it improves the uniformity and surface smoothness of a film thickness, improves the adhesiveness of a liquid crystal aligning film and a board | substrate, or changes the dielectric constant or electroconductivity of a liquid crystal aligning film, Black may further include an additive that can increase the compactness of the liquid crystal alignment layer. Examples of such additives include various solvents, surfactant I, silane-based compounds, dielectric or crosslinkable compounds, and the like. On the other hand, according to another embodiment of the invention, a liquid crystal aligning film including the liquid crystal aligning agent described above is provided.
상기에서 액정 배향막이 액정 배향제를 포함한다는 것은 액정 배향막이 액정 배향제 그 자체를 포함하거나 흑은 액정 배향막이 액정 배향제의 화학적 반웅을 통해 얻은 생성물 (예를 들어 경화물)을 포함함을 모두 의미한다.  In the above, the fact that the liquid crystal aligning film includes a liquid crystal aligning agent means that the liquid crystal aligning film includes the liquid crystal aligning agent itself or the black liquid crystal aligning film includes a product (for example, a cured product) obtained through chemical reaction of the liquid crystal aligning agent. it means.
상기 액정 배향막은 상술한 액정 배향제를 사용하는 것을 제외하면 본 발명이 속한 기술분야에 알려져 있는 다양한 방법을 통해 형성될 수 있다. Except that the said liquid crystal aligning film uses the liquid crystal aligning agent mentioned above It can be formed through various methods known in the art.
일례로 , 상술한 액정 배향제를 기판에 도포하여 도막을 형성하는 단계 (단계 1) ; 상기 도막을 건조하는 단계 (단계 2) ; 상기 건조 단계 직후의 도막에 광을 조사하거나 러빙 처리하여 배향 처리하는 단계 (단계 3) ; 및 상기 배향 처리된 도막을 열처리하여 경화하는 단계 (단계 4)를 포함하는， 액정 배향막의 제조 방법을사용할수 있다.  For example, the step (step 1) which forms the coating film by apply | coating the liquid crystal aligning agent mentioned above to a board | substrate; Drying the coating film (step 2); Irradiating or rubbing the light onto the coating film immediately after the drying step (step 3); And a step (step 4) of curing the alignment-treated coating film (step 4).
상기 단계 1은， 상술한 액정 배향제를 기판에 도포하여 도막을 형성하는 단계이다.  Step 1 is a step of coating the liquid crystal aligning agent on the substrate to form a coating film.
상기 액정 배향제를 기판에 도포하는 방법은 특별히 제한되지 않으며， 예컨대 스크린 인쇄， 오프셋 인쇄， 플렉소 인쇄， 잉크젯 등의 방법이 이용될 수 있다.  The method of applying the liquid crystal aligning agent to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, inkjet, or the like may be used.
그리고， 상기 액정 배향제는 유기 용매에 용해 또는 분산시킨 것일 수 있다. 상기 유기 용매의 구체적인 예로는 Ν, Ν-디메틸포름아미드， Ν , Ν- 디메틸아세트아미드， Ν-메틸 -2-피를리돈， Ν—메틸카프로락탐, 2-피를리돈， Ν-에틸피를리돈， Νᅳ비닐피를리돈, 디메틸술폭사이드， 테트라메틸우레아, 피리딘, 디메틸술폰， 핵사메틸술폭사이드， Υ -부티로락톤， 3-메특시 -Ν , Ν- 디메틸프로판아미드， 3-에특시 -Ν ,Ν-디메틸프로판아미드， 3-부록시 -Ν ,Ν— 디메틸프로판아미드， 1 , 3-디메틸 -이미다졸리디논, 에틸아밀케톤， 메틸노닐케톤， 메틸에틸케톤 메틸이소아밀케톤， 메틸이소프로필케톤, 사이클로핵사논, 에틸렌카보네이트， 프로필렌카보네이트， 디글라임, 4- 하이드록시 -4-메틸 -2-펜타논， 에틸렌 글리콜 모노메틸 에테르， 에틸렌 글리콜 모노메틸 에테르 아세테이트， 에틸렌 글리콜 모노에틸 에테르， 에틸렌 글리콜 모노에틸 에테르 아세테이트 에틸렌 글리콜 모노프로필 에테르 에틸렌 글리콜 모노프로필 에테르 아세테이트, 에틸렌 글리콜 모노이소프로필 에테르， 에틸렌 글리콜 모노이소프로필 에테르 아세테이트 , 에틸렌 글리콜 모노뷰틸 에테르， 에틸렌 글리콜 모노뷰틸 에테르 아세테이트 등을 들 수 있다. 이들은 단독으로 사용될 수도 있고， 흔합하여 사용될 수도 있다.  The liquid crystal aligning agent may be dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2-pyridone, Ν-methylcaprolactam, 2-pyridone, and Ν-ethylpyri. Lidon, Ν ᅳ vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, Υ-butyrolactone, 3-methoxy-N, Ν-dimethylpropanamide, 3-especial -Ν, Ν-dimethylpropanamide, 3-Buroxy-Ν, Ν- dimethylpropanamide, 1, 3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone methyl iso amyl ketone, Methyl isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether ， Ethylene glycol monoethyl ether acetate ethylene glycol monopropyl ether ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and the like. . These may be used alone or in combination.
또한， 상기 액정 배향제는 유기 용매 외에 다른 성분을 추가로 포함할 수 있다. 비제한적인 예로， 상기 액정 배향제가 도포되었을 때， 막 두께의 균일성이나 표면 평활성을 향상시키거나， 혹은 액정 배향막과 기판의 밀착성을 향상시키거나， 혹은 액정 배향막의 유전율이나 도전성을 변화시키거나， 혹은 액정 배향막의 치밀성을 증가시킬 수 있는 첨가제가 추가로 포함될 수 있다. 이러한 첨가제로는 각종 용매， 계면 활성거 1 , 실란계 화합물， 유전체 또는 가교성 화합물 등이 예시될 수 있다. In addition, the liquid crystal aligning agent may further contain other components in addition to the organic solvent. It may include. As a non-limiting example, when the liquid crystal aligning agent is applied, it improves the uniformity and surface smoothness of the film thickness, improves the adhesion between the liquid crystal aligning film and the substrate, or changes the dielectric constant or conductivity of the liquid crystal aligning film, Alternatively, an additive that may increase the compactness of the liquid crystal alignment layer may be further included. Such additives may be exemplified by various solvents, surfactant 1, silane-based compounds, dielectric or crosslinkable compounds.
상기 단계 2는， 상기 액정 배향제를 기판에 도포하여 형성된 도막을 건조하는 단계이다.  The said step 2 is a step of drying the coating film formed by apply | coating the said liquid crystal aligning agent to a board | substrate.
상기 도막을 건조하는 단계는 도막의 가열, 진공 증발 등의 방법을 이용할 수 있으며 , 50 °C 내지 150 °C , 또는 60 °C 내지 140 °C 에서 수행되는 것이 바람직하다. Drying the coating film may be a method such as heating, vacuum evaporation of the coating film, it is preferably carried out at 50 ° C to 150 ° C, or 60 ° C to 140 ° C.
상기 단계 3은, 상기 건조 단계 직후의 도막에 광을 조사하거나 러빙 처리하여 배향 처리하는 단계이다.  Step 3 is a step of performing alignment treatment by irradiating light or rubbing the coating film immediately after the drying step.
본 명세서에서 상기 "건조 단계 직후의 도막"은 건조 단계 이후에 건조 단계 이상의 온도로 열처리하는 단계의 진행 없이 바로 광 조사하는 것을 의미하며, 열처리 이외의 다른 단계는 부가가 가능하다.  In the present specification, the "coating film immediately after the drying step" means immediately irradiating the light without proceeding the heat treatment step at a temperature higher than the drying step after the drying step, and other steps other than the heat treatment may be added.
보다 구체적으로， 기존에 폴리아믹산 또는 폴리아믹산에스테르를 포함하는 액정 배향제를 사용하여 액정 배향막을 제조하는 경우에는 폴리아믹산의 이미드화를 위하여 필수적으로 고온의 열처리를 진행한 후 광을 조사하는 단계를 포함하지만， 상술한 일 구현예의 액정 배향제를 이용하여 액정 배향막을 제조하는 경우에는 상기 열처리 단계를 포함하지 않고， 바로 광을 조사하여 배향 처리한 후， 배향 처리된 도막을 열처리하여 경화함으로써 배향막을 제조할 수 있다.  More specifically, when manufacturing a liquid crystal aligning film using a liquid crystal aligning agent containing a polyamic acid or a polyamic acid ester, the step of irradiating light after performing a high temperature heat treatment essentially for the imidization of the polyamic acid However, when the liquid crystal aligning film is manufactured by using the liquid crystal aligning agent of the above-described embodiment, the alignment film is not formed by directly irradiating the light without the heat treatment step, and then curing the alignment film by heat-treating the alignment-treated coating film. It can manufacture.
그리고， 상기 배향 처리하는 단계에서 광 조사는 150 ran 내지 450 ran 파장의 편광된 자외선을 조사하는 것일 수 있다. 이 때， 노광의 세기는 액정 배향제용 중합체의 종류에 따라 다르며， 10 mJ/cm2 내지 10 J/crf의 에너지， 바람직하게는 30 mJ/ciii2 내지 2 J/cuf의 에너지를 조사할 수 있다. 상기 자의선으로는， 석영유리， 소다라임 유리， 소다라임프리 유리 등의 투명 기판 표면에 유전이방성의 물질이 코팅된 기판을 이용한 편광 장치， 미세하게 알루미늄 또는 금속 와이어가 증착된 편광판， 또는 석영유리의 반사에 의한 브루스터 편광 장치 등을 통과 또는 반사하는 방법으로 편광 처리된 자외선 중에서 선택된 편광 자외선을 조사하여 배향 처리를 한다. 이때 편광된 자외선은 기판면에 수직으로 조사할 수도 있고， 특정한 각으로 입사각을 경사하여 조사할 수도 있다. 이러한 방법에 의하여 액정분자의 배향 능력이 도막에 부여되게 된다. In addition, the light irradiation in the alignment treatment may be to irradiate polarized ultraviolet rays having a wavelength of 150 ran to 450 ran. In this case, the intensity of exposure depends on the type of polymer for the liquid crystal aligning agent, and energy of 10 mJ / cm 2 to 10 J / crf, preferably 30 mJ / ciii 2 to 2 J / cuf, can be irradiated. . As the self-directed line, a polarizer 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, a polarizing plate on which fine aluminum or metal wire is deposited, or An alignment treatment is performed by irradiating polarized ultraviolet rays selected from polarized ultraviolet rays by a method of passing or reflecting through a Brewster polarizer or the like by reflection of quartz glass. In this case, the polarized ultraviolet rays may be irradiated perpendicularly to the substrate surface, or may be irradiated at an inclined angle at a specific angle. In this way, the alignment ability of the liquid crystal molecules is imparted to the coating film.
또한， 상기 배향 처리하는 단계에서 러빙 처리는 러빙천을 이용하는 방법을 사용할 수 있다. 보다 구체적으로， 상기 러방 처리는 금속 를러에 러빙천의 옷감을 붙인 러빙 를러를 회전시키면서 열처리 단계 이후의 도막의 표면을 한 방향으로 러빙할 수 있다.  In addition, 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 with the cloth of rubbing cloth attached to the metal ruler.
