WO2008053848A1 - Agent pour traitement d'alignement d'un cristal liquide et élément de dispositif d'affichage à cristaux liquides utilisant celui-ci - Google Patents

Agent pour traitement d'alignement d'un cristal liquide et élément de dispositif d'affichage à cristaux liquides utilisant celui-ci Download PDF

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WO2008053848A1
WO2008053848A1 PCT/JP2007/071045 JP2007071045W WO2008053848A1 WO 2008053848 A1 WO2008053848 A1 WO 2008053848A1 JP 2007071045 W JP2007071045 W JP 2007071045W WO 2008053848 A1 WO2008053848 A1 WO 2008053848A1
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Prior art keywords
liquid crystal
ring
aligning agent
carbon atoms
component
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PCT/JP2007/071045
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English (en)
Japanese (ja)
Inventor
Kazuyoshi Hosaka
Kohei Goto
Noritoshi Miki
Kenzo Yada
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Nissan Chemical Industries, Ltd.
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Priority to JP2008542107A priority Critical patent/JP5218062B2/ja
Priority to CN200780040292XA priority patent/CN101600989B/zh
Priority to KR1020097008679A priority patent/KR101455418B1/ko
Publication of WO2008053848A1 publication Critical patent/WO2008053848A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1525—Four-membered rings
    • 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
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film, and a liquid crystal display element using the same.
  • a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction.
  • the main liquid crystal alignment film that is industrially used is produced by applying a polyimide-based liquid crystal alignment treatment agent composed of a polyimide precursor, a polyamic acid or a polyimide solution, onto a substrate, and forming a film.
  • a surface stretching process is further performed by rubbing after film formation.
  • a method using an anisotropic photochemical reaction such as irradiation with polarized ultraviolet rays has been proposed. In recent years, studies for industrialization have been conducted.
  • the liquid crystal alignment film is used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal, the performance of the liquid crystal display element becomes higher, and the range of use expands year by year. Among them, the stability of the pretilt angle which is not just a predetermined pretilt angle can be obtained.
  • liquid crystal display elements in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is sometimes isotropically treated by heat treatment after sealing the liquid crystal. If the pretilt angle stability is low, if the pretilt angle of the desired size cannot be obtained after this isotropic treatment, or if the pretilt angle has a variation force S! /, Problems arise.
  • liquid crystal display elements that use a backlight that generates a large amount of heat to obtain high brightness and liquid crystal display elements that are used in in-vehicle applications, such as car navigation systems.
  • the one panel may be used or left in a high temperature environment for a long time. Under such severe conditions, if the pretilt angle changes gradually, problems such as failure to obtain initial display characteristics and uneven display may occur.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-234410
  • the present invention has been made in view of the above circumstances, and its problem is to provide a liquid crystal aligning agent having excellent pretilt angle stability even under a high temperature environment for a long time, and pretilt. To provide a liquid crystal display element with little change in corners and excellent display reliability.
  • the present invention also provides a liquid crystal aligning agent that does not deteriorate the alignment of the liquid crystal even under weak rubbing conditions, that is, regardless of the rubbing conditions. Make it an issue
  • the present invention has the following gist.
  • a liquid crystal aligning agent containing the following (i) component and (ii) component.
  • At least one polymer selected from the group consisting of polyamic acid and polyimide (ii) A crosslinkable compound having at least two oxetane groups represented by the following formula [1] in the molecule.
  • X represents N, NH, CO, 0, S, SO, Si, cinoresesquioxane, polysiloxa
  • an organic group having 1 to 20 carbon atoms and the organic group may contain a heteroatom (N, 0, S, Si).
  • X and X are each independently , Single bond, NH, CO, 0,
  • Y are each independently a carbon number
  • n and n each independently represents an integer of 0 to 20, and may contain heteroatoms (N, 0, S, Si). And m + n is an integer from 2 to 20)
  • X and X are each independently a single bond, NH, CO, 0, S, SO, or
  • 2 3 2 represents an organic group having 2 to 2 carbon atoms;! -20, and the organic group may contain heteroatoms (N, 0, S, Si). Y and Y are independent of each other. Indicating an organic group with 20 to 20 carbon atoms
  • the organic group may contain hetero atoms (N, 0, S, Si).
