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WO2019139115A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2019139115A1
WO2019139115A1 PCT/JP2019/000652 JP2019000652W WO2019139115A1 WO 2019139115 A1 WO2019139115 A1 WO 2019139115A1 JP 2019000652 W JP2019000652 W JP 2019000652W WO 2019139115 A1 WO2019139115 A1 WO 2019139115A1
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Prior art keywords
liquid crystal
group
aligning agent
crystal aligning
formula
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English (en)
Japanese (ja)
Inventor
奈穂 国見
正人 森内
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Nissan Chemical Corp
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Nissan Chemical Corp
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element which give a liquid crystal aligning film excellent in voltage holding characteristics of a liquid crystal cell.
  • a general liquid crystal display element is configured by sandwiching a liquid crystal which changes direction in response to an electric field between a pair of transparent substrates provided with electrodes for applying the electric field to the liquid crystal.
  • a liquid crystal aligning film is one of the members which comprise a liquid crystal display element, Comprising: It is formed in the surface which contact
  • a rubbing method in which the surface of an organic film formed on a substrate is rubbed with a cloth on which fibers such as cotton, nylon and polyester are flocked is formed in a fixed direction, an organic film formed on a substrate
  • An optical alignment method is known which imparts anisotropy to a film structure by irradiating the film with polarized ultraviolet light.
  • a decomposition type photoalignment method is known as one of the above photoalignment methods.
  • it is a method in which a polyimide film is irradiated with polarized ultraviolet light, anisotropic decomposition is caused by utilizing the polarization direction dependency of ultraviolet absorption of molecular structure, and liquid crystal is aligned with polyimide left without decomposition.
  • Patent Document 1 See, for example, Patent Document 1).
  • a method of forming a polyimide film for forming a liquid crystal alignment film on a substrate a method of applying a liquid crystal alignment agent containing polyamic acid which is a polyimide precursor on a substrate and baking it to form a polyimide film, or solvent solubility
  • a liquid crystal aligning agent containing an imide group containing polyamic acid using an imide group containing diamine is coated on a substrate other than a method of applying a liquid crystal aligning agent containing a polyimide on a substrate and removing a solvent to form a polyimide film.
  • Methods are known (see, for example, Patent Document 2).
  • the liquid crystal display element which can endure a long time use has been required.
  • the liquid crystal alignment film in which the display characteristics do not largely change by the irradiation of the back light has come to be required.
  • the liquid crystal alignment film produced by the step of applying and drying a liquid crystal aligning agent containing a polyamic acid on a substrate, and then irradiating it with polarized ultraviolet light and then baking does not necessarily have sufficient stability of the liquid crystal alignment.
  • liquid crystal molecules are switched in-plane, so that alignment deviation of the liquid crystal after liquid crystal drive tends to occur, and good residual image characteristics can not be obtained due to this liquid crystal alignment deviation. There was a problem.
  • the first object of the present invention is to produce a liquid crystal alignment film by a photoalignment method, and still have a good voltage holding ratio even when the backlight light is continuously irradiated for a long time
  • Another object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film, and further providing a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having a small decrease in voltage holding ratio even when back light is applied for a long time.
  • a second object of the present invention is, in addition to the first object, a liquid crystal alignment film which can obtain a liquid crystal alignment film having good residual image characteristics even if it is a liquid crystal alignment film manufactured by a step of irradiating light and then baking. To provide the agent.
  • R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 is necessarily CH 3 or CF 3
  • W 1 and W 2 represent phenylene
  • phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, cyano Group, a dialkylamino group (the alkyl group is each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, or 1 carbon atom And may be substituted with a substituent selected from the group consisting of to 10 linear or branched acyl groups, carboxyl groups, aldehyde groups, nitro groups, and Boc-protected amino groups, L1 and L2 are
  • the liquid crystal aligning agent of said ⁇ 1> whose at least one of n1 and n2 is 0 in each of L1 and L2 of ⁇ 2> Formula (1).
  • the liquid crystal aligning agent of said ⁇ 1> whose value of n1 + n2 + m is an even number in each of L1 and L2 of ⁇ 3> Formula (1).
  • liquid crystal aligning agent according to any one of ⁇ 1> to ⁇ 3>, wherein 10 to 100 mol% in the diamine component is a diamine represented by the formula (1).