상기 단계 4는， 상기 배향 처리된 도막을 열처리하여 경화하는 단계이다.  Step 4 is a step of curing the alignment-treated coating film by heat treatment.
상기 배향 처리된 도막을 열처리하여 경화하는 단계는 기존에 폴리아믹산 또는 폴리아믹산 에스테르를 포함하는 액정 배향제용 중합체를 이용하여 액정 배향막을 제조하는 방법에서도 광 조사 이후에 실시하는 단계로， 액정 배향제를 기판에 도포하고, 광을 조사하기 이전에, 또는 광을 조사하면서 액정 배향제를 이미드화 시키기 위하여 실시하는 열처리 단계와는 구분된다.  The curing of the alignment-treated coating film may be performed after irradiation with light even in a method of manufacturing a liquid crystal alignment film using a polymer for liquid crystal aligning agent including polyamic acid or polyamic acid ester. It is distinguished from the heat treatment step applied to the substrate and carried out to imidize the liquid crystal aligning agent before irradiating light or while irradiating light.
이때， 상기 열처리는 핫 플레이트， 열풍 순환로， 적외선로 등의 가열 수단에 의해 실시될 수 있으며， 150 °C 내지 300 °C , 또는 180 °C 내지 250 °C에서 수행되는 것이 바람직하다. At this time, the heat treatment may be carried out by a heating means such as a hot plate, hot air circulation furnace, infrared furnace, it is preferable to be carried out at 150 ° C to 300 ° C, or 180 ° C to 250 ° C.
한편， 상기 도막을 건조하는 단계 (단계 2) 이후에 필요에 따라, 상기 건조 단계 직후의 도막에 건조 단계 이상의 온도로 열처리하는 단계를 더 포함할 수 있다. 상기 열처리는 핫 플레이트， 열풍 순환로， 적외선로 등의 가열 수단에 의해 실시될 수 있으며， 150 °C 내지 250 °C에서 수행되는 것이 바람직하다. 이 과정에서 액정 배향제를 이미드화 시킬 수 있다. On the other hand, after the step of drying the coating film (step 2), if necessary, the coating film immediately after the drying step may further comprise the step of heat treatment at a temperature above the drying step. The heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and is preferably performed at 150 ° C to 250 ° C. In this process, the liquid crystal aligning agent can be imidated.
즉， 상기 액정 배향막의 제조 방법은 상술한 액정 배향제를 기판에 도포하여 도막을 형성하는 단계 (단계 1) ; 상기 도막을 건조하는 단계 (단계 2)； 상기 건조 단계 직후의 도막에 건조 단계 이상의 온도로 열처리하는 단계 (단계 3) ; 상기 열처리된 도막에 광을 조사하거나 러빙 처리하여 배향 처리하는 단계 (단계 4) 및 상기 배향 처리된 도막을 열처리하여 경화하는 단계 (단계 5)를 포함할 수 있다. 한편， 발명의 또 다른 구현예에 따르면， 상술한 액정 배향막을 포함하는 액정표시소자가 제공된다. That is, the manufacturing method of the liquid crystal aligning film includes the steps of applying the above-mentioned liquid crystal aligning 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 to a temperature above the drying step (step 3); Irradiating or rubbing the light to the heat-treated coating film (step 4) and curing the heat-treated coating film by heat treatment. Step (step 5). On the other hand, according to another embodiment of the invention, there is provided a liquid crystal display device comprising the liquid crystal alignment film described above.
상기 액정 배향막은 공지의 방법에 의해 액정 샐에 도입될 수 있으며， 상기 액정 셀은 마찬가지로 공지의 방법에 의해 액정표시소자에 도입될 수 있다. 상기 액정 배향막은 상기 화학식 1 내지 3의 반복 단위를 포함하는 중합체로부터 제조되어 우수한 제반 물성과 함께 뛰어난 안정성을 구현할 수 있다. 이에 따라， 높은 신뢰도를 나타낼 수 있는 액정표시소자를 제공하게 된다.  The liquid crystal alignment layer may be introduced into the liquid crystal sal by a known method, and the liquid crystal cell may likewise be introduced into the liquid crystal display device by a known method. The liquid crystal alignment layer may be prepared from a polymer including the repeating units of Chemical Formulas 1 to 3 to implement excellent stability with excellent physical properties. Accordingly, a liquid crystal display device capable of exhibiting high reliability is provided.
[발명의 효과]  [Effects of the Invention]
본 발명에 따르면， 액정 배향성 및 전기적 특성이 우수한 액정 배향제용 중합체， 및 이의 제조방법이 제공될 수 있다.  According to the present invention, a polymer for a liquid crystal aligning agent excellent in liquid crystal alignment and electrical properties, and a method of manufacturing the same can be provided.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐， 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다.  The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples.
<제조예 1 내지 3: 디아민의 제조: Preparation Examples 1 to 3: Preparation of Diamine:
제조예 1
Figure imgf000025_0001
Preparation Example 1
Figure imgf000025_0001
18.3g( 100隱 ol )의 2-클로로 -5-니트로피리딘 (2_chloro-5- ni tropyr idine , 화합물 1)， 12.5g(98.6mmol )의 파라페닐렌디아민 (p_PDA, 화합물 2)를 200mL의 디메틸술폭사이드 (Dimethyl sul foxide , DMS0)에 완전히 녹인 후， 23.4g(200匪 ol )의 트리에틸아민 (tr imethylamine , TEA)을 첨가하고 상온에서 12시간동안 교반하였다. 반웅이 종결되면 반웅물을 500mL의 물이 담긴 용기에 투입하고 1시간동안 교반하였다. 이를 여과하여 얻은 고체를 200mL의 물과 200mL의 에탄올로 세척하여 16g(61.3隱 ol )의 화합물 3을 합성하 :60%)
Figure imgf000026_0001
18.3 g (100 μl ol) of 2-chloro-5-nitropyridine (Compound 1), 12.5 g (98.6 mmol) of paraphenylenediamine (p_PDA, Compound 2) were added to 200 mL of dimethyl. After completely dissolved in sulfoxide (Dimethyl sul foxide, DMS0), 23.4 g (200 μl) of triethylamine (tr imethylamine, TEA) was added and stirred at room temperature for 12 hours. When the reaction was finished, the reaction product was added to a vessel containing 500 mL of water and stirred for 1 hour. The solid obtained by filtration was washed with 200 mL of water and 200 mL of ethanol to obtain 16 g (61.3 隱 ol) of Compound 3. 60%)
Figure imgf000026_0001
상기 화합물 3을 에틸아세테이트 (ethyl acetate , EA)와 THF를 1 : 1로 흔합한 200mL 용액에 녹인 후, 0.8g의 팔라듐 (Pd)/탄소 (C)를 투입하고 수소 환경하에서 12시간 동안 교반하였다. 반웅 종료 후 셀라이트 패트에 여과한 여액을 농축하여 llg의 화합물 4 디아민을 제조하였다. (수율 : 89%) 제조예 2  Compound 3 was dissolved in 200 mL solution of ethyl acetate (EA) and THF 1: 1, and 0.8 g of palladium (Pd) / carbon (C) was added thereto, followed by stirring for 12 hours in a hydrogen environment. . After completion of reaction, the filtrate was concentrated in a celite pad to prepare llg compound 4 diamine. (Yield: 89%) Preparation Example 2
Figure imgf000026_0002
Figure imgf000026_0002
상기 파라페닐렌디아민 (p— PDA， 화합물 2) 대신에 메타페닐렌디아민 (m- PDA)을 사용한 것을 제외하고는 상기 제조예 1과 동일한 방법으로 제조예 2의 디아민을 제조하였다.  The diamine of Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that metaphenylenediamine (m-PDA) was used instead of the paraphenylenediamine (p—PDA, Compound 2).
Figure imgf000026_0003
상기 2-클로로 -5-니트로피리딘 (2-chloro-5-nitropyridine, 화합물 1) 대신에 2-클로로 -4-니트로피리딘 (2-chloro-4-nitropyridine)을 사용한 것을 제외하고는 상기 제조예 1과 동일한 방법으로 제조예 3의 디아민을 제조하였다.
Figure imgf000026_0003
Preparation Example 1 except that 2-chloro-4-nitropyridine was used instead of 2-chloro-5-nitropyridine (Compound 1). In the same manner as in the diamine of Preparation Example 3 was prepared.
<합성예 및 비교합성예: 액정배향제용 중합체의 합성 > Synthesis Example and Comparative Synthesis Example: Synthesis of Polymer for Liquid Crystal Alignment
합성예 1 ： 액정배향용 중합체 P-1  Synthesis Example 1 Polymer P-1 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 19.743 g(0.099隱 ol)을 무수 N- 메틸피롤리돈 (anhydrous N-methyl pyrrol i done: NMP) 225.213 g에 완전히 녹였다.  19.743 g (0.099 μl) of diamine prepared in Preparation Example 1 was completely dissolved in 225.213 g of anhydrous N-methyl pyrrolidone (NMP).
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel 1 it ic di anhydride, PMDA) 20. Og (0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-1을 제조하였다. GPC를 통해 상기 중합체 P-1의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 27,000g/ii )l이었다. 합성예 2 ： 액정배향용 중합체 P-2  Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-1 for liquid crystal alignment. It was. As a result of confirming the molecular weight of the polymer P-1 through GPC, the weight average molecular weight (Mw) was 27,000 g / ii) l. Synthesis Example 2 Polymer P-2 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 14.637 g (0.073隱 ol) 을 무수 N- 메틸피를리돈 (anhydrous N-methyl pyrrol idone: NMP) 225.213 g에 완전히 녹였다.  14.637 g (0.073 μl) of diamine prepared in Preparation Example 1 was completely dissolved in 225.213 g of anhydrous N-methyl pyrrol idone (NMP).
그리고, ice bath 하에서 3，3'，4，4'-바이페닐테트라카복실산 디무수물 (3，3' ,4,4'-Biphenyl Tetracarboxyl ic Acid Di anhydride, BPDA) 20. Og (0.068 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-2을 제조하였다. GPC를 통해 상기 중합체 P-2의 분자량을 확인한 결과， 중량평균분자량 Ok)이 24,000g/m 이었다. 합성예 3 ： 액정배향용 중합체 P-3  And 20, Og (0.068 隱 ol) was added to 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Di anhydride, BPDA) in an ice bath. It was added to the solution and stirred for 16 hours at room temperature to prepare a liquid crystal alignment polymer P-2. As a result of confirming the molecular weight of the polymer P-2 through GPC, the weight average molecular weight Ok) was 24,000 g / m. Synthesis Example 3 Polymer P-3 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 19.211 g (0.096隱 ol) 을 무수 N- 메틸피롤리돈 (anhydrous N-methyl pyrrol idone: NMP) 222.194 g 에 완전히 녹였다. 19.211 g (0.096 隱 ol) of diamine prepared in Preparation Example 1 was completely added to 222.194 g of anhydrous N-methyl pyrrol idone (NMP). Melted.