  • Z is a single bond, NH, N (CH), NHCO, CONH, NHCONH, CO, COO , 0, S, SO, CF,
  • X is NH, N (CH), NHCO, CONH, NHCONH, CO, COO, OC
  • Y and Y each independently represent an alkyl group having carbon number;! -10
  • M and n are integers from 0 to 20, and m + n is an integer from 2 to 20.
  • liquid crystal aligning agent according to any one of (1) to (6) above, further containing an organic solvent.
  • liquid crystal alignment treatment agent of the present invention By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film having excellent pretilt angle stability can be obtained even under a high temperature environment for a long time, and a liquid crystal display element having this liquid crystal alignment film Is excellent in reliability.
  • the liquid crystal alignment treatment agent of the present invention is particularly useful in applications that require rubbing treatment because the orientation of the liquid crystal does not decrease even under weak rubbing conditions in which the stretchability of the polymer by rubbing is difficult to be inhibited. is there.
  • the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide.
  • the specific structures of the polyamic acid and polyimide are not particularly limited, and may be, for example, polyamic acid or polyimide contained in a known liquid crystal aligning agent.
  • the polyamic acid can be easily obtained by reacting tetracarboxylic acid or a tetracarboxylic acid derivative with diamine.
  • the method for producing the polyamic acid and polyimide as the component (A) used in the present invention is not particularly limited.
  • a polycarboxylic acid is reacted with a tetracarboxylic acid component selected from tetracarboxylic acids and derivatives thereof and a diamine component consisting of one or more diamine compounds to form a polyamic acid.
  • a method is used in which the polyamic acid is imidized to form a polyimide.
  • the polyamic acid obtained is obtained by using a force S to make a monopolymer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.
  • tetracarboxylic acid and its derivatives are tetracarboxylic acid, tetracarboxylic acid dihalide, and tetracarboxylic dianhydride.
  • tetracarboxylic dianhydride is preferred because it has a high reactivity with diamine compounds! /.
  • Examples include tetracarboxylic acids such as 5, 9, and 10 tetracarboxylic acids. Furthermore, these dicarboxylic acid tetrahalides and dianhydrides of tetracarboxylic acids can be mentioned. [0018] Particularly for liquid crystal alignment film applications, alicyclic tetracarboxylic acids and their dianhydrides and their dicarboxylic acid diacid halides are particularly preferred from the viewpoint of transparency of the coating film.
  • the tetracarboxylic acid and its derivatives exemplified above are used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding characteristics, accumulated charges, etc. in the case of forming a liquid crystal alignment film. It ’s the power to do.
  • the diamine used for the polyamic acid synthesis reaction is not particularly limited.
  • diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a complex ring, and a macrocyclic substituent comprising them in the diamine side chain can be exemplified.
  • R represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group
  • R is CO ⁇ , OC ⁇ , C ⁇ NH, NHCO, CH, ⁇ , CO, or
  • NH represents R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkyl group
  • R represents ⁇ , OCH, CH ⁇ , COOCH, or CHOC ⁇ .
  • R represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group.
  • R represents COO, OCO, CONH, NHCO, COOCH, C
  • R is alkyl having 1 to 22 carbon atoms
  • R represents COO, OCO, CONH, NHCO, COOCH, CH
  • R is a fluorine group, cyan group, trif
  • diaminosiloxanes represented by the following formula [A21] can also be mentioned.
  • the above-mentioned jamines can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
  • a raw material having a hydroxyl group or a carboxyl group among the above-described raw materials for synthesizing a polyamic acid can increase the reaction efficiency between the polyamic acid or polyimide and a crosslinkable compound described later.
  • Specific examples of such raw materials include 2,5 diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzol alcohol, 2,4 diaminophenol.
  • R represents COO, OCO, CONH, NHCO, CH, 0, CO, or Represents NH
  • R represents COO, OCO, CONH
  • H represents O OCO, CH 0, OCH, CH, 0, or NH
  • R represents a hydroxyl group or a carboxy group.
  • the organic solvent used for synthesizing the polyamic acid is not particularly limited as long as the produced polyamic acid can be dissolved.
  • Specific examples include N, N dimethylenoformamide, N, N dimethylacetamide, N methyl 2-pyrrolidone, N methylcaprolatatam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, ⁇ Butyrolatatone, isopropyl alcohol, methoxymethyl pentanol mononole, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethino ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl bitanol, ethino recanole bittone, ethylene glycol Ethylene glycol mononomonoacetate, ethylene
  • a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent within a range where the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes the resulting polyamic acid to hydrolyze, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • a method of reacting tetracarboxylic acid and its derivative with diamine in an organic solvent when synthesizing polyamic acid the solution in which diamine is dispersed in an organic solvent is stirred, and the tetracarboxylic acid and dicarboxylic acid are stirred.