  • the liquid crystal alignment film obtained by the light alignment method from the liquid crystal alignment agent of this invention can obtain the liquid crystal display element which has a favorable voltage holding ratio, even if it continues irradiating back light for a long time.
  • the liquid crystal aligning agent of the present invention is a polymer selected from a polyamic acid obtained by using a diamine component containing a specific diamine and a tetracarboxylic acid dianhydride component and its imidate (hereinafter also referred to as a specific polymer), and It is a liquid crystal aligning agent containing an organic solvent. Each condition will be described in detail below.
  • the specific diamine used in the present invention is a diamine represented by the following formula (1).
  • R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 is necessarily one Represents CH 3 or CF 3 .
  • two of R 1 , R 2 , R 3 and R 4 are CH 3 and the remainder is H. More preferably, R 1 and R 4 or R 2 and R 3 are CH 3 and the remainder is H.
  • W 1 and W 2 represent phenylene, preferably 1,4-phenylene.
  • the phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group or a dialkylamino group (wherein Each alkyl group is independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, a linear or branched chain having 1 to 10 carbon atoms It may be substituted by a substituent selected from the group consisting of a branched chain acyl group, a carboxyl group, an aldehyde group, a nitro group, and a Boc-protected amino group.
  • the L1 and L2 independently, - (O) n1 - ( CH 2) m - (O) n2 - is a divalent group represented by 0 n1 and n2 independently Or 1 and m is an integer of 1 to 10.
  • m is an integer of 1 to 10.
  • n1 and n2 are 0 in each of L1 and L2 in the formula (1), from the viewpoint of less decrease in voltage holding ratio when the backlight is irradiated for a long time. That is, n1 + n2 is preferably 0 or 1 in each of L1 and L2. Taking the above structure as an example, the structure represented by the formula (1-1), (1-2) or (1-4) is preferable.
  • the formula ( In each of L1 and L2 of 1) the value of n1 + n2 + m is preferably an even number.
  • m is preferably an odd number in the formulas (1-1) and (1-2), and m is an even number in the formulas (1-3) and (1-4). Is preferred.
  • the diamine component for obtaining the specific polymer is a substance containing at least one kind of diamine represented by the above formula (1), may be one kind of diamine, and is composed of two or more kinds of diamines. It may be When a diamine component consists of two or more types of diamine, other diamine may be included with the diamine represented by Formula (1). It is preferable that the ratio of the diamine represented by Formula (1) in the diamine component for obtaining a specific polymer is 10 to 100 mol%, More preferably, it is 30 to 100 mol%, More preferably, it is 50 to 100 mol %.
  • the diamine used together with the diamine represented by Formula (1) is not particularly limited as a diamine component for obtaining a specific polymer, but for example, a diamine represented by the following Formula (2) and represented by the above Formula (1) And compounds other than.
  • Y is a divalent organic group, and more preferably a divalent organic group having 6 to 50 carbon atoms.
  • the organic group is, for example, a divalent hydrocarbon group, a carbon-carbon bond of a divalent hydrocarbon group, -O-, -COO-, -COS-, -CO-, -CONR a- , A hetero atom-containing group such as -S-, -NR a- , -SO 2- , -Si (R 8 ) 2 -or the like (provided that R a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 8 Is a monovalent hydrocarbon group having 1 to 12 carbon atoms)) or a divalent group having a heterocycle.
  • At least one of the hydrogen atoms bonded to a carbon atom may be substituted by a substituent.
  • substituents include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a nitro group, an amino group, a carboxyl group, a thiol group, -Si (R 9) 3 (provided that, R 9 Is a C 1-10 alkyl group or an alkoxy group, and a plurality of R 9 may be the same or different), an alkoxy group and the like.
  • hydrocarbon group is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • Chain hydrocarbon group means a hydrocarbon group composed of only a chain structure, which does not contain a cyclic structure in the main chain. However, the chain structure may be linear or branched, and may be saturated or unsaturated.
  • alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has chain structure in the part is also included.
  • aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or a structure of alicyclic hydrocarbon may be included in part thereof.