그리고， ice bath 하에서 1,2,4,5-시클로핵산테트라카복실산 디무수물 (l,2,4,5-Cyclohexanetetracarboxylic Di anhydride, HPMDA) 20. Og (0.089 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-3을 제조하였다. GPC를 통해 상기 중합체 P-3의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 26,500g/mol이었다. 합성예 4 ： 액정배향용 중합체 P-4  Then, 20, Og (0.089 隱 ol) was added to the solution at room temperature in an ice bath to add 1,2,4,5-cyclotetracarboxylic acid anhydride (l, 2,4,5-Cyclohexanetetracarboxylic dianhydride, HPMDA). Stirred for 16 hours to prepare a polymer P-3 for liquid crystal alignment. When the molecular weight of the polymer P-3 was confirmed through GPC, the weight average molecular weight (Mw) was 26,500 g / mol. Synthesis Example 4 Polymer P-4 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 1.974 g (0.01 匪 ol), p- 페닐렌디아민 (p-phenylenediamine, p-PDA) 9.596 g(0.089 匪 ol)을 무수 N- 메틸 피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 178.897g에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine prepared in Preparation Example 1 and 9.596 g (0.089 μl ol) of p-phenylenediamine (p-PDA) were dried using anhydrous N-methyl pyridone (anhydrous N-methyl). pyrrol i done: NMP) completely dissolved in 178.897g.
그리고, ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20.0g(0.092 mmol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-4을 제조하였다. GPC를 통해 상기 중합체 P-4의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 24,500g/irol이었다. 합성예 5 ： 액정배향용 중합체 P-5  Then, 20.0 g (0.092 mmol) of pyromellitic di anhydride (PMDA) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-4 for liquid crystal alignment. When the molecular weight of the polymer P-4 was confirmed through GPC, the weight average molecular weight (Mw) was 24,500 g / irol. Synthesis Example 5 Polymer P-5 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 9.872 g (0.049 誦 ol) p- 페닐렌디아민 (p-phenylenedi amine, p-PDA) 5.331 g (0.049 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 199.482g 에 완전히 녹였다. Diamine 9.8 7 2 g (0.049 誦 ol) p-phenylenediamine (p-phenylenediamine (p-PDA) 5.331 g (0.049 隱 ol) prepared in Preparation Example 1 was added with anhydrous N-methylpyridone (anhydrous N -Methyl pyrrol i done: NMP) was completely dissolved in 199.482g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel lit ic di anhydride, PMDA) 20.0g(0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P— 5를 제조하였다. GPC를 통해 상기 중합체 P-5의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 27,500g/iMl이었다. 합성예 6 ： 액정배향용 중합체 P-6 상기 제조예 1에서 제조된 디아민 1.974 g (0.01 隱 ol), 4,4- 옥시디아닐린 (4,4'-oxydiani line, ODA) 17.768 g(0.089 隱 ol)을 무수 N_ 메틸피를리돈 (anhydrous N-methyl pyrrol idone: NMP) 225.208g 에 완전히 녹였다. Then, 20.0 g (0.092 隱 ol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer P-5 for liquid crystal orientation. When the molecular weight of the polymer P-5 was confirmed through GPC, the weight average molecular weight (Mw) was 27,500 g / iMl. Synthesis Example 6 Polymer P-6 for Liquid Crystal Alignment 1.974 g (0.01 μl ol) of diamine prepared in Preparation Example 1 and 17.768 g (0.089 μl ol) of 4,4-oxydianiline (4,4 -′- oxydiani line (ODA)) were dissolved in anhydrous N_methylpyrrolidone (anhydrous). N-methyl pyrrol idone: NMP) was completely dissolved in 225.208 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20. Og (0.092 國 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-6을 제조하였다. GPC를 통해 상기 중합체 P-6의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 28,500g/nK)l이었다. 합성예 7 ： 액정배향용 중합체 P-7  Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 國 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-6 for liquid crystal orientation. The molecular weight of the polymer P-6 was confirmed by GPC. As a result, the weight average molecular weight (Mw) was 28,500 g / nK) l. Synthesis Example 7 Polymer P-7 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 9.872g (0.049 mmol) 4,4'- 옥시디아닐린 (4， 4 '—oxydi aniline, ODA) 9.871 g (0.049 隱 ol)을 무수 N- 메틸피롤리돈 (anhydrous N-methyl pyrrol idone: 匪 P) 225.21g 에 완전히 녹였다.  9.872 g (0.049 mmol) of diamine 4,4′-oxydianiline (4,4′-oxydi aniline, ODA) prepared in Preparation Example 1 was added 9.871 g (0.049 μl ol) of anhydrous N-methylpyrrolidone (anhydrous). N-methyl pyrrol idone: 匪 P) was completely dissolved in 225.21 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20. Og (0.092 隱 ol)을 상기 용액에 첨가하여 상은에서 16 시간 동안 교반하여 액정배향용 중합체 P-7 제조하였다. GPC를 통해 상기 중합체 P— 7 의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 27,000g/n )l이었다. 합성예 8 ： 액정배향용 중합체 P-8  Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred for 16 hours in phase silver to prepare Polymer P-7 for liquid crystal orientation. The molecular weight of the polymer P-7 was confirmed by GPC, and a weight average molecular weight (Mw) was 27,000 g / n) l. Synthesis Example 8 Polymer P-8 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 1.974 g (0.01 匪 ol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 17.593 g(0.089 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol idone: 匪 P) 224.218g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine, 4,4′-methylenedianiline (MDA) prepared in Preparation Example 1, 17.593 g (0.089 μl ol) was dissolved in anhydrous N-methylpyridone ( anhydrous N-methyl pyrrol idone: 匪 P) completely dissolved in 224.218 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20. Og (0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-8을 제조하였다. GPC를 통해 상기 중합체 P-8의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 29,500g/tix)l이었다. 합성예 9 ： 액정배향용 중합체 P-9 Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer P-8 for liquid crystal orientation. As a result of confirming the molecular weight of the polymer P-8 through GPC, the weight average molecular weight (Mw) is 29,500 g / tix) l. Synthesis Example 9 Polymer P-9 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 9.872 g (0.049 匪 ol) 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 9.774 g (0.049 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 224.66g 에 완전히 녹였다.  9.872 g (0.049 μl ol) of diamine prepared in Preparation Example 1, 4.774 g (0.049 μl ol) of 4,4′-Methylenedianiline (MDA) was added to anhydrous N-methylpyridone (anhydrous). N-methyl pyrrol i done: NMP) was completely dissolved in 224.66 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20. Og (0.092 瞧 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-9를 제조하였다. GPC를 통해 상기 중합체 P— 9의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 28,000g/n)l이었다. 합성예 10 ： 액정배향용 중합체 P-10  Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 瞧 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-9 for liquid crystal orientation. The molecular weight of the polymer P-9 was confirmed by GPC, and the weight average molecular weight (Mw) was 28,000 g / n) l. Synthesis Example 10 ： Polymer P-10 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 1.464 g (0.007 腿 ol), p- 페닐렌디아민 (p-phenylenediamine, p-PDA) 7.114 g(0.066 瞧 ol)을 무수 N- 메틸 피를리돈 (anhydrous N-methyl pyrrolidone: NMP)161.939g에 완전히 녹였다.  1.464 g (0.007 μl ol) of diamine prepared in Preparation Example 1 and 7.114 g (0.066 μl ol) of p-phenylenediamine (p-PDA) were anhydrous N-methyl pyridone (anhydrous N-methyl). It was completely dissolved in 161.939 g of pyrrolidone: NMP).
그리고， ice bath 하에서 3，3'，4，4'-바이페닐테트라카복실산 디무수물 (3,3' ,4,4'-Biphenyl Tetracarboxylic Acid Di anhydride, BPDA) 20. Og (0.068 隱 ol)을 상기 용'액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-10을 제조하였다. GPC를 통해 상기 중합체 P-10의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 27,500g/ii l이었다.  And 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Dihydride, BPDA) 20.Og (0.068 隱 ol) It was added to the solution 'and stirred for 16 hours at room temperature to prepare a liquid crystal alignment polymer P-10. The molecular weight of the polymer P-10 was confirmed by GPC. The weight average molecular weight (Mw) was 27,500 g / ii l.
합성예 11 ： 액정배향용 중합체 P-11 상기 제조예 1에서 제조된 디아민 1.464 g (0.007 醒 ol), 4,4'- 옥시디아닐린 (4,4 '—oxydi aniline, 0DA) 13.172 g(0.066 瞧 ol)을 무수 N- 메틸피롤리돈 (anhydrous N-methyl pyrrolidone: NMP) 196.272g 에 완전히 녹였다.  Synthesis Example 11 Polymer for Liquid Crystal Alignment P-11 1.464 g (0.007 醒 ol) of diamine prepared in Preparation Example 1, 4,4′-oxydianiline (4,4′—oxydi aniline, 0DA) 13.172 g (0.066) Xol) was completely dissolved in 196.272 g of anhydrous N-methylpyrrolidone (NMP).
그리고， ice bath 하에서 3，3'，4，4'-바이페닐테트라카복실산 디무수물 (3，3'，4，4'— Biphenyl Tetracarboxyl ic Acid Di anhydride, BPDA) 20. Og (0.068 醒 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-11을 제조하였다. GPC를 통해 상기 중합체 P-11의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 25,500g/mol이었다. 합성예 12 ： 액정배향용 중합체 P-12 And 3, 3 ', 4, 4'-biphenyltetracarboxylic acid under ice bath Dianhydride (3, 3 ', 4, 4'—Biphenyl Tetracarboxylic Acid Dihydride, BPDA) 20. Og (0.068 醒 ol) was added to the solution and stirred for 16 hours at room temperature to give a liquid crystal alignment polymer P-11. Was prepared. When the molecular weight of the polymer P-11 was confirmed through GPC, the weight average molecular weight (Mw) was 25,500 g / mol. Synthesis Example 12 ： Polymer P-12 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 1.464 g (0.007 隱 ol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 13.043 g(0.066 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol i done: MP) 195.537g 에 완전히 녹였다.  1.464 g (0.007 μl ol) of diamine and 4,4′-methylenedianiline (MDA) 13.043 g (0.066 μl ol) prepared in Preparation Example 1 were added with anhydrous N-methylpyridone ( anhydrous N-methyl pyrrol i done: MP) completely dissolved in 195.537g.
그리고， ice bath 하에서 3,3'，4，4'-바이페닐테트라카복실산 디무수물 (3，3' ,4,4'-Biphenyl Tetracarboxyl ic Acid Di anhydride, BPDA) 20. Og (0.068 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-12을 제조하였다. GPC를 통해 상기 중합체 P-12의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 27,000g/nrol이었다. 합성예 13 ： 액정배향용 중합체 P-13  And 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Di anhydride, BPDA) 20.Og (0.068 隱 ol) It was added to the solution and stirred for 16 hours at room temperature to prepare a liquid crystal alignment polymer P-12. The molecular weight of the polymer P-12 was confirmed by GPC, and the weight average molecular weight (Mw) was 27,000 g / nrol. Synthesis Example 13 Polymer P-13 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 匪 ol), p- 페닐렌디아민 (p—phenylenedi amine, p-PDA) 9.337 g (0.086隱01)을 무수 N- 메틸 피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 177.128g에 완전히 녹였다.  1.921 g (0.01 匪 ol) of diamine prepared in Preparation Example 1 and 9.337 g (0.086 隱 01) of p-phenylenediamine (p-phenylenedi amine, p-PDA) were added to anhydrous N-methyl pyridone (anhydrous N- methyl pyrrol i done: NMP) completely dissolved in 177.128g.