  • a method in which the derivative is added as it is or after being dispersed or dissolved in an organic solvent and conversely, a method in which diamine is added to a solution in which tetracarboxylic acid and its derivative are dispersed or dissolved in an organic solvent, tetracarboxylic acid and its Examples thereof include a method of alternately adding a derivative and diamine. Any of these methods may be used.
  • tetracarboxylic acid and its derivatives or diamines when they are composed of a plurality of types of compounds, they may be reacted in a premixed state or individually, or they may be reacted individually, and further reacted individually. May be mixed to form a high molecular weight product.
  • the temperature at which the polyamic acid is synthesized is a force capable of selecting an arbitrary temperature of -20 ° C to 150 ° C, and preferably -5 ° C to 100 ° C.
  • the reaction can be performed at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the reaction solution becomes too viscous and uniform stirring is difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction may be performed at a high concentration, and then an organic solvent may be added.
  • the ratio of the number of moles of the diamine component to the number of moles of the tetracarboxylic acid and its derivative is 0.8 to 1.2; A force of 1 is preferable. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • Catalytic imidation can be performed by stirring polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the reaction temperature at this time is 120 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times that of the amic acid group, and the amount of the acid anhydride is !! to 50 mol times, preferably 3 to 30 mole times. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it is difficult to completely remove the reaction after the reaction is completed.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the organic solvent is not limited as long as it dissolves the polyamic acid. Specific examples include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, dimethylsulfoxide, tetramethyl. Urea, dimethinolesnorephone, hexamethinoresnorexoxide, ⁇ -butyrolatatone, etc.
  • the imidization rate by catalytic imidation is controlled by the control force S by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the produced polyimide can be obtained by charging the reaction solution into a poor solvent and collecting the produced precipitate.
  • the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polyimide deposited in a poor solvent and filtered can be powdered by filtering at normal temperature or reduced pressure at room temperature or by heating.
  • the polyimide powder can also be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating 2 to 10 times. It is preferable to carry out this purification process when impurities cannot be removed by a single precipitation recovery operation!
  • the molecular weight of the specific polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight from the viewpoints of handling and stability of characteristics when a film is formed, and more Preferably, it is 4,000-50,000. It is determined by molecular weight (also GPC (genore- nomi-emission chromatography).
  • liquid crystal aligning agent of the present invention has the following formula in the molecule.
  • crosslinkable compound having at least two oxetane groups represented by [1] hereinafter referred to as a specific crosslinkable compound.
  • an oxetane group reacts with a carboxyl group or a hydroxyl group in the presence of heat or an acid catalyst. Therefore, a specific crosslinkable compound reacts with a carboxyl group or a hydroxyl group contained in polyamic acid or polyimide to form a film crosslinked between polymers. Further, The oxetane group causes a self-polymerization reaction in addition to the reaction with a carboxyl group or a hydroxyl group. In particular, since the oxetane group has a higher nucleophilicity than the epoxy group, a polymer having a high final conversion and a high degree of polymerization can be obtained. That is, the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention is a film having high heat resistance due to a polymer formed by cross-linking between polymers and self-polymerization of oxetane groups.
  • the oxetane group has a four-membered ring structure, when it reacts with a carboxyl group or a hydroxyl group and when it self-polymerizes, a methylene group is present at the bonding site compared to an epoxy group that has a three-membered ring structure One more. Therefore, the film obtained from the liquid crystal aligning agent of the present invention has high toughness when stretched as compared with a film using an epoxy-based crosslinkable compound, so that the stretchability of the polymer by rubbing is inhibited. It is hard to be done.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is more stable to the heat of the pretilt angle than the liquid crystal alignment film containing no crosslinkable compound or the liquid crystal alignment film containing an epoxy crosslinkable compound. And the liquid crystal orientation does not deteriorate even under weak rubbing conditions.
  • the number of oxetane groups possessed by the specific crosslinkable compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 50, more preferably 2 ⁇ 20.
  • the specific structure of the specific crosslinkable compound is not particularly limited, and examples thereof include a compound represented by the following formula [2].