  • heterocycle examples include aliphatic heterocycles such as piperidine ring, piperazine ring, pyrrolidine ring, azetidine ring, oxetane ring and aziridine ring, pyrrole ring, furan ring, thiophene ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, iso 5-membered aromatic heterocycles such as oxazole ring, thiazole ring and isothiazole ring, 6-membered aromatic heterocycles such as pyridine ring, pyrimidine ring, pyridazine ring and pyrazine ring, polycyclic rings such as indole ring and benzimidazole ring Aromatic heterocycles and the like can be mentioned.
  • aliphatic heterocycles such as piperidine ring, piperazine ring, pyrrolidine ring, azetidine ring,
  • a preferred example of Y is preferably a divalent group containing one or more phenylene structures, and more preferably a divalent organic group selected from the following formulas (Y-1) to (Y-3).
  • R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or a methyl group is more preferable.
  • a 1 and A 4 are each independently a single bond, —O—, —CO—, —CO—O—, —OCO—, —NR— (R is a hydrogen atom, a methyl group, tert- Butoxycarbonyl group), -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or methyl) Group), -COS-, -NR 1 -CO-NR 2- (R 1 and R 2 each independently represent a hydrogen atom or a methyl group), -CH 2 -,-(CH 2 ) n - (n is an integer of 2-20), or the -.
  • n - any CH 2 is, -O -, - CO -, - CO-O -, - NRCO- ( R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group) , -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NQ 1 -CO-NQ 2- (Q 1 and Q 2 each independently represent a hydrogen atom or a methyl group.
  • R represents a hydrogen atom, a methyl group or a tert-butoxycarbonyl group
  • a 2 represents a halogen atom or a hydroxyl group
  • a 3 is a definition as given for A 1 or A 4 other than a single bond
  • a plurality of A 3 may be the same or different, a is an integer of 0 to 4, and when a is 2 or more, the structures of A 2 may be the same or different, b and c are Each of them is independently an integer of 1 to 2.
  • d is Or it is one of the integer.
  • the monovalent organic group having 1 to 10 carbon atoms in A 2 is, for example, an alkyl group having 1 to 3 carbon atoms such as a methyl group, a part or all of hydrogen atoms of the alkyl group having 1 to 3 carbon atoms.
  • Examples thereof include a group substituted with a halogen atom such as a fluorine atom and a chlorine atom, a group having —NHD, and a group having —N (D) 2 .
  • D represents a carbamate-based protecting group
  • examples of the carbamate-based protecting group include a tert-butoxycarbonyl group or 9-fluorenylmethoxycarbonyl group.
  • N is an integer of 1 to 5 And the like.
  • tetracarboxylic acid dianhydride component As a tetracarboxylic acid dianhydride component for obtaining a specific polymer, the compound represented by following formula (3) is mentioned.
  • the tetracarboxylic acid dianhydride component for obtaining a specific polymer may consist of one type of compound or may consist of two or more types of compounds.
  • A is a tetravalent organic group, preferably a tetravalent organic group having 4 to 30 carbon atoms.
  • the organic group means a group in which two hydrogen atoms are further removed from the above-described divalent organic group.
  • a tetravalent organic group having at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a benzene ring and a heterocyclic ring or a 1,2,3,4-butanetetracarboxylic acid dibasic It is a tetravalent organic group derived from an anhydride.
  • (A-1) and (A-2) are preferable from the viewpoint of further improvement of photoalignment, and (A-4) is preferable from the viewpoint of further improvement of the relaxation rate of accumulated charge, (A-15) to (A-17) are preferable from the viewpoint of further improving the liquid crystal alignment property and the relaxation rate of the accumulated charge.
  • the specific polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid obtained by using a diamine component containing a diamine represented by the above formula (1) and a tetracarboxylic acid dianhydride component, and an imidized product thereof. It is a polymer of choice.
  • the method for obtaining the polyamic acid from the diamine component and the tetracarboxylic acid dianhydride component is not particularly limited, and one example is as follows.
  • the diamine component and the tetracarboxylic acid dianhydride component are mixed in the presence of an organic solvent and stirred at -20 to 150 ° C, preferably 0 to 70 ° C, for 30 minutes to 24 hours, preferably 1 to 12 hours. Let it react.
  • an end capping agent such as monoamine or dicarboxylic acid anhydride may be added for the purpose of adjusting the molecular weight of the polymer.