그리고， ice bath 하에서 1，2，4,5—시클로핵산테트라카복실산 디무수물 (l,2,4,5-Cyclohexanetetracarboxylic Di anhydride, HPMDA) 20. Og (0.089 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-13을 제조하였다. GPC를 통해 상기 중합체 P-13의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 23,500g/m이이었다. 합성예 14 ： 액정배향용 중합체 P-14  Then, 20, Og (0.089 隱 ol) was added to the solution at room temperature under l, 2,4,5—cyclohexanetetracarboxylic acid anhydride (HPMDA) under an ice bath. Stirring for 16 hours to prepare a polymer P-13 for liquid crystal alignment. When the molecular weight of the polymer P-13 was confirmed through GPC, the weight average molecular weight (Mw) was 23,500 g / m. Synthesis Example 14 Polymer P-14 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 隱 ol), 4,4' - 옥시디아닐린 (4,4 '-oxydiani line, ODA) 17.289 g (0.086 隱 ol)을 무수 N- 메틸피를리돈 (anhydrous N-methyl pyrrolidone: NMP) 222.189g 에 완전히 녹였다. 1.921 g (0.01 μl ol) of diamine prepared in Preparation Example 1, 4,4 ′ 17.289 g (0.086 隱 ol) of oxydianiline (4,4'-oxydiani line, ODA) was completely dissolved in 222.189 g of anhydrous N-methyl pyrrolidone (NMP).
그리고， ice bath 하에서 1ᅳ2，4，5-시클로핵산테트라카복실산 디무수물 (l,2,4,5-Cyclohexanetetracarboxylic Di anhydride, HPMDA) 20. Og (0.089 瞧 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-14을 제조하였다. GPC를 통해 상기 중합체 P-14의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 26,500g/m 이었다. 합성예 15 ： 액정배향용 중합체 P-15 Then, 1,2,4,5-cyclotetracarboxylic acid anhydride (l, 2,4,5-Cyclohexanetetracarboxylic Di anhydride, HPMDA) is added to the solution at room temperature under an ice bath. Stirring for 16 hours to prepare a polymer P-14 for liquid crystal alignment. As a result of confirming the molecular weight of the polymer P-14 through GPC, the weight average molecular weight (Mw) was 26,500 g / m. Synthesis Example 15 Polymer P-15 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 mmol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 17.119 g (0.086 隱 ol)을 무수 N-메틸 괴롤리돈 (anhydrous N-methyl pyrrolidone: NMP) 177.128g 에 완전히 녹였다.  1.921 g (0.01 mmol) of diamine prepared in Preparation Example 1, and 17.119 g (0.086 mmol) of 4,4'-methylenedianiline (MDA) were dissolved in anhydrous N-methyl gorrolidone (anhydrous). N-methyl pyrrolidone: NMP) was completely dissolved in 177.128 g.
그리고， ice bath 하에서 1,2，4，5-시클로핵산테트라카복실산 디무수물 (l,2,4,5-Cyclohexanetetracarboxylic Di anhydride, HPMDA) 20. Og (0.089 瞧 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-15을 제조하였다. GPC를 통해 상기 중합체 P-15의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 25,000g/m 이었다. 합성예 16 ： 액정배향용 중합체 P-16  Then, 1,2,4,5-cyclotetracarboxylic acid anhydride (l, 2,4,5-Cyclohexanetetracarboxylic Dihydride, HPMDA) 20.Og (0.089 瞧 ol) was added to the solution at room temperature in an ice bath. Stirring for 16 hours to prepare a polymer P-15 for liquid crystal alignment. The molecular weight of the polymer P-15 was confirmed by GPC. As a result, the weight average molecular weight (Mw) was 25,000 g / m. Synthesis Example 16 Polymer P-16 for liquid crystal alignment
상기 제조예 2에서 제조된 디아민 1.974 g (0.01 隱 ol), p- 페닐렌디아민 (p-phenylenedi amine, p-PDA) 9.596 g(0.089 讓 ol)을 무수 N- 메틸 피롤리돈 (anhydrous N-methyl pyrrolidone: NMP) 178.897g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine prepared in Preparation Example 2 and 9.596 g (0.089 μl ol) of p-phenylenediamine (p-PDA) were anhydrous N-methyl pyrrolidone (anhydrous N- methyl pyrrolidone: NMP) was completely dissolved in 178.897 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20.0g( 0.092 腿 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-16을 제조하였다. GPC를 통해 상기 중합체 P-16의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 22,500g/nK)l이었다. 합성예 17 ： 액정배향용 중합체 P-17 Then, 20.0 g (0.092 腿 ol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-16 for liquid crystal orientation. When the molecular weight of the polymer P-16 was confirmed through GPC, the weight average molecular weight (Mw) was 22,500 g / nK) l. Synthesis Example 17 Polymer P-17 for Liquid Crystal Alignment
상기 제조예 2에서 제조된 디아민 1.974 g (0.01 讓 ol), 4,4'- 옥시디아닐린 (4,4' -oxydi aniline, ODA) 17.768 g(0.089 隱 ol)을 무수 N- 메틸피를리돈 (anhydrous N-methyl pyrrolidone: NMP) 225.208g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine and 4,4′-oxydianiline (ODA) prepared in Preparation Example 2, 17.768 g (0.089 μl ol) of anhydrous N-methylpyrrolidone (anhydrous N-methyl pyrrolidone: NMP) was completely dissolved in 225.208 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel 1 it ic di anhydride, PMDA)20.0g (0.092 醒 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-17을 제조하였다. GPC를 통해 상기 중합체 P-17의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 24,500g/nK)l이었다. 합성예 18 ： 액정배향용 중합체 P-18.  Then, 20.0 g (0.092 醒 ol) of pyromellitic acid anhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer P-17 for liquid crystal alignment. . The molecular weight of the polymer P-17 was confirmed by GPC. The weight average molecular weight (Mw) was 24,500 g / nK) l. Synthesis Example 18 Polymer P-18 for liquid crystal alignment.
상기 제조예 2에서 제조된 디아민 1.974 g (0.01 隱 ol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 17.593 g(0.089 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrolidone: NMP) 224.218g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine and 4,4′-methylenedianiline (MDA) prepared in Preparation Example 2 were added 17.593 g (0.089 μl ol) of anhydrous N-methylpyridone ( anhydrous N-methyl pyrrolidone (NMP) was completely dissolved in 224.218 g.
그리고, ice bath 하에서 피로멜리틱산 디무수물 (pyromel lit ic di anhydride, PMDA)20.0g (0.092 匪 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-18을 제조하였다. GPC를 통해 상기 중합체 P-18의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 23,000g/ti)l이었다. 합성예 19 ： 액정배향용 중합체 P-19  Then, 20.0 g (0.092 匪 ol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer P-18 for liquid crystal alignment. The molecular weight of the polymer P-18 was confirmed by GPC. As a result, the weight average molecular weight (Mw) was 23,000 g / ti) l. Synthesis Example 19 ： Polymer P-19 for liquid crystal orientation
상기 제조예 3에서 제조된 디아민 1.974 g (0.01 mmol), p— 페닐렌디아민 (p-phenylenedi amine, p-PDA) 9.596 g(0.089 醒 ol)을 무수 N- 메틸 피를리돈 (anhydrous N-methyl pyrrolidone: NMP) 178.897g 에 완전히 녹였다. ' 1.974 g (0.01 mmol) of diamine prepared in Preparation Example 3 and 9.596 g (0.089 醒 ol) of p—phenylenediamine (p-PDA) were anhydrous N-methyl pyridone (anhydrous N-methyl). pyrrolidone: NMP) was completely dissolved in 178.897 g. '
그리고, ice bath 하에서 피로멜리틱산 디무수물 (pyromel 1 it ic di anhydride, PMDA) 20.0g(0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-19을 제조하였다. GPC를 통해 상기 중합체 P-19의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 21,500g/m이이었다. 합성예 20 ： 액정배향용 중합체 P-20 Then, 20.0 g (0.092 隱 ol) of pyromellitic acid anhydride (PMDA) was added to the solution at room temperature under an ice bath. Stirring for 16 hours to prepare polymer P-19 for liquid crystal alignment. The molecular weight of the polymer P-19 was confirmed by GPC. The weight average molecular weight (Mw) was 21,500 g / m. Synthesis Example 20 ： Polymer P-20 for liquid crystal alignment
상기 제조예 3에서 제조된 디아민 1.974 g (0.01 瞧 ol), 4,4'- 옥시디아닐린(4，4'-(« (^31^1^ ， 0DA) 17.768 g(0.089 醒 ol)을 무수 N- 메틸피를리돈 (anhydrous N-methyl pyrrol idone: NMP) 225.208g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine, 4,4′-oxydianiline (4,4 ′-(«(^ 31 ^ 1 ^, 0DA) prepared in Preparation Example 3, 17.768 g (0.089 μl ol) were dried. It was completely dissolved in 225.208 g of N-methyl pyrrol idone (NMP).
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel 1 it ic di anhydride, PMDA) 20. Og (0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-20을 제조하였다. GPC를 통해 상기 중합체 P-20의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 24,500g/irol이었다. 합성예 21 ： 액정배향용 중합체 P-21  Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare a liquid crystal alignment polymer P-20. It was. As a result of checking the molecular weight of the polymer P-20 through GPC, the weight average molecular weight (Mw) was 24,500 g / irol. Synthesis Example 21 Polymer P-21 for Liquid Crystal Alignment
상기 제조예 3에서 제조된 디아민 1.974 g (0.01 隱 ol), 4,4'- 메틸렌디아닐린 (4，4'— Methylenedianiline DA) 17.593 g(0.089 隱 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol idone: NMP) 224.218g 에 완전히 녹였다.  1.974 g (0.01 μl ol) of diamine and 4,4′-methylenedianiline (4,4′—Methylenedianiline DA) prepared in Preparation Example 3 were added 17.593 g (0.089 μl ol) of anhydrous N-methylpyridone (anhydrous). N-methyl pyrrol idone: NMP) was completely dissolved in 224.218 g.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel litic di anhydride, PMDA) 20. Og (0.092 匪 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-21을 제조하였다. GPC를 통해 상기 중합체 P-21의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 21,000g/m 이었다. 합성예 22 ： 액정배향용 중합체 P-22  Then, pyromel litic dianhydride (PMDA) 20. Og (0.092 匪 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-21 for liquid crystal orientation. When the molecular weight of the polymer P-21 was confirmed through GPC, the weight average molecular weight (Mw) was 21,000 g / m. Synthesis Example 22 ： Polymer P-22 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 隱 ol), p- 페닐렌디아민 (p-phenylenedi amine, p-PDA) 9.337 g(0.086 隱 ol)을 무수 N_ 메틸피를리돈 (anhydrous N-methyl pyrrol idone: NMP) 177.128g 에 완전히 녹였다. 1.921 g (0.01 隱 ol) of diamine prepared in Preparation Example 1 and 9.337 g (0.086 9.3 ol) of p-phenylenediamine (p-PDA) were added to anhydrous N_methylpyrilidone (anhydrous N-methyl). pyrrol idone: NMP) 177.128g fully Melted.