  • X represents N, NH, CO, 0, S, SO, Si. Cinolesesquioxane, polysiloxa
  • the organic group having 1 to 20 carbon atoms may contain a heteroatom (N, 0, S, Si).
  • the organic group having 1 to 20 carbon atoms of X may include an organic group having a cyclic structure. Specifically, cyclopropane ring, cyclobutane ring, cyclo Pentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cyclohe Ptadecane ring, cyclodecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tri
  • 2 3 2 represents an organic group having a prime number !!-20, and the organic group may contain a heteroatom (N, 0, S, Si).
  • Y and Y are each independently an organic compound having a carbon number;! To 20, preferably 1 to 15 carbon atoms.
  • a hetero atom N, 0, S, Si
  • N, 0, S, Si a hetero atom
  • n and n each independently represents an integer of 0 to 20, preferably 0 to 15; and m + n represents an integer of 2 to 20, preferably 2 to 15;
  • X force N, NH, CO 2, 0, silsesquioxane, polysiloxane, or an organic group having 1 to 10 carbon atoms is preferable.
  • the organic group may contain heteroatoms (N, O), and the carbon number of X;!
  • To 10 organic groups include cyclohexane ring, benzene ring, naphthalene Ring, fluorene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, force rubazole ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, or quinoxaline ring
  • An organic group having may be contained.
  • X and X Each independently NH, CO, COO, OCO, 0, CONH, or NHCO, and Y and ⁇ are each independently an alkyl group having 1 to 10 carbon atoms, m, n Respectively
  • n is an integer of 2 to 20.
  • Examples include a structure selected from S 1] to [S4].
  • polysiloxane having at least one structure selected from the group consisting of general formulas [P 1], [P2], [P3], and [P4].
  • R, R, R, R and R in the formulas [P 1] to [P4] are each independently a hydrogen atom or a hydroxyl group
  • a group having 1 to 10 carbon atoms a group selected from an alkyl group, an alkoxy group, an aliphatic ring group, or an aromatic ring group.
  • formula [2] include structures of the following formulas [3] to [8].
  • X and X are each independently a single bond, NH, CO, 0, S, SO, or
  • 2 3 2 Indicates an organic group having 2 to 2 carbon atoms,! ⁇ 20, and the organic group may contain a heteroatom (N, 0, S, Si). Y and Y are independent of each other. Carbon number;! ⁇ 20, preferably charcoal
  • a prime number;! To 15 represents an organic group, and the organic group may include a heteroatom (N, 0, S, Si).
  • Z is a single bond, NH, N (CH), NHCO, CONH, NHCONH, CO, C 00, 0, S, SO, CF, C (CF), Si (CH), OSi (CH), Si (CH) 0, OSi (C
  • H 0 or an alkyl group having 1 to 10 carbon atoms; m and n are each independently 0 to 5
  • n is an integer of 2 to 10, preferably an integer of 2 to 6.
  • M and n are each independently an integer of 0 to 5, preferably an integer of 0 to 3, and m + n is an integer of 2 to; an integer of 10 and preferably an integer of 2 to 6.
  • X is MH, N (CH), NHCO, CONH, NHCONH, CO, COO, O
  • Y and Y each independently represent an alkyl group having carbon atoms;! -10
  • An alkyl group having 1 to 5 carbon atoms is preferred.
  • X in the formula [5] is N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or charcoal
  • An alkylene having 1 to 20 prime atoms preferably N, an aliphatic ring having 1 to 15 carbon atoms, an aromatic ring having 1 to 15 carbon atoms, or an aromatic ring having 1 to 15 carbon atoms, or an alkylene having 1 to 15 carbon atoms, more preferably
  • X is N, an aliphatic ring having 1 to 10 carbon atoms, an aromatic ring having 1 to 10 carbon atoms, or an alkylene having 1 to 10 carbon atoms.
  • Y and Y in the formula [5] each represents an alkyl group having! To 10 carbon atoms, preferably,
  • Each is an alkyl group having 1 to 5 carbon atoms.
  • M and n in the formula [5] represent an integer of 0 to 20, and m + n is an integer of 2 to 20.
  • m and n are integers from 0 to 15, and m + n is an integer from 2 to 15. More preferably, m and n represent an integer of 0 to 0, and m + n is an integer of 2 to 10;
  • M and n are integers from 0 to 20, and m + n is an integer from 2 to 20.