  • the organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of the solubility of monomers and polymers, and one or more of these may be mixed You may use it.
  • the concentration of the reaction solution is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of a polymer hardly occurs and a polymer can be easily obtained.
  • the imidized polyamic acid in the present invention is a polymer obtained by imidizing the polyamic acid obtained as described above.
  • the imidization of polyamic acid is convenient to chemical imidization in which a catalyst is added to a solution of polyamic acid. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature, and molecular weight reduction of the polymer does not easily occur in the imidization process.
  • One example of chemical imidization is as follows.
  • the polyamic acid to be imidized and the basic catalyst are mixed in the presence of an acid anhydride and an organic solvent, and stirred at ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., for 1 to 100 hours.
  • the solvent used for the polymerization reaction of the polyamic acid mentioned above can be used.
  • Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
  • As the acid anhydride acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction.
  • the amount of basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of the amic acid structure of the polyamic acid, and the amount of acid anhydride is 1 to 50 times mol of the amic acid structure, preferably It is 3 to 30 times mol.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time.
  • the polyamic acid and its imidized product obtained as described above can be recovered by precipitating a polymer by pouring the reaction solution into a poor solvent while well stirring it.
  • the polyamic acid is chemically imidized, since the catalyst and the like remain in the reaction liquid, it is preferable to use the liquid crystal aligning agent of the present invention after recovering and purifying the polymer.
  • the purification of the polymer can be carried out by washing the polymer precipitated above with a poor solvent and then drying at room temperature or by heating.
  • the poor solvent used for polymer precipitation and washing is not particularly limited, but water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned, with preference given to water, methanol, ethanol, 2-propanol and the like .
  • the liquid crystal aligning agent of this invention is a composition containing said specific polymer and an organic solvent, and may contain 2 or more types of specific polymers of a different structure.
  • the liquid crystal aligning agent of the present invention may contain a polymer other than the specific polymer (hereinafter, also referred to as a second polymer) and various additives as long as the effects described in the present invention can be exhibited. Good.
  • the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and an example thereof is 5 to 95% by mass.
  • the second polymer includes polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivative thereof, poly (styrene-phenylmaleimide) derivative, poly (meth) An acrylate etc. can be mentioned.
  • a polyamic acid obtained from a tetracarboxylic acid dianhydride component and a diamine component not containing a diamine represented by the above formula (1) is preferable as the second polymer .
  • Examples of the tetracarboxylic acid dianhydride component for obtaining the second polyamic acid include the compounds represented by the above formula (3), and a structure preferable as A in the formula (3) and the reason therefor are also the above specific Same as described for the polymer.
  • the tetracarboxylic acid dianhydride component for obtaining the second polyamic acid may be one kind of tetracarboxylic acid dianhydride, or two or more kinds of tetracarboxylic acid dianhydrides may be used in combination. .
  • the compound represented by said Formula (2) and the compound except the diamine represented by said Formula (1) can be mentioned.
  • the diamine component for obtaining the second polyamic acid may be one kind of diamine, or two or more kinds of diamines may be used in combination.
  • the molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as a uniform and defect-free coating film can be formed on the substrate. If it dares to cite an example, it is 2,000 to 500,000, preferably 5,000 to 300,000, more preferably 10,000 to 100,000 in weight average molecular weight. In addition, the number average molecular weight is 1,000 to 250,000, preferably 2,500 to 150,000, more preferably 5,000 to 50,000.
  • the concentration of the polymer in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the point of forming a uniform, defect-free coating film, 1% by mass or more It is preferable that it is 10 mass% or less from the point of the storage stability of a solution.
  • the particularly preferred concentration of the polymer is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if a polymer component melt
  • dissolves uniformly include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination of two or more. Moreover, even if it is a solvent which can not melt
  • the organic solvent contained in a liquid crystal aligning agent uses the mixed solvent which used together the solvent which improves the surface smoothness of the coating property at the time of applying a liquid crystal aligning agent in addition to the above solvents and a liquid crystal aligning agent.
  • a mixed solvent is suitably used also in the liquid crystal aligning agent of the present invention.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6- Dimethi -4-Heptanol, 1,2-ethanedi
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • Formula [D-3] among, D 3 is an alkyl group having 1 to 4 carbon atoms.