그리고, ice bath 하에서 1, 3-디메틸-사이클로부탄 -1， 2,3， 4- 테트라카복실산 디무수물 (DMCBDA) 20. Og (0.089 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-22을 제조하였다. GPC를 통해 상기 중합체 P-22의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 20,000g/nral이었다. 합성예 23 ： 액정배향용 중합체 P-23  And, 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic acid dianhydride (DMCBDA) 20. Og (0.089 隱 ol) was added to the solution and stirred at room temperature for 16 hours under an ice bath. Liquid crystal alignment polymer P-22 was prepared. The molecular weight of the polymer P-22 was confirmed by GPC. The weight average molecular weight (Mw) was 20,000 g / nral. Synthesis Example 23 Polymer P-23 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 19.211 g (0.096 醒 ol)을 무수 N- 메틸피롤리돈 (anhydrous N-methyl pyrrol i done: NMP) 222.194g 에 완전히 녹였다.  19.211 g of diamine prepared in Preparation Example 1 (0.096 μl) was completely dissolved in 222.194 g of anhydrous N-methyl pyrrolidone (NMP).
그리고， ice bath 하에서 1，3-디메틸-사이클로부탄 -1， 2ᅳ 3,4- 테트라카복실산 디무수물 (DMCBDA) 20.0g (0.089 瞧 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-23을 제조하였다. GPC를 통해 상기 중합체 P-23의 분자량을 확인한 결과, 중량평균분자량 (Mw)이 20,500g/m 이었다. 합성예 24 ： 액정배향용 중합체 P-24  Then, 20.0 g (0.089) ol) of 1,3-dimethyl-cyclobutane-1,2 ᅳ 3,4-tetracarboxylic acid dianhydride (DMCBDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to form a liquid crystal. Orientation Polymer P-23 was prepared. The molecular weight of the polymer P-23 was confirmed by GPC, and the weight average molecular weight (Mw) was 20,500 g / m. Synthesis Example 24 Polymer P-24 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 誦 ol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 17.119 g(0.086 醒 ol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 221.225g 에 완전히 녹였다. .  1.921 g (0.01 μl ol) of diamine, 4,4′-methylenedianiline (MDA) prepared in Preparation Example 1, and 17.119 g (0.086 μl ol) of anhydrous N-methylpyrrolidone ( anhydrous N-methyl pyrrol i done: NMP) was completely dissolved in 221.225 g. .
그리고， ice bath 하에서 1,3-디메틸-사이클로부탄 -1，2，3，4- 테트라카복실산 디무수물 (DMCBDA) 20.0g (0.089 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P-24을 제조하였다. GPC를 통해 상기 중합체 P-24꾀 분자량을 확인한 결과， 중량평균분자량 (Mw)이 22,000g/n l이었다. 합성예 25 ： 액정배향용 중합체 P-25 Then, 20.0 g (0.089 隱 ol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to form a liquid crystal. Orientation Polymer P-24 was prepared. The molecular weight of the polymer P-24 was confirmed by GPC, and a weight average molecular weight (Mw) was 22,000 g / nl. Synthesis Example 25 ： Polymer P-25 for liquid crystal alignment
상기 제조예 1에서 제조된 디아민 1.921 g (0.01 隱 ol), 4,4'- 메틸렌디아닐린 (4,4'-Methylenedianiline,MDA) 17.119 g(0.086 mmol)을 무수 N-메틸피를리돈 (anhydrous N-methyl pyrrol i done: 匪 P) 219.696g 에 완전히 녹였다. 1.921 g (0.01 μl ol) of diamine prepared in Preparation Example 1, 4,4′- 17.119 g (0.086 mmol) of methylenedianiline (4,4'-Methylenedianiline, MDA) was completely dissolved in 219.696 g of anhydrous N-methyl pyrrol i done (X P).
그리고， ice bath 하에서 1,3-디메틸-사이클로부탄 -1， 2,3，4- 테트라카복실산 디무수물 (DMCBDA) 10. Og (0.045 隱 ol)와 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 9.73g (0.045 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 P- 25을 제조하였다. GPC를 통해 상기 중합체 P-25의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 24,000g/mol이었다. 비교 합성예 1 ： 액정배향용 중합체 R-1  And 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) under ice bath 10.Og (0.045 隱 ol) and pyromellitic di anhydride (PMDA) 9.73 g (0.045 μl ol) was added to the solution, followed by stirring at room temperature for 16 hours to prepare polymer P-25 for liquid crystal alignment. The molecular weight of the polymer P-25 was confirmed by GPC. As a result, the weight average molecular weight (Mw) was 24,000 g / mol. Comparative Synthesis Example 1 Polymer R-1 for Liquid Crystal Alignment
P-페닐렌디아민 (P— phenyl enedi amine, p-PDA) 26.852 g(0.099 瞧 ol)을 무수 N-메틸 피롤리돈 (anhydrous N-methyl pyrrol i done: NMP) 265.496g 에 완전히 녹였다.  26.852 g (0.099 瞧 ol) of P-phenylenediamine (p-PDA) was completely dissolved in 265.496 g of anhydrous N-methyl pyrrolidone (NMP).
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel litic di anhydride, PMDA) 20. Og (0.092 隱 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 R-1를 제조하였다. GPC를 통해 상기 중합체 R-1의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 26,000g/mol이었다. 비교 합성예 2 ： 액정배향용 중합체 R-2  Then, pyromel litic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer R-1 for liquid crystal orientation. When the molecular weight of the polymer R-1 was confirmed through GPC, the weight average molecular weight (Mw) was 26,000 g / mol. Comparative Synthesis Example 2 Polymer R-2 for Liquid Crystal Alignment
4,4'-옥시디아닐린(4,4'-0 311^ ， 0DA) 19.743 g(0.099誦 ol)을 무수 N-메틸 피를리돈 (anhydrous N-methyl pyrrol i done: NMP) 225.208g 에 완전히 녹였다. 19.743 g (0.099 μl) of 4,4'-oxydianiline (4,4'- 0 311 ^, 0DA) was completely added to 225.208 g of anhydrous N-methyl pyrrol i done (NMP). Melted.
그리고， ice bath 하에서 피로멜리틱산 디무수물 (pyromel 1 it ic di anhydride, PMDA) 20. Og (0.092 醒 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 R-2를 제조하였다. GPC를 통해 상기 중합체 R-2의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 21,000g/iii()l이었다. 비교 합성예 3 ： 액정배향용 중합체 R-3 Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 醒 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare a polymer for liquid crystal alignment R-2. It was. When the molecular weight of the polymer R-2 was confirmed through GPC, the weight average molecular weight (Mw) was 21,000 g / iii () l. Comparative Synthesis Example 3 Polymer R-3 for Liquid Crystal Alignment
4,4'-메틸렌디아닐린(4,4'—¾1 11 161 (1131^1 ，1 ) 19.548 g(0.089 mmol)을 무수 N-메틸 피롤리돈 (anhydrous N-methyl pyrrol i done: MP) 224.218g 에 완전히 녹였다.  4,4'-methylenedianiline (4,4'—¾1 11 161 (1131 ^ 1,1) 19.548 g (0.089 mmol) was added anhydrous N-methyl pyrrol i done (MP) 224.218 completely dissolved in g.
그리고, ice bath 하에서 피로멜리틱산 디무수물 (pyromellitic di anhydride, PMDA) 20. Og (0.092 讓 ol)을 상기 용액에 첨가하여 상온에서 16 시간 동안 교반하여 액정배향용 중합체 R-3를 제조하였다. GPC를 통해 상기 중합체 R-3의 분자량을 확인한 결과， 중량평균분자량 (Mw)이 23,000g/m 이었다. 비교 합성예 4: 액정 배향제용 중합체 R-4  Then, pyromellitic di anhydride (PMDA) 20. Og (0.092 讓 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer R-3 for liquid crystal orientation. When the molecular weight of the polymer R-3 was confirmed through GPC, the weight average molecular weight (Mw) was 23,000 g / m. Comparative Synthesis Example 4: Polymer R-4 for Liquid Crystal Alignment
상기 제조예 1에서 제조된 디아민 대신 하기 화학식 A로 표시되는 6- (4-아미노페닐)피리딘 -3-아민 [6-(4-aminophenyl )pyr idin-3-amine]를 사용한 것을 제외하고는 상기 합성예 1과 동일한 방법으로 액정 배향제용 중합체 R- 4를 제조하였다.  Except for using the 6- (4-aminophenyl) pyridine-3-amine [6- (4-aminophenyl) pyr idin-3-amine] represented by the following formula A instead of the diamine prepared in Preparation Example 1 Polymer R-4 for the liquid crystal aligning agent was prepared in the same manner as in Synthesis example 1.
[화학식 A]
Figure imgf000037_0001
[Formula A]
Figure imgf000037_0001
비교 합성예 5: 액정 배향제용 중합체 R-5 Comparative Synthesis Example 5: Polymer R-5 for Liquid Crystal Alignment Agent
상기 제조예 1에서 제조된 디아민 대신 하기 화학식 B로 표시되는 Instead of the diamine prepared in Preparation Example 1 represented by the following formula (B)
4，4'-디아미노디페닐아민 [4,4'-diaminodiphenylamine]를 사용한 것을 제외하고는 상기 합성예 1과 동일한 방법으로 액정 배향제용 중합체 R-5를 제조하였다. Polymer R-5 was prepared in the same manner as in Synthesis Example 1, except that 4,4'-diaminodiphenylamine [4,4'-diaminodiphenylamine] was used.
Figure imgf000037_0002
비교 합성예 6 : 액정 배향제용 중합체 R-6
Figure imgf000037_0002
Comparative Synthesis Example 6: Polymer R-6 for Liquid Crystal Alignment Agent
상기 제조예 1에서 제조된 디아민 대신 하기 화학식 C로 표시되는 화합물을 사용한 것을 제외하고는 상기 합성예 1과 동일한 방법으로 액정 배향제용 중합체 R— 6를 제조하였다.  Polymer R-6 was prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following Formula C was used instead of the diamine prepared in Preparation Example 1.
[화학식 C]  [Formula C]
Figure imgf000038_0001
Figure imgf000038_0001
<실시예 및 비교예: 액정배향제의 제조 > <Examples and Comparative Examples: Preparation of the liquid crystal aligning agent>
실시예 1  Example 1
상기 합성예 1의 액정배향제용 중합체 (P-1) 20 g을 NMP 8.65 g, GBL 20 g of the polymer for liquid crystal aligning agent (P-1) of Synthesis Example 1 was used as NMP 8.65 g and GBL.