  • X is N, an aliphatic ring having 1 to 15 carbon atoms, an aliphatic ring having 1 to 15 carbon atoms, an aromatic ring having 15 carbon atoms or an alkylene having 1 to 15 carbon atoms, and Y and Y each have 1 to 5 alkyl
  • X is N, an aliphatic ring having 1 to 10 carbon atoms, an aliphatic ring having 1 to 10 carbon atoms, an aromatic ring having 10 carbon atoms or an alkylene having 1 to 10 carbon atoms, and Y and Y are each a carbon number. ;! ⁇ 5 al
  • n is an integer from 0 to 10 and m + n is an integer from 2 to 10;
  • Examples of the aliphatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclodecane ring, a cyclododecane ring, and a cyclotridecane.
  • aromatic ring examples include decahydronaphthalene ring, benzene ring, naphthalene ring, tetrahydro Naphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, azole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline Ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, phenanthorin ring
  • Y and Y are each independently an alkyl group having 1 to 10 carbon atoms, preferably
  • n is an integer of 1 to 10, preferably an integer of 1 to 5.
  • Y and ⁇ ⁇ ⁇ ⁇ are each independently an alkyl group having from 10 to 10 carbon atoms, preferably
  • a C1-C5 alkyl group is shown, (eta) is an integer of 1-10, Preferably an integer of 1-5 is shown.
  • ⁇ and ⁇ are each independently an alkyl group having 1 to 10 carbon atoms, preferably carbon
  • a prime number is an alkyl group having 1 to 5, and ⁇ is an integer of 1 to 10, preferably an integer of 1 to 5. More specific specific crosslinkable compounds include compounds of the formulas [9] to [; 19].
  • the said compound is an example of a specific crosslinkable compound, It is not limited to these. Further, the specific crosslinkable compound contained in the liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.
  • the content of the component (B) (specific crosslinkable compound) is 0. with respect to 100 parts by mass of the component (A) (polymer component) made of polyamic acid and / or polyimide. It is more preferably 0.;! To 100 parts by mass in order that a crosslinking reaction that preferably proceeds to 150 parts by mass proceeds to produce the desired film curability and does not deteriorate the orientation of the liquid crystal. , In particular;! ⁇ 50 parts by weight.
  • the liquid crystal aligning agent of the present invention is not particularly limited, but it is usually necessary to form a uniform thin film of 0.01 to 1.0 m on the substrate when preparing the liquid crystal alignment film. Therefore, the coating solution preferably contains an organic solvent that dissolves these components in addition to the components (A) and (B).
  • the liquid crystal aligning agent of the present invention contains the organic solvent, from the viewpoint of forming a uniform thin film by coating, the content of the organic solvent is liquid crystal alignment. In the treatment agent, it is preferably 90 to 99% by mass, more preferably 92 to 97% by mass.
  • the content of component (A) is preferably 0.4 to 9.9% by mass, particularly preferably 0.5 to 9.9% by mass, and the content of component (B) is preferably 0. ;! ⁇ 9.6 mass%, particularly preferably 0.;! ⁇ 9.5 mass%.
  • organic solvent to be contained in the liquid crystal aligning agent of the present invention include organic solvents used in the above-described synthesis reaction of polyamic acid. Particularly preferred are N 2, N dimethylformamide, N, N dimethylacetamide, N methyl 2-pyrrolidone, dimethyl sulfoxide, and ⁇ -butyrolatatone. These organic solvents may be used alone or in combination of two or more.
  • ethilce mouth solve, butyno cerero sonoreb, ethinorecanolebitonore, butinorecanolebitonore, diethyleneglyconoresi Ethenoleethenore, Diethyleneglycolenomethinoretinotenole, Diethyleneglycolenoremo Nobuchinoleetenore, Ethinorecanolebitonoreacetate, Ethyleneglycolanol, Ethyleneglycolmonohexylether, 1-methoxy-2- Propanol, 1 Ethoxy-2-Prono Norole, 1-Butoxy-1-2-Prono Norole, 1-Phenoxy 2-Prono Norole, Propyrendalol Monoacetate, Propylene Glycol Diacetate, Propylene Glycol Monore 1 Monomethinoreate Nore 2 —Acetate, propylene
  • the liquid crystal aligning agent of the present invention contains the component (A), the component (B), and the organic solvent as well as the additive component as long as the effect of the present invention is not impaired. You can be! / Examples of the additive component include a compound for improving the adhesion between the liquid crystal alignment film and the substrate, and a surfactant for improving the flatness of the coating film.