  • the liquid crystal aligning agent of the present invention is, besides the above, a dielectric or a conductive substance for the purpose of changing electric properties such as dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
  • Silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound for the purpose of enhancing the hardness and density of the film when forming the liquid crystal alignment film, and polyamics when firing the coating
  • An imidization accelerator for the purpose of efficiently advancing imidization of an acid may be added.
  • the crosslinkable compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 part by mass, no effect can be expected. If the amount is more than 30 parts by mass, the orientation of the liquid crystal is reduced.
  • the liquid crystal aligning film of this invention is obtained from said liquid crystal aligning agent, and the existing method can be used for the method of producing a liquid crystal aligning film.
  • Typical examples include a coating process, a drying process, a baking process, and an alignment treatment process.
  • the orientation treatment step may be before the firing step, simultaneously with the firing step, or after the firing step.
  • a coating method of a liquid crystal aligning agent As a coating method of a liquid crystal aligning agent, a spin coat method, a printing method, an inkjet method etc. are mentioned.
  • the substrate to which the liquid crystal aligning agent is applied include plastic substrates such as a glass substrate, a silicon nitride substrate, an acrylic substrate, and a polycarbonate substrate.
  • plastic substrates such as a glass substrate, a silicon nitride substrate, an acrylic substrate, and a polycarbonate substrate.
  • substrate with which the ITO electrode etc. for liquid crystal drive were formed from the point of the simplification of a process When using for a liquid crystal display element etc., it is preferable to use the board
  • the drying step after the application of the liquid crystal aligning agent can be performed at any temperature and time. Usually, the reaction is carried out at 50 ° C. to 120 ° C. for 1 minute to 10 minutes in order to sufficiently remove the contained organic solvent.
  • the baking process of the liquid crystal aligning agent is performed, for example, at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes.
  • thermal imidization occurs in this firing step, and the polyamic acid changes to a polyimide.
  • the thickness of the coating after firing is not particularly limited, and is, for example, 5 to 300 nm, preferably 10 to 200 nm, and more preferably 50 nm to 150 nm.
  • a rubbing method As an orientation treatment process, a rubbing method, an optical orientation method, etc. are mentioned.
  • the rubbing method can be performed using an existing rubbing apparatus. Cotton, nylon, rayon etc. are mentioned as a material of the rubbing cloth in this case.
  • the conditions for the rubbing treatment generally, conditions of a rotational speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm / s, and a pressing amount of 0.1 to 1.0 mm are used. Thereafter, ultrasonic cleaning is performed using pure water, alcohol or the like to remove the residue generated by rubbing.
  • a specific example of the light alignment method is a method of irradiating the surface of the coated film with polarized radiation.
  • radiation ultraviolet light and visible light having a wavelength of 100 nm to 800 nm can be used.
  • ultraviolet light having a wavelength of 100 nm to 400 nm is preferable, and one having a wavelength of 200 nm to 400 nm is particularly preferable.
  • the dose of radiation is preferably 1 ⁇ 10,000mJ / cm 2, particularly preferably 100 ⁇ 5,000mJ / cm 2.
  • the higher the extinction ratio of polarized ultraviolet light the higher the anisotropy that can be imparted.
  • the extinction ratio of the linearly polarized ultraviolet light is preferably 10: 1 or more, more preferably 20: 1 or more.
  • the photoaligned film may be washed with a solvent containing at least one selected from water and an organic solvent. It will not specifically limit, if it is a solvent which melt
  • At least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable.
  • Water, 2-propane and a mixed solvent of water and 2-propanol are particularly preferred.
  • a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone or drying, or both You may
  • the film subjected to the orientation treatment as described above may be heat-treated at 150 ° C. or more for the purpose of increasing the anisotropy of the film.
  • An increase in the anisotropy of the film is achieved by the reorientation of molecular chains by heat.
  • the heating temperature is preferably 150 to 300.degree. The higher the temperature, the more the reorientation of the molecular chain is promoted, but it is preferable to keep the temperature at which the molecular chain does not decompose, for example, 180 to 250 ° C. is more preferable, and 200 to 230 ° C. is particularly preferable.
  • the heating time is, for example, 5 minutes to 120 minutes.