19.95 g, 2-부록시에탄을 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 A-1을 제조하였다. 실시예 2 19.95 g and 2-butoxyethane were dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-1. Example 2
상기 합성예 2의 액정배향제용 중합체 (P-2) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고, 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 A-2을 제조하였다. 실시예 3  20 g of the liquid crystal aligning agent polymer (P-2) of Synthesis Example 2 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-2. Example 3
상기 합성예 3의 액정배향제용 중합체 (P-3) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고, 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1//m인 필터로 가압 여과하여 액정 배향제 A-3을 제조하였다. 실시예 4 20 g of the liquid crystal aligning agent polymer (P-3) of Synthesis Example 3 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. And the obtained solution was filtered under pressure with the filter whose pore size of the poly (tetrafluorene ethylene) material is 0.01 // m, and manufactured liquid crystal aligning agent A-3. Example 4
상기 합성예 4의 액정배향제용 중합체 (P-4) 20 g을 匪 P 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 B-1을 제조하였다. 실시예 5  20 g of the polymer for liquid crystal aligning agent (P-4) of Synthesis Example 4 was dissolved in a mixed solvent of 匪 P 8.65 g, GBL 19.95 g, and 2-butrocethanol 11.4 g to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-1. Example 5
상기 합성예 5의 액정배향제용 중합체 (P-5) 20 g을 NMP 8.65 g, GBL 19.95 gᅳ 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1//m인 필터로 가압 여과하여 액정 배향제 Bᅳ 2을 제조하였다. 실시예 6  20 g of the liquid crystal aligning agent polymer (P-5) of Synthesis Example 5 was dissolved in a mixed solvent of 8.65 g of NMP and 11.4 g of GBL 19.95 g ᅳ 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (l / m) of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B # 2. Example 6
상기 합성예 6의 액정배향제용 중합체 (P-6) 20 g을 NMP 8.65 g, GBL 19.95 g, 2—부록시에탄을 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1/ 인 필터로 가압 여과하여 액정 배향제 B-3을 제조하였다. 실시예 7  20 g of the liquid crystal aligning agent polymer (P-6) of Synthesis Example 6 was dissolved in NMP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (poly / tetrafluoreneethylene) material to prepare a liquid crystal aligning agent B-3. Example 7
상기 합성예 7의 액정배향제용 중합체 (P-7) 20 g을 NMP 8.65. g, GBL 20 g of the polymer for liquid crystal aligning agent of Synthesis Example 7 (P-7) was NMP 8.65. g, GBL
19.95 g, 2ᅳ부록시에탄을 11.4g의 혼합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 B-4을 제조하였다. 실시예 8 19.95 g and 2'butoxyethane were dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-4. Example 8
상기 합성예 8의 액정배향제용 중합체 (P-8) 20 g을 丽 P 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고, 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 Bᅳ 5을 제조하였다. 실시예 9 20 g of the liquid crystal aligning agent polymer (P-8) of Synthesis Example 8 was dissolved in a mixture of P 8.65 g, GBL 19.95 g, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B # 5. Example 9
상기 합성예 9의 액정배향제용 중합체 (P-9) 20 g을 NMP 8.65 g , GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질꾀 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 B-6을 제조하였다. 실시예 10  20 g of the liquid crystal aligning agent polymer (P-9) of Synthesis Example 9 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a poly (tetrafluoreneethylene) material pore size of 0.1 to prepare a liquid crystal aligning agent B-6. Example 10
상기 합성예 10의 액정배향제용 중합체 (P-10) 20 g을 NMP 8.65 g , GBL 19.95 g , 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 m인 필터로 가압 여과하여 액정 배향제 C-1을 제조하였다. 실시예 11  20 g of the liquid crystal aligning agent polymer (P-10) of Synthesis Example 10 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 m of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent C-1. Example 11
상기 합성예 11의 액정배향제용 중합체 (P-11) 20 g을 NMP 8.65 g , GBL 19.95 g , 2-부특시에탄올 11 .4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1/皿인 필터로 가압 여과하여 액정 배향제 C— 2을 제조하였다. 실시예 12  20 g of the liquid crystal aligning agent polymer (P-11) of Synthesis Example 11 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 / mm3 of a poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent C-2. Example 12
상기 합성예 12의 액정배향제용 중합체 (P-12) 20 g을 NMP 8.65 g , 20 g of the liquid crystal aligning agent polymer (P-12) of Synthesis Example 12 was replaced with NMP 8.65 g,
GBL 19.95 g, 2-부특시에탄을 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1/ m인 필터로 가압 여과하여 액정 배향제 C-3을 제조하였다. 실시예 13 19.95 g of GBL and 2-butoxetane were dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (m / m) made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent C-3. Example 13
상기 합성예 13의 액정배향제용 중합체 (P-13) 20 g을 NMP 8.65 g , GBL 19.95 g , 2-부록시에탄올 11 .4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 D-1을 제조하였다. 실시예 14 20 g of the liquid crystal aligning agent polymer (P-13) of Synthesis Example 13 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent D-1. Example 14
상기 합성예 14의 액정배향제용 중합체 (P-14) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부특시에탄을 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 D-2을 제조하였다. 실시예 15  20 g of the liquid crystal aligning agent polymer (P-14) of Synthesis Example 14 was dissolved in NMP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent D-2. Example 15
상기 합성예 15의 액정배향제용 중합체 (P-15) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 D-3을 제조하였다. 실시예 16  20 g of the liquid crystal aligning agent polymer (P-15) of Synthesis Example 15 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent D-3. Example 16
상기 합성예 16의 액정배향제용 중합체 (P-16) 20 g을 丽 P 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 E-1을 제조하였다. 실시예 17  20 g of the liquid crystal aligning agent polymer (P-16) of Synthesis Example 16 was dissolved in a mixed solvent of P 8.65 g, GBL 19.95 g, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent E-1. Example 17
상기 합성예 17의 액정배향제용 중합체 (P-17) 20 g을 NMP 8.65 g, NMP 8.65 g, 20 g of the polymer for liquid crystal aligning agent (P-17) of Synthesis Example 17;
GBL 19.95 g, 2ᅳ부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0.1/zm인 필터로 가압 여과하여 액정 배향제 E-2을 제조하였다. 실시예 18 It was dissolved in a mixed solvent of 19.95 g of GBL and 11.4 g of 2′butoxyethanol to obtain a 5 wt solution. And the obtained solution was filtered under pressure with the filter whose pore size of poly (tetrafluoreneethylene) material is 0.1 / zm, and the liquid crystal aligning agent E-2 was manufactured. Example 18
상기 합성예 18의 액정배향제용 중합체 (P— 18) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0.1//m인 필터로 가압 여과하여 액정 배향제 E-3을 제조하였다. 실시예 19 20 g of the liquid crystal aligning agent polymer (P-18) of Synthesis Example 18 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. And the obtained solution was filtered under pressure with the filter whose pore size of poly (tetrafluorene ethylene) material is 0.1 // m, and the liquid crystal aligning agent E-3 was manufactured. Example 19
상기 합성예 19의 액정배향제용 중합체 (P-19) 20 g을 MP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈 0. 1 인 필터로 가압 여과하여 액정 배향제 F— 1을 제조하였다. 실시예 20  20 g of the liquid crystal aligning agent polymer (P-19) of Synthesis Example 19 was dissolved in a mixed solvent of MP 8.65 g, GBL 19.95 g, and 2-buteethanol 11.4 g to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-1. Example 20
상기 합성예 20의 액정배향제용 중합체 (P-20) 20 g을 NMP 8.65 g, GBL 19.95 g, 2—부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 F-2을 제조하였다. 실시예 21  20 g of the liquid crystal aligning agent polymer (P-20) of Synthesis Example 20 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-2. Example 21
상기 합성예 21의 액정배향제용 중합체 (P-21) 20 g을 NMP 8.65 g , GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 F-3을 제조하였다. 실시예 22  20 g of the liquid crystal aligning agent polymer (P-21) of Synthesis Example 21 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-3. Example 22
상기 합성예 22의 액정배향제용 중합체 (P-22) 20 g을 NMP 8.65 g, NMP 8.65 g, 20 g of the liquid crystal aligning agent polymer (P-22) of Synthesis Example 22;
GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 인 필터로 가압 여과하여 액정 배향제 G-1을 제조하였다. 실시예 23 It was dissolved in a mixed solvent of 19.95 g of GBL and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent G-1. Example 23
상기 합성예 23의 액정배향제용 중합체 (P-23) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 G-2을 제조하였다. 실시예 24 20 g of the liquid crystal aligning agent polymer (P-23) of Synthesis Example 23 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent G-2. Example 24
상기 합성예 24의 액정배향제용 중합체 (P-24) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부톡시에탄을 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 O.lΛπ인 필터로 가압 여과하여 액정 배향제 G— 3을 제조하였다. 실시예 25  20 g of the liquid crystal aligning agent polymer (P-24) of Synthesis Example 24 was dissolved in NMP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt% solution. And the obtained solution was filtered under pressure with the filter whose pore size of poly (tetrafluoreneethylene) material is 0.1L (pi), and the liquid crystal aligning agent G-3 was manufactured. Example 25
상기 합성예 25의 액정배향제용 중합체 (P-25) 20 g을 MP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어잔용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 O.l m인 필터로 가압 여과하여 액정 배향제 G-4을 제조하였다. 비교예 1  20 g of the liquid crystal aligning agent polymer (P-25) of Synthesis Example 25 was dissolved in a mixed solvent of MP 8.65 g, GBL 19.95 g, and 2-buteethanol 11.4 g to obtain a 5 wt% solution. Then, the obtained residual solution was filtered under pressure with a filter having a pore size of 0.1 m of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent G-4. Comparative Example 1
상기 비교합성예 1의 액정배향제용 중합체 (R-1) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0.1 인 필터로 가압 여과하여 액정 배향제 R'-l을 제조하였다. 비교예 2  20 g of the liquid crystal aligning agent polymer (R-1) of Comparative Synthesis Example 1 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of poly (tetrafluoreneethylene) material of 0.1 to prepare a liquid crystal aligning agent R'-1. Comparative Example 2
상기 비교합성예 2의 액정배향제용 중합체 (R-2) 20 g을 NMP 8.65 g, NMP 8.65 g, 20 g of the polymer (R-2) for liquid crystal aligning agent of Comparative Synthesis Example 2,
GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라풀루오렌에틸렌) 재질의 기공 사이즈가 0.1/m인 필터로 가압 여과하여 액정 배향제 R'-2을 제조하였다. 비교예 3 It was dissolved in a mixed solvent of 19.95 g of GBL and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. And the obtained solution was filtered under pressure with the filter whose pore size of poly (tetra pullene ethylene) material is 0.1 / m, and the liquid crystal aligning agent R'-2 was produced. Comparative Example 3
상기 비교합성예 3의 액정배향제용 중합체 (R-3) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부특시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0.1 인 필터로 가압 여과하여 액정 배향제 R'-3을 제조하였다. 비교예 4 20 g of the liquid crystal aligning agent polymer (R-3) of Comparative Synthesis Example 3 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of poly (tetrafluoreneethylene) material of 0.1 to prepare a liquid crystal aligning agent R'-3. Comparative Example 4
상기 비교합성예 4의 액정배향제용 중합체 (R— 4) 20 g을 NMP 8.65 g, GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1/ΛΠ인 필터로 가압 여과하여 액정 배향제 R ' -4을 제조하였다. 비교예 5  20 g of the liquid crystal aligning agent polymer (R-4) of Comparative Synthesis Example 4 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 / Λπ of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent R'-4. Comparative Example 5
상기 비교합성예 5의 액정배향제용 중합체 (R-5) 20 g을 MP 8.65 g, GBL 19.95 g, 2-부특시에탄을 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1 인 필터로 가압 여과하여 액정 배향제 R' -5을 제조하였다. 비교예 6  20 g of the liquid crystal aligning agent polymer (R-5) of Comparative Synthesis Example 5 was dissolved in MP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent R'-5. Comparative Example 6
상기 비교합성예 6의 액정배향제용 중합체 (R-6) 20 g을 NMP 8.65 g , GBL 19.95 g, 2-부록시에탄올 11.4g의 흔합 용매에 녹여 5 wt% 용액을 얻었다. 그리고， 얻어진 용액을 폴리 (테트라플루오렌에틸렌) 재질의 기공 사이즈가 0. 1/im인 필터로 가압 여과하여 액정 배향제 R' -6을 제조하였다.  20 g of the liquid crystal aligning agent polymer (R-6) of Comparative Synthesis Example 6 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (im / im) of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent R'-6.