  • Specific examples of the compound that improves the adhesion between the coating film and the substrate include the following.
  • Examples of the surfactant for improving the flatness of the coating film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafuk F171, F173, R-30 (above, manufactured by Dainippon Ink), Florad FC430, FC431 ( (Made by Sumitomo 3EM), Asahi Guard AG710, Surflon S-382, SC101, SC 102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Shishiko).
  • the ratio of these surfactants to be used is preferably 0.0;! To 2 parts by mass, more preferably 0.0;! To 1 part by mass with respect to 100 parts by mass of the polymer component.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. .
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate; a plastic substrate such as an acrylic substrate or a polycarbonate substrate; it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process.
  • a reflective liquid crystal display element an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used according to the purpose.
  • Firing after applying the liquid crystal aligning agent can be performed at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 150 to 250 ° C. This firing can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
  • the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. , More preferably 10 to! OOnm.
  • the baked coating film is treated with rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method. It is.
  • a pair of substrates with a liquid crystal alignment film is prepared.
  • the thickness of the spacer at this time is preferably;! -30 m, more preferably 2--10 ⁇ m.
  • the liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a liquid crystal display device having excellent pretilt angle stability, including a TN element, STN element, TFT liquid crystal element, Furthermore, it is useful for a vertical alignment type liquid crystal display element.
  • CBDA 1, 2, 3, 4 cyclobutane tetracarboxylic dianhydride
  • DADPA 4, 4'-diaminodiphenylamine
  • Oxetane C (OX-SC)
  • Epoxy A YH-434L (manufactured by Tohto Kasei)
  • Epoxy B Epolide GT-401 (4-functional alicyclic epoxy resin) (manufactured by Daicel Chemical Industries); modified with epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) ⁇
  • the molecular weight of polyimide in the synthesis example is
  • Standard samples for preparing calibration curves TSK standard polyethylene oxide (molecules !: approx. 9000,000, 150,000, 100,000, 30,000) manufactured by Tosohichi Co., Ltd. and polyethylene glycol (molecular weight approx. ).
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard ⁇ 5 mm, manufactured by Kusano Kagaku Co., Ltd.) and mix with deuterated dimethyl sulfoxide (DMSO-d, 0.05% TMS)
  • NMR sample tube NMR sampling tube standard ⁇ 5 mm, manufactured by Kusano Kagaku Co., Ltd.
  • DMSO-d deuterated dimethyl sulfoxide
  • X is the accumulated proton peak value derived from the NH group of the amic acid
  • y is the accumulated peak value of the reference proton
  • ⁇ is the aprotic group proton of the amic acid in the case of polyamic acid (imidation rate is 0%) 1 This is the ratio of the number of reference protons to one.
  • CBDA (5.lg, 26.Ommol), p-PDA (2.53g, 23.4mmol), AP18 (0.98g, 2.6 mmol) were mixed in NMP (81.5g) at 25 ° C. The mixture was reacted for 6 hours to obtain a polyamic acid solution (A).
  • the number average molecular weight of this polyamic acid solution (A) was 22000, and the weight average molecular weight was 78900.
  • CBDA (3.04 g, 15.5 mmol), p—PDA (1.56 g, 14.4 mmol), PCH (0.61 g, 1.6 mmol) were mixed in NMP (22. Og) at 25 ° C. The mixture was reacted for 5 hours to obtain a polyamic acid solution (B).
  • This polyamic acid solution (B) had a number average molecular weight of 25,000 and a weight average molecular weight of 94,000.
  • BODA (16.9 g, 68 mmol), p-PDA (8. 74 g, 81 mmol), PCH (3.43 g, 9 mmol) were mixed in NMP (100. lg) and reacted at 40 ° C for 3 hours. Thereafter, CBDA (4. lg, 21 mmol) and NMP (52.2 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution (C).
  • the number average molecular weight of this polyamic acid (C) was 20500, and the weight average molecular weight was 76500.
  • (E) was obtained.
  • the imidation ratio of this polyimide was 54%, the number average molecular weight was 18300, and the weight average molecular weight was 45300.
  • the coating surface is rubbed with a roll diameter of 120mm and a rayon cloth rubbing device under the conditions of a rotation speed of 70 Orpm, a moving speed of 40mm / sec, and an indentation amount of 0.3mm.