  • the above-mentioned firing step can also serve as a heating step for the purpose of increasing the anisotropy of the above-mentioned film.
  • the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a liquid crystal display element of a lateral electric field type such as IPS type or FFS type, and particularly useful as a liquid crystal alignment film of a liquid crystal display element of FFS type.
  • the liquid crystal display element of this invention has a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention,
  • the form and manufacturing method are not specifically limited. For example, after a substrate with a liquid crystal alignment film is obtained by the method for producing a liquid crystal alignment film, a liquid crystal cell is produced by a known method and used to make a liquid crystal display element.
  • the present invention is not limited thereto.
  • a set of glass substrates provided with electrodes for driving liquid crystal is prepared, and the liquid crystal alignment film of the present invention is formed on the substrates by the above method.
  • bead spacers are dispersed on the alignment film surface of one of the substrates, and a seal material is printed.
  • the bead spacer may be mixed in the sealing material, and instead of using the bead spacer, a substrate on which a columnar spacer is formed in advance may be used.
  • liquid crystal alignment film surface is made to face the above-mentioned substrate and the other substrate, and the liquid crystal composition is sealed in the space surrounded by the two substrates and the sealing material to form a liquid crystal cell.
  • the liquid crystal composition may be enclosed by a vacuum injection method or a liquid crystal dropping method (ODF).
  • ODF liquid crystal dropping method
  • the liquid crystal display element of the present invention can be obtained by using the liquid crystal cell manufactured by the above steps.
  • DA-1 Compound DA-2 represented by the following structural formula (DA-1): compound DA-3 represented by the following structural formula (DA-2): represented by the following structural formula (DA-3)
  • Compound DA-4 Compound DA-5 represented by the following structural formula (DA-4):
  • Compound DA-6 represented by the following structural formula (DA-5): represented by the following structural formula (DA-6)
  • Compound DA-7 Compound DA-8 represented by the following structural formula (DA-7):
  • DA-9 represented by the following structural formula (DA-8): Table represented by the following structural formula (DA-9)
  • Compound DA-10 Compound DA-11 represented by the following Structural Formula (DA-10): Compound CA-1 represented by the following Structural Formula (DA-11): By the following Structural Formula (CA-1)
  • Compound CA-2 represented:
  • DA-1 to DA-5 are novel compounds which have not been published in the literature or the like, and their synthesis methods will be described in detail in the following synthesis examples 1 to 9.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • BCS butyl cellosolve
  • THF tetrahydrofuran
  • DMF N, N-dimethylformamide
  • CH 2 Cl 2 dichloromethane
  • MeOH methanol.
  • EtOH ethanol.
  • IPA isopropyl alcohol.
  • [DA-1-3] (62.6 g, 230 mmol) and NMP (900 g) were added to a 2 L four-necked flask, and 1,3-DMCBDA (25.5 g, 114 mmol) was added in a water bath, then at room temperature Stir for 6 h. Subsequently, pyridine (54.5 g, 690 mmol) and acetic anhydride (35.2 g, 345 mmol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (4 L), and the precipitate was separated by filtration. MeOH (500 g) was added to the obtained crude product, and repulping was performed at room temperature to obtain 82.0 g of [DA-1-4].
  • [DA-4-1] (73.9 g, 225 mmol) and NMP (700 g) were added to a 2 L four-necked flask, and 1,3-DMCBDA (23.7 g, 106 mmol) was added in a water bath, then at room temperature Stir for 6 h. Subsequently, pyridine (53.4 g, 675 mmol) and acetic anhydride (34.5 g, 338 mol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. EtOH (1000 g) was added to the obtained crude product, and repulping was performed at room temperature to obtain 85.4 g of [DA-4-2].
  • [DA-5-1] (48.0 g, 120 mmol) and NMP (480 g) were added to a 3 L four-necked flask, and after adding 1,3-DMCBDA (13.4 g, 60 mmol) in a water bath, at room temperature Stir for 6 h. Subsequently, pyridine (28.4 g, 360 mmol) and acetic anhydride (18.4 g, 180 mmol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. MeOH (400 ml) was added to the obtained crude product, and repulping was performed at room temperature to obtain 42.5 g of [DA-5-2].