<실험예: 실시예 및 비교예에서 얻어진 액정 배향제의 물성 측정 > 상기 실시예 및 비교예에서 얻어진 액정 배향제를 이용하여 액정 배향셀을 제조하고， 액정 배향셀로부터 각각의 물성을 하기 방법으로 측정하였으며， 그 결과를 표 1에 나타내었다. <Experimental Example: Measurement of physical properties of liquid crystal aligning agents obtained in Examples and Comparative Examples> A liquid crystal aligning cell was prepared using the liquid crystal aligning agents obtained in the above Examples and Comparative Examples, and the respective physical properties were obtained from the liquid crystal aligning cells by the following method. It measured, and the result is shown in Table 1.
구체적으로， 2.5 cm X 2.7 cm의 크기를 갖는 사각형 유리기판 상에 두께 60 nm， 면적 1 cm X 1 cm의 ITO 전극이 패턴된 전압유지비율 (VHR)용 상，하 기판 각각에 스핀 코팅 방식으로 상기 실시예 및 비교예에서 얻어진 액정 배향제를 도포하였다. 이어서, 액정 배향제가 도포된 기판을 약 80 °C의 핫플레이트 위에 두어 2분간 건조하여 용매를 증발시켰다. Specifically, the ITO electrode having a thickness of 60 nm and an area of 1 cm X 1 cm on a rectangular glass substrate having a size of 2.5 cm X 2.7 cm is spin-coated on each of the upper and lower substrates for the voltage holding ratio (VHR) patterned. The liquid crystal aligning agent obtained by the said Example and the comparative example was apply | coated. Subsequently, the substrate to which the liquid crystal aligning agent was applied was placed on a hot plate of about 80 ° C., dried for 2 minutes to evaporate the solvent.
이후， 건조 처리된 상 /하판을 약 230 °C의 오븐에서 2000초간 소성 (경화)한 이후， 이렇게 얻어진 도막을 배향 처리하기 위해， 금속 를러에 러빙천의 옷감을 붙인 러빙 롤러를 회전시키면서 도막의 표면을 한 방향으로 러빙하였다. Then, after firing (curing) the dried upper and lower plates in an oven at about 230 ° C. for 2000 seconds, in order to orient the coating film thus obtained, while rotating the rubbing rollers having a cloth of rubbing cloth attached to the metal roller, Surface Rubbing in the direction.
이후， 배향 처리된 상 /하판을 약 230 °C의 오본에서 15분간 소성 (경화)하여 막 두께 0. 1 의 도막을 얻었다. 이후， 4.5 urn 크기의 볼 스페이서가 함침된 실링제 (seal ing agent )를 액정 주입구를 제외한 상판의 가장자리에 도포하였다. 그리고， 상판 및 하판에 형성된 배향막이 서로 마주 보며 배향 방향이 서로 나란하도록 정열시킨 후， 상하판을 합착하고 실링제를 UV 및 열 경화함으로써 빈 셀을 제조하였다. 그리고， 상기 빈 셀에 액정을 주입하고 주입구를 실링제로 밀봉하여， 액정 배향셀을 제조하였다. Thereafter, the orientation-treated upper and lower plates were baked (cured) for 15 minutes in an Aubon at about 230 ° C. to obtain a coating film having a film thickness of 0.1. Thereafter, a sealing agent impregnated with a 4.5 urn ball spacer was applied to the edges of the upper plate except for the liquid crystal injection hole. The alignment films formed on the upper and lower plates face each other and are aligned so that the alignment directions are parallel to each other. Then, the upper and lower plates are bonded to each other, and an empty cell is prepared by UV and thermal curing the sealing agent. Then, a 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.
1. 전압보유율 (voltage holding ratio, VHR) 1.Voltage holding ratio (VHR)
상기 액정 배향셀에 대하여， 측정 장비로 T0Y0 corporat ion의 6254C 장비를 사용하여， 1Hz , 60 °C 온도에서 전압 보유율을 측정했다. 2. AC잔상 With respect to the liquid crystal cell aligned, using the equipment of 6254C T0Y0 corporat ion to the measuring equipment, to measure the voltage retention rate at 1Hz, 60 ° C temperature. 2. AC afterimage
액정셀의 상판 및 하판에 편광판을 서로 수직이 되도록 부착하였다. 상기 편광판이 부탁된 액정셀을 7 , 000 cd/ri의 백라이트 위에 부착하고 블랙 상태의 휘도를 휘도 밝기 측정 장비인 PR-880 장비를 이용해 측정하였다. 그리고， 상기 액정셀을 상온에서 교류전압 5V로 24시간 구동하였다. 이후， 액정셀의 전압을 끈 상태에서 상술한 바와 동일하게 블랙 상태의 휘도를 측정하였다. 액정셀의 구동 전 측정된 초기 휘도 (L0)와 구동 후 측정된 나중 휘도 (L1) 간의 차이를 초기 휘도 (L0) 값으로 나누고 100을 곱하여 휘도 변동율을 계산하였다. 이렇게 계산된 휘도 변동율은 TO에 가까을수록 배향 안정성이 우수함을 의미한다. 이러한 휘도 변화율의 측정 결과를 통해 다음 기준하에 잔상 수준을 평가하였다.  The polarizing plates were attached to the upper and lower plates of the liquid crystal cell so as to be perpendicular to each other. The liquid crystal cell to which the polarizing plate was attached was attached to a backlight of 7,000 cd / ri, and the luminance of the black state was measured using the PR-880 equipment, which is a luminance brightness measuring instrument. Then, the liquid crystal cell was driven for 24 hours at 5V at room temperature. Then, the brightness of the black state was measured in the same manner as described above with the voltage of the liquid crystal cell turned off. The difference between the initial luminance L0 measured before driving the liquid crystal cell and the later luminance L1 measured after driving was divided by the initial luminance L0 value and multiplied by 100 to calculate the luminance variation rate. The calculated luminance fluctuation rate means that the closer to TO, the better the orientation stability. The afterimage level was evaluated based on the following criteria through the measurement results of the luminance change rate.
우수 : 휘도 변동율이 10% 미만임  Excellent: Less than 10% luminance change
보통 ： 휘도 변동율이 10% 내지 20%임  Normal: Luminance variation rate is 10% to 20%
3. 이미드화전환율 (%) 3. Imidization Conversion Rate (%)
상기 실시예 1， 2 및 비교예 4，5，6의 액정 배향제로부터 얻어진 액정 배향막에 대하여， ATR법으로 FT-IR스펙트럼을 측정하여 포함된 중합체 분자 내 이미드 구조 비율을 측정하였다. Liquid crystal obtained from the liquid crystal aligning agent of said Example 1, 2 and Comparative Examples 4, 5, 6 About the alignment film, the FT-IR spectrum was measured by the ATR method, and the imide structure ratio in the polymer molecule contained was measured.
【표 1】 Table 1
실시예 및 비교예의 실험예 측정 결과  Experimental Example Measurement Results of Examples and Comparative Examples
Figure imgf000046_0001
Figure imgf000046_0001
Figure imgf000047_0001
비교예 5 R-5 화학식 B PMDA 73 보통 79
Figure imgf000047_0001
Comparative Example 5 R-5 Formula B PMDA 73 Normal 79
비교예 6 R-6 화학식 C PMDA 53 불량 73 상기 표 1에 나타난 바와 같이， 실시예의 액정 배향제는 제조예 1 내지 3과 같은 비대칭 구조의 디아민을 포함한 반웅물로부터 제조된 중합체를 포함함에 따라， 전압 보유율 (VHR)이 80% 이상으로 높게 향상되었고， AC 잔상은 동등 수준 이상을 유지할 수 있다는 것을 확인하였다. Comparative Example 6 R-6 Formula C PMDA 53 Defect 73 As shown in Table 1 above, the liquid crystal aligning agent of the example included a polymer prepared from a semi-ungmul containing a diamine having an asymmetric structure as in Preparation Examples 1 to 3, It was confirmed that the voltage retention (VHR) was improved to 80% or higher, and that the AC afterimage can be maintained at an equivalent level or higher.
특히， 실시예 22 내지 25의 액정배향제의 경우, 전압 보유율 (VHR) 향상과 함께, 휘도 변동율이 10% 미만으로 측정되어 AC잔상특성이 매우 우수하게 향상되는 것으로 확인되었다.  In particular, in the case of the liquid crystal aligning agents of Examples 22 to 25, the luminance variation was measured to be less than 10% with the improvement of the voltage retention (VHR), and it was confirmed that the AC afterimage characteristic was improved very well.
반면， 비교예의 액정 배향제는 중합체 제조시 반응물에 제조예 1 내지 On the other hand, the liquid crystal aligning agent of the comparative example is prepared in Preparation Example 1 to the reactants in the polymer preparation
3과 같은 비대칭 구조의 디아민이 함유되지 않아， 실시예에 비해 현저히 낮은 55% 내지 73%의 전압 보유율 (VHR)을 나타내며, 휘도 변동율이 10% 내지 20%로 증가해 AC 잔상 특성이 불량하다는 점을 확인할 수 있었다. 특히， 비교예 4 내지 6에서 얻어진 액정배향제의 경우， 230 °C 에서 80% 미만의 이미드화율을 나타내어， 89% 이상의 이미드화율을 나타내는 실시예에 비해 이미드화 정도가 낮음을 확인할 수 있었다. It does not contain a diamine having an asymmetric structure such as 3, and shows a significantly lower voltage retention (VHR) of 55% to 73% compared to the embodiment, and the brightness fluctuation rate increases from 10% to 20%, resulting in poor AC afterimage characteristics. Could confirm. In particular, in the case of the liquid crystal aligning agent obtained in Comparative Examples 4 to 6, the imidation ratio of less than 80% at 230 ° C., it was confirmed that the degree of imidization is lower than the embodiment showing an imidation ratio of 89% or more. .