  • a substrate with a liquid crystal alignment film was obtained. Prepare two substrates with a liquid crystal alignment film, sandwich the 50 m spacer with the liquid crystal alignment film surface on the inside, combine them so that the rubbing direction is reversed, and bond the periphery with a sealant. An empty cell was prepared. Liquid crystal ZLI-2293 (manufactured by Merck & Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an antiparallel aligned nematic liquid crystal cell.
  • the pretilt angle (degrees) at the initial stage after the liquid crystal injection and after the heat treatment at 120 ° C for 5 hours was measured with a pretilt angle measuring device (Model PA S-301, manufactured by ELSICON). ) At room temperature. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • Oxetane (A) (0.06 g), NMP (4.05 g), and BCS (2.35 g) were added to the polyamic acid solution (A) (6.05 g) obtained in Synthesis Example 1, and the mixture was stirred.
  • An alignment agent [2] was obtained.
  • a liquid crystal cell was prepared in the same manner as in Example 1, and the heat treatment was performed at 120 ° C. for 5 hours at the initial stage after the liquid crystal was injected at an indentation amount of 0.3 mm. The subsequent pretilt angle was measured.
  • the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.
  • the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure. Table 1 shows the measurement results of the pretilt angle.
  • the pretilt angle was measured at the initial stage after the liquid crystal injection and after the heat treatment for 5 hours at 120 ° C. As a result of confirming the alignment uniformity of the liquid crystal by observation with a polarizing microscope, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • liquid crystal alignment treatment agent [4] Using the obtained liquid crystal alignment treatment agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and heat treatment was performed at 120 ° C. for 5 hours at the initial stage after injecting the liquid crystal at an indentation amount of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.
  • Table 1 shows the measurement results of the pretilt angle.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was prepared using the obtained liquid crystal aligning agent [6] in the same manner as in Example 1, and heat treatment was performed at 120 ° C for 5 hours at the initial stage after injecting the liquid crystal at a pushing amount of rubbing treatment of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.
  • Table 1 shows the measurement results of the pretilt angle.
  • the obtained liquid crystal alignment treatment agent [7] was used! A liquid crystal cell was prepared in the same manner as in Example 1 and the initial stage after liquid crystal injection at a rubbing treatment push amount of 0.3 mm, at 120 ° C for 5 hours. The pretilt angle after the heat treatment was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.
  • Table 1 shows the measurement results of the pretilt angle.
  • Epoxy (A) (0. l lg), N MP (4. 75 g), and BCS (2.52 g) were added to the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1 and stirred.
  • a liquid crystal aligning agent [8] was obtained.
  • a liquid crystal cell was prepared using the obtained liquid crystal aligning agent [8] in the same manner as in Example 1, and the initial stage after injecting the liquid crystal at a rubbing amount of 0.3 mm, after heat treatment at 120 ° C. for 5 hours.
  • the pretilt angle was measured.
  • a so-called fluid alignment was observed in which the liquid crystal was aligned in the direction in which the crystals flowed. Furthermore, this flow orientation did not disappear at each stage after the heat treatment, and in addition, a disclination line was generated by the heat treatment. Because of such alignment failure, the pretilt angle of this liquid crystal cell could not be measured.
  • Table 1 shows the measurement results of the pretilt angle.
  • Epoxy (A) (0.06 g), N MP (4.03 g), BCS (2.34 g) were added to the polyamic acid solution (A) (6.05 g) obtained in Synthesis Example 1 and stirred.
  • a liquid crystal aligning agent [9] was obtained.
  • a liquid crystal cell was prepared in the same manner as in Example 1, and the initial stage after injecting the liquid crystal at a rubbing amount of 0.3 mm, after heat treatment at 120 ° C. for 5 hours.
  • the pretilt angle was measured.
  • the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.
  • the liquid crystal with no alignment failure was uniformly aligned, but a disclination line was generated after heating at 120 ° C for 5 hours. did. For this reason, it was impossible to measure the pretilt angle of the liquid crystal cell after heating at 120 ° C for 5 hours.
  • Table 1 shows the measurement results of the pretilt angle.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [11] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [12] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • the pretilt angle was measured at the initial stage after the liquid crystal injection and after the heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [13] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.