  • Synthesis Examples 8 to 15 Polyamic acids (a-2) to (a-5) and (c-1) can be prepared by using tetracarboxylic acid components, diamine components, and NMP as shown in the following table and carrying out them in the same manner as in Synthesis Example 7, respectively. And solutions of (b-1) to (b-3) were obtained.
  • Example 1 6.25 g of the solution of polyamic acid (a-1) obtained in Synthesis Example 7 is taken in a 100 ml Erlenmeyer flask, 0.50 g of NMP, 4.50 g of GBL and 3.75 g of BCS are added, and it is 3 hours at room temperature Stir to obtain a liquid crystal aligning agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.
  • Example 6 In a 100 ml conical flask, 2.50 g of the solution of polyamic acid (a-2) obtained in Synthesis Example 8 and 3.00 g of the solution of polyamic acid (b-1) obtained in Synthesis Example 13 are added to NMP 1 .25g, 4.50g of GBL, and 3.75g of BCS were added, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.
  • Example 7 The liquid crystal aligning agent shown in the following table is carried out in the same manner as in Example 6, except that the solution of polyamic acid obtained in Synthesis Example 14 to 15 is used instead of the solution of polyamic acid (b-1). (7) to (8) were obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.
  • Examples 9 to 16 and Comparative Example 2 A liquid crystal cell was produced in the following procedure using the liquid crystal aligning agent obtained above, and the voltage retention was measured.
  • Two substrates obtained with the liquid crystal alignment film thus obtained are combined into one set, and a bead spacer having a diameter of 4 ⁇ m is dispersed on the alignment film surface of one of the substrates, and a sealing material is printed.
  • the sealing material is cured to produce an empty cell.
  • a liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
  • the irradiation amount of polarized ultraviolet light in the liquid crystal cell manufacturing process is irradiated in advance in the range of 0.1 to 1.0 J / cm 2 for each liquid crystal aligning agent used to manufacture a liquid crystal cell, and the alignment property of liquid crystal Adopted the best dose.
  • the liquid crystal cell had no defect in the alignment of the liquid crystal, and the liquid crystal alignment state was good.
  • liquid crystal aligning agents (1) to (4) containing a polymer using a diamine in which at least one of n1 and n2 in each of L1 and L2 is 0, and (6) to (8) are compared with the liquid crystal aligning agent (5) containing a polymer using a diamine in which n1 and n2 are both 1 in L1 and L2 respectively, and the voltage holding ratio by the backlight left standing It was confirmed that the decrease in
  • Examples 17 to 24 An FFS-driven liquid crystal cell was produced according to the following procedure using the liquid crystal aligning agent obtained above, and residual image characteristics were confirmed.
  • the liquid crystal cell for the Fringe Field Switching (FFS) mode has the FOP (Finger on Plate) electrode layer consisting of a plane-shaped common electrode-insulation layer-comb-shaped pixel electrode formed on the surface.
  • a glass substrate of No. 1 and a second glass substrate having a columnar spacer with a height of 4 ⁇ m on the front surface and an ITO film for charging prevention formed on the back surface are one set.
  • the pixel electrode has a comb-tooth shape in which a plurality of electrode elements each having a width of 3 ⁇ m whose central portion is bent at an internal angle of 160 ° are arranged in parallel with an interval of 6 ⁇ m.
  • the liquid crystal alignment film formed on the first glass substrate is subjected to alignment processing so that the alignment direction of the liquid crystal is orthogonal to the direction equally dividing the inner angle of the bent pixel, and the liquid crystal alignment film formed on the second glass substrate is The alignment treatment is performed so that the alignment direction of the liquid crystal on the first substrate and the alignment direction of the liquid crystal on the second substrate coincide with each other when the liquid crystal cell is manufactured.
  • a liquid crystal aligning agent filtered with a 1.0 ⁇ m filter was applied by spin coating on the surface of each of the above-mentioned pair of glass substrates, and dried for 2 minutes on a hot plate at 80 ° C. Thereafter, a predetermined amount of UV light with a wavelength of 254 nm linearly polarized with an extinction ratio of 26: 1 is irradiated to the coated film surface through a polarizing plate, and then baked for 30 minutes in a hot air circulating oven at 230 ° C. A substrate with an alignment film was obtained.
