Classifications

• • 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
  • C09K19/60—Pleochroic dyes
  • C09K19/601—Azoic
• • 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
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/02—Disazo dyes
  • C09B31/08—Disazo dyes from a coupling component "C" containing directive hydroxyl and amino groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal elements
• • 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
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133528—Polarisers
• • 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
  • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
  • C09K2323/03—Viewing layer characterised by chemical composition
  • C09K2323/031—Polarizer or dye
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/91—Product with molecular orientation

Definitions

• the present invention relates to a liquid crystalline coating solution and a polarizing film produced using the same.
• a polarizing plate In a liquid crystal panel, a polarizing plate is used to control the optical rotation of light passing through the liquid crystal.
• polarizing plates polarizing plates obtained by dyeing a resin film such as polyvinyl alcohol with iodine or a dichroic dye and stretching in one direction are widely used.
• the above polarizing plate has a problem that heat resistance and light resistance are not sufficient depending on the type of the pigment or the resin film, and the film manufacturing apparatus is increased in size as the liquid crystal panel is increased in size.
• a method of forming a polarizing film by casting a liquid crystalline coating solution containing a lyotropic liquid crystal compound on a substrate such as a glass plate or a resin film and aligning the lyotropic liquid crystal compound is known.
• a lyotropic liquid crystal compound forms a supramolecular aggregate exhibiting liquid crystallinity in a solution, and when the liquid crystalline coating solution containing this is cast by applying a shear stress, the major axis direction of the supramolecular aggregate is cast. Oriented in the direction.
• One such lyotropic liquid crystal compound is an azo compound (Patent Document 1).
• the polarizing film of the lyotropic liquid crystal compound does not need to be stretched, and since there is no contraction in the width direction due to stretching, it is easy to obtain a polarizing film having a wide width. Moreover, since the film thickness can be remarkably reduced, the future is expected.
• the object of the present invention is a polarizing film obtained from a liquid crystalline coating solution containing an azo compound, in which fine crystals are deposited in the film during the drying process, resulting in an increase in the haze (light scattering) of the polarizing film and a deterioration in transparency. It is an object of the present invention to provide a liquid crystal coating solution containing a novel azo compound that solves the above-mentioned problem.
• the gist of the present invention is as follows.
• the liquid crystalline coating liquid of the present invention comprises an azo compound represented by the following general formula (1) and a solvent for dissolving the azo compound.
• Q 1 represents an aryl group which may have a substituent
• Q 2 represents an arylene group which may have a substituent
• R represents a hydrogen atom
• 1 to 3 carbon atoms Represents an alkyl group, an acetyl group, a benzoyl group or a phenyl group (these groups may have a substituent)
• M represents a counter ion.
• the liquid crystalline coating liquid of the present invention is characterized in that the concentration of the azo compound is 0.5 wt% to 50 wt%.
• the liquid crystalline coating liquid of the present invention is characterized in that the liquid crystalline coating liquid has a pH of 5 to 9. (4)
• the polarizing film of the present invention is obtained by casting the liquid crystalline coating liquid into a thin film and drying it
• the liquid crystalline coating liquid of the present invention containing the above azo compound is considered to suppress the precipitation of fine crystals when the liquid crystalline coating liquid is cast and dried. As a result, it is considered that the number of fine crystals that cause haze is much smaller than in the past, and haze is reduced.
• the liquid crystalline coating liquid of the present invention introduces an aminonaphthol skeleton, which is likely to be a poorly soluble site due to its high flatness in the structure of the azo compound contained therein, and introduces a sulfonic acid group at a specific position. It is thought that the precipitation of fine crystals could be suppressed by making it easier to dissolve.
• the liquid crystalline coating liquid of the present invention contains an azo compound represented by the following general formula (1) and a solvent for dissolving the azo compound.
• Q 1 represents an aryl group which may have a substituent
• Q 2 represents an arylene group which may have a substituent
• R represents a hydrogen atom
• 1 to 3 carbon atoms Represents an alkyl group, an acetyl group, a benzoyl group or a phenyl group (these groups may have a substituent)
• M represents a counter ion.
• the above azo compound forms a supramolecular aggregate in the liquid and exhibits a liquid crystal phase.
• a liquid crystal phase A nematic liquid crystal phase, a hexagonal liquid crystal phase, etc. are mentioned. These liquid crystal phases can be identified and confirmed by observing the optical pattern with a polarizing microscope.
• the concentration of the above azo compound in the liquid crystalline coating solution of the present invention is preferably 0.5% by weight to 50% by weight.
• a liquid crystalline coating solution exhibiting a stable liquid crystal phase at at least part of the concentration in the above range is obtained, and a polarizing film having a target thickness (for example, 0.4 ⁇