  • Table 1 shows the measurement results of the pretilt angle. [0113] (Example 9)
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [14] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was prepared in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [15] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [16] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Then press the rubbing process The pretilt angle was measured at the initial stage after liquid crystal injection at a depth of 0.3 mm and after heat treatment at 120 ° C for 5 hours. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell. The liquid crystal was uniformly aligned.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [17] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell. The liquid crystal was uniformly aligned.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [18] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [19] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • NMP (17.7 g) was added to the polyimide powder (G) (3.00 g) obtained in Synthesis Example 7, and stirred at 80 ° C. for 40 hours for dissolution.
  • NMP (4.35 g) and BCS (25. lg) were added and stirred to obtain a liquid crystal aligning agent [20].
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [20] was used and the liquid crystal was MLC-6608 (manufactured by Merck & Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [21] was used and the liquid crystal was MLC-6608 (manufactured by Merck & Japan).
  • the plethys after the heat treatment at 120 ° C. for 5 hours.
  • the tilt angle was measured.
  • so-called fluid alignment was observed in which the liquid crystal was aligned in the direction in which the liquid crystal flowed when the liquid crystal was injected.
  • this flow orientation was not canceled at each stage after the heat treatment, and in addition, a discrimination line was generated by the heat treatment. Because of such alignment failure, it was not possible to measure the pretilt angle of this liquid crystal senore.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [22] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [23] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • a liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [24] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.
  • Table 1 shows the measurement results of the pretilt angle.
  • each pretilt angle is an average value obtained by measuring the center of the liquid crystal cell and the upper and lower lcm points.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has a specific cross-linking.
  • the orientation of the liquid crystal was not changed, and The pretilt angle after high-temperature treatment changed by less than 1 degree, and the stability of the pretilt angle was greatly improved.
  • liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film excellent in the stability of the pretilt angle of the liquid crystal can be obtained.
  • the liquid crystal display element having this liquid crystal alignment film has excellent reliability, it is useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.

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Abstract

L'invention concerne un agent pour le traitement d'alignement d'un cristal liquide, qui a un angle de pré-inclinaison extrêmement stabilisé. L'invention concerne également un élément de dispositif d'affichage à cristaux liquides qui a moins de changement dans un angle de pré-inclinaison et a également une excellente fiabilité d'affichage. L'agent pour le traitement d'alignement d'un cristal liquide comprend au moins un polymère choisi dans le groupe consistué par l'acide polyamique et le polyimide et un composé réticulable ayant au moins deux groupes oxétane représentés par la formule [I] dans la molécule.
PCT/JP2007/071045 2006-11-01 2007-10-29 Agent pour traitement d'alignement d'un cristal liquide et élément de dispositif d'affichage à cristaux liquides utilisant celui-ci WO2008053848A1 (fr)

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JP2008542107A JP5218062B2 (ja) 2006-11-01 2007-10-29 液晶配向処理剤及びそれを用いた液晶表示素子
CN200780040292XA CN101600989B (zh) 2006-11-01 2007-10-29 液晶定向处理剂及使用了该处理剂的液晶显示元件
KR1020097008679A KR101455418B1 (ko) 2006-11-01 2007-10-29 액정 배향 처리제 및 그것을 사용한 액정 표시 소자

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JP2008191655A (ja) * 2007-01-09 2008-08-21 Jsr Corp 液晶配向剤および液晶表示素子
JP2009300465A (ja) * 2008-06-10 2009-12-24 Jsr Corp 液晶配向剤および液晶表示素子
WO2011078132A1 (fr) * 2009-12-25 2011-06-30 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
EP3054345A1 (fr) * 2015-02-09 2016-08-10 Samsung Display Co., Ltd. Unité d'affichage à cristaux liquides

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KR101988067B1 (ko) * 2011-12-28 2019-06-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 표시 소자, 액정 표시 소자의 제조 방법 및 중합성 화합물
WO2016076413A1 (fr) * 2014-11-13 2016-05-19 日産化学工業株式会社 Agent de traitement servant à l'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
CN108034434A (zh) * 2017-12-19 2018-05-15 深圳市华星光电技术有限公司 热聚合自取向液晶材料及液晶显示面板的制作方法
TWI679217B (zh) * 2018-03-02 2019-12-11 達興材料股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件

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KR101455418B1 (ko) 2014-10-27
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JP5218062B2 (ja) 2013-06-26
CN101600989A (zh) 2009-12-09
TW200841093A (en) 2008-10-16
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JPWO2008053848A1 (ja) 2010-02-25

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