Claims

【청구범위】 [Claim]
【청구항 1】  [Claim 1]
하기 화학식 1로 표시되는 반복 단위， 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는， 액정 배향제용 중합체:  A polymer for a liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 3:
[화학식 1]  [Formula 1]
' '
Figure imgf000049_0001
Figure imgf000049_0001
[화학식 2]  [Formula 2]
Figure imgf000049_0002
Figure imgf000049_0002
[화학식 3]  [Formula 3]
Figure imgf000049_0003
Figure imgf000049_0003
상기 화학식 l 내지 3에서，  In Chemical Formulas 1 to 3,
R1 및 R2 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고， 나머지는 수소이며， At least one of R 1 and R 2 is an alkyl group having 1 to 10 carbon atoms, and the rest are hydrogen;
X1내지 X3는 각각 독립적으로 4가의 유기기이고, X 1 to X 3 are each independently a tetravalent organic group,
Y1 내지 Y3은 각각 독립적으로 하기 화학식 4로 표시되는 2가의 유기기이고， Y 1 to Y 3 are each independently a divalent organic group represented by the following formula (4),
[화학식 4]
Figure imgf000050_0001
상기 화학식 4에서， [Formula 4]
Figure imgf000050_0001
In Chemical Formula 4,
A는 15족 원소이고，  A is a group 15 element,
¾는 수소， 또는 탄소수 1 내지 10의 알킬기이며，  ¾ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
a는 1 내지 3의 정수이고,  a is an integer of 1 to 3,
Zi 내지 Z4중 적어도 하나는 질소이고， 나머지는 탄소이다. At least one of Zi to Z 4 is nitrogen and the other is carbon.
【청구항 2】 [Claim 2]
제 1항에 있어서,  The method of claim 1,
상기 화학식 4에서, ΊΛ 내지 Ζ4 중 하나가 질소이고， 나머지는 탄소인 액정 배향제용 중합체 . In Chemical Formula 4, one of ΊΛ to Ζ 4 is nitrogen, the remaining carbon is a polymer for a liquid crystal aligning agent.
【청구항 3] [Claim 3]
거 U항에 있어서，  In U,
상기 화학식 4에서，
Figure imgf000050_0002
또는 Ζ3 중 하나가 질소이고 나머지는 탄소이몌 ¾ 및 Ζ4 는 탄소인， 액정 배향제용 중합체. In Chemical Formula 4,
Figure imgf000050_0002
Or one of X 3 is nitrogen and the other is carbon ¾ and X 4 are carbon.
【청구항 4] [Claim 4]
거 U항에 있어서，  In U,
상기 화학식 4에서, Α는 질소이고， ¾은 수소이며, a는 1 인， 액정 배향제용 중합체 .  In Formula 4, A is nitrogen, ¾ is hydrogen, a is 1, a polymer for a liquid crystal aligning agent.
【청구항 5】 [Claim 5]
거 U항에 있어서,  In U,
상기 화학식 4는 하기 화학식 4-1， 화학식 4-2 및 화학식 4-3으로 이루어진 군에서 선택된 1종 이상의 반복단위를 포함하는， 액정 배향제용 중합체： [화학식 4-U 、八 Formula 4 is a polymer for a liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of Formula 4-1, Formula 4-2 and Formula 4-3: [Formula 4-U, 8
[화학식 4-2][Formula 4-2]
Figure imgf000051_0001
Figure imgf000051_0001
[화학식 4-3]
Figure imgf000051_0002
[Formula 4-3]
Figure imgf000051_0002
【청구항 6】 [Claim 6]
게 1항에 있어서,  According to claim 1,
상기 X1 내지 X3는 각각 독립적으 하기 화학식 5에 기재된 4가의 유기기를 포함하는, 액정 배향제용 중합체 X 1 to X 3 are each independently a tetravalent organic group represented by the formula (5), a polymer for a liquid crystal aligning agent
[화학식 5]
Figure imgf000051_0003
Figure imgf000051_0004
상기 화학식 5에서, [Formula 5]
Figure imgf000051_0003
Figure imgf000051_0004
In Chemical Formula 5,
R9 내지 Ri4는 각각 독립적으로 수소， 또는 탄소수 1 내지 10의 알킬기이고， R 9 to Ri 4 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
L2는 직접 결합， -0-， -CO-, -S-, -SO-, -S02-, -CR15R16-, -C0NH-, - C00-, -(C¾)b—， , -C00-(CH2)b-0C0-, 페닐렌 또는 이들의 조합으로 이루어진 군에서 선택된 어느 하나이며， L 2 is a direct bond, -0-, -CO-, -S-, -SO-, -S0 2- , -CR15R16-, -C0NH-, -C00-,-(C¾) b —,, -C00- (CH 2 ) b -0C0-, phenylene or any one selected from the group consisting of
Ris 및 Ris는 각각 수소， 탄소수 1 내지 10의 알킬기， 또는 탄소수 1 내지 10의 플루오로알킬기이고, b는 1 내지 10의 정수이다.  Ris and Ris are each hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, and b is an integer of 1 to 10.
【청구항 7】 [Claim 7]
게 1항에 있어서，  According to claim 1,
하기 화학식 11로 표시되는 반복 단위， 하기 화학식 12로 표시되는 반복 단위 및 하기 화학식 13으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함하는， 액정 배향제용 중합체 :  Further comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (11), a repeating unit represented by the following formula (12) and a repeating unit represented by the following formula (13), a polymer for a liquid crystal aligning agent:
[ 11]  [11]
Figure imgf000052_0001
Figure imgf000052_0001
[화학식 13]  [Formula 13]
HO HO
0 0  0 0
상기 화학식 11 내지 13에서 R3 및 R4 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고, 나머지는 수소이며， In Chemical Formulas 11 to 13 At least one of R 3 and R 4 is an alkyl group having 1 to 10 carbon atoms, and the rest are hydrogen;
X4내지 X6는 각각 독립적으로 4가의 유기기이고， X 4 to X 6 are each independently a tetravalent organic group,
Y4 내지 Y6은 각각 독립적으로 하기 화학식 14 로 표시되는 2가의 유기기이고， Y 4 to Y 6 are each independently a divalent organic group represented by Formula 14,
[화학식 W]
Figure imgf000053_0001
[Formula W]
Figure imgf000053_0001
상기 화학식 14에서，  In Chemical Formula 14,
R5 및 R6는 각각 독립적으로 수소， 할로겐， 시아노， 알킬， C2-10 알케닐， d-10 알콕시， 플루오로알킬, 또는 d-u)풀루오로알콕시이고， P 및 q는 각각 독립적으로 0 내지 4의 정수이고, R 5 and R 6 are each independently hydrogen, halogen, cyano, alkyl, C 2 - 10 alkenyl, alkoxy, d- 10 alkoxy, fluoroalkyl, or du) pool Luo, P and q are each independently Is an integer from 0 to 4,
L1은 단일결합， -0-， -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, ᅳ—CONH一， -C00-, _(CH2)Z -， -0(CH2)z0-, -0(CH2)z-, -NH-, -NH(CH2)Z-NH-, -NH(CH2)z0-, -0CH2-C(CH3)2-CH20-, -C00-(CH2)z-0C0-, 또는 -0C0-(CH2)z-C00-이며, L 1 is a single bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , ᅳ —CONH 一, -C00-, _ (CH 2 ) Z- , -0 (CH 2 ) z 0-, -0 (CH 2 ) z- , -NH-, -NH (CH 2 ) Z -NH-, -NH (CH 2 ) z 0 -, -0CH 2 -C (CH 3 ) 2 -CH 2 0-, -C00- (CH 2 ) z -0C0-, or -0C0- (CH 2 ) z -C00-,
z는 1 내지 10의 정수이고，  z is an integer from 1 to 10,
k 및 m은 각각 독립적으로 0 내지 3ᅳ 또는 1 내지 3의 정수이고, n은 0 내지 3의 정수이다. .  k and m are each independently an integer of 0-3 kHz or 1-3, and n is an integer of 0-3. .
【청구항 8】 [Claim 8]
제 7항에 있어서，  The method of claim 7,
상기 화학식 14는 하기 화학식 15 또는 화학식 16인 , 액정 배향제용 중합체:  Formula 14 is a formula 15 or 16, a polymer for a liquid crystal aligning agent:
[화학식 15]
Figure imgf000053_0002
[Formula 15]
Figure imgf000053_0002
[화학식 16]
Figure imgf000054_0001
상기 화학식 16에서, [Formula 16]
Figure imgf000054_0001
In Chemical Formula 16,
D는 직접결합, 0， S02 또는 C(R7) (R8)이고， 여기서， R7 및 ¾는 각각 독립적으로 수소， 또는 탄소수 1 내지 10의 알킬기이다. D is a direct bond, 0, S0 2 or C (R 7 ) (R 8 ), wherein R 7 and ¾ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
[청구항 9】 [Claim 9]
거 U항에 있어서，  In U,
상기 액정 배향제용 중합체의 중량평균 분자량이 1000 g/mol 내지 200,000 g/mc)l인， 액정 배향제용 중합체 .  The polymer for liquid crystal aligning agents whose weight average molecular weights of the said polymer for liquid crystal aligning agents are 1000 g / mol-200,000 g / mc) l.
【청구항 10】 [Claim 10]
제 1항의 액정 배향제용 중합체를 포함하는， 액정 배향제 . [청구항 11】  The liquid crystal aligning agent containing the polymer for liquid crystal aligning agents of Claim 1. [Claim 11]
제 10항의 액정 배향제를 포함하는， 액정 배향막.  The liquid crystal aligning film containing the liquid crystal aligning agent of Claim 10.
【청구항 12】 [Claim 12]
제 11항의 액정 배향막을 포함하는， 액정표시소자.  A liquid crystal display device comprising the liquid crystal alignment film of claim 11.
PCT/KR2018/005505 2017-05-22 2018-05-14 Polymer for liquid crystal aligning agent, liquid crystal aligning agent comprising same, and liquid crystal alignment film and liquid crystal display device using same liquid crystal aligning agent WO2018216939A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070112134A1 (en) * 2005-11-15 2007-05-17 Fujifilm Corporation Colored curable composition, color filter and method of producing thereof
KR20120084253A (en) * 2011-01-19 2012-07-27 제이에스알 가부시끼가이샤 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device, and compound and polymer used for producing the same
KR20170030045A (en) * 2015-09-08 2017-03-16 주식회사 엘지화학 Polymer for liquid crystal aligning agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070112134A1 (en) * 2005-11-15 2007-05-17 Fujifilm Corporation Colored curable composition, color filter and method of producing thereof
KR20120084253A (en) * 2011-01-19 2012-07-27 제이에스알 가부시끼가이샤 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device, and compound and polymer used for producing the same
KR20170030045A (en) * 2015-09-08 2017-03-16 주식회사 엘지화학 Polymer for liquid crystal aligning agent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUAN, Y. ET AL.: "Highly Refractive Polyimides Containing Pyridine and Sulfur Units: Synthesis and Thermal, Mechanical, Solubility and Optical Properties", POLYMER INTERNATIONAL, vol. 66, 3 April 2017 (2017-04-03), pages 1044 - 1054, XP055559417 *
JUNG, JONG-MO ET AL.: "Characterization of Polyimimide: Application of Hydrolysis and Reactive-pyrolysis for Composition Analysis", POLYMER SCIENCE AND TECHNOLOGY, vol. 16, no. 1, 2005, pages 93 - 100 *

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