  • a sealing material was printed on one of the pair of glass substrates with a liquid crystal alignment film, the other substrate was bonded so that the liquid crystal alignment film faces face one another, and the sealing material was cured to produce an empty cell.
  • a liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
  • the obtained liquid crystal cell was heated at 110 ° C. for 1 hour, allowed to stand overnight, and evaluated for residual image characteristics.
  • the liquid crystal cell had no defect in the alignment of the liquid crystal, and the liquid crystal alignment state was good.
  • a liquid crystal cell is placed between two polarizing plates disposed so that the polarization axes are orthogonal, and the backlight is turned on, so that the transmitted light intensity in the first region of the pixel is minimized. Adjust the placement angle of. Next, the rotation angle required when rotating the liquid crystal cell is determined so as to minimize the transmitted light intensity in the second region of the pixel. It can be said that the afterimage characteristic by long-term alternating current drive is better as the value of the rotation angle is smaller.
  • the liquid crystal aligning agent of this invention can manufacture a liquid crystal aligning film by the photo-alignment method.
  • the liquid crystal display element manufactured using the liquid crystal aligning agent of this invention is excellent in productivity and reliability, and can be suitably utilized for a large screen and a high definition liquid crystal television etc.
  • the liquid crystal alignment film of the present invention is excellent in reliability, and can also be used for a variable phase shifter using liquid crystal, and this variable phase shifter is suitable, for example, for an antenna or the like capable of varying the resonance frequency. Available.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui est caractéristique en ce qu'il comprend : un polymère choisi parmi un acide polyamique obtenu à l'aide d'un composant dianhydride tétracarboxylique et d'un composant amine contenant un amine représenté par la formule (1), et un produit d'imidation de celui-ci ; et un solvant organique. Dans la formule (1), Ｒ１, Ｒ２, Ｒ３ et Ｒ４ représentent, chacun indépendamment, Ｈ, ＣＨ３ ou ＣＦ３, cependant, parmi Ｒ１, Ｒ２, Ｒ３ et Ｒ４, au moins un représente ＣＨ３ ou ＣＦ３, Ｗ１ et Ｗ２ représentent un phénylène, L1 et L2 représentent indépendamment un groupe divalent représenté par －（Ｏ）ｎ１－（ＣＨ２）ｍ－（Ｏ）ｎ２－, ｎ１ et ｎ２ représentent indépendamment 0 ou 1, et m représente un entier de 1 à 10. Selon l'invention, il est possible de fabriquer un film d'alignement de cristaux liquides selon un procédé de photo-alignement, et il est possible de fournir un agent d'alignement de cristaux liquides qui permet d'obtenir le film d'alignement de cristaux liquides ayant un taux de rétention de tension satisfaisant y compris dans le cas d'une irradiation prolongée au moyen d'une lumière de rétroéclairage pendant une longue durée.
PCT/JP2019/000652 2018-01-15 2019-01-11 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides Ceased WO2019139115A1 (fr)

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WO2021210252A1 (fr) * 2020-04-15 2021-10-21 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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TWI834894B (zh) * 2020-07-13 2024-03-11 奇美實業股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
WO2025169938A1 (fr) * 2024-02-07 2025-08-14 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

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JPH09185064A (ja) * 1995-12-28 1997-07-15 Japan Synthetic Rubber Co Ltd イミド基含有ポリアミック酸およびその製造方法並びに液晶配向剤
KR20170040087A (ko) * 2015-10-02 2017-04-12 주식회사 엘지화학 광배향막의 제조 방법
WO2017082579A1 (fr) * 2015-11-11 2017-05-18 주식회사 엘지화학 Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

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JPH09185064A (ja) * 1995-12-28 1997-07-15 Japan Synthetic Rubber Co Ltd イミド基含有ポリアミック酸およびその製造方法並びに液晶配向剤
KR20170040087A (ko) * 2015-10-02 2017-04-12 주식회사 엘지화학 광배향막의 제조 방법
WO2017082579A1 (fr) * 2015-11-11 2017-05-18 주식회사 엘지화학 Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021210252A1 (fr) * 2020-04-15 2021-10-21 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JPWO2021210252A1 (fr) * 2020-04-15 2021-10-21
JP7582305B2 (ja) 2020-04-15 2024-11-13 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子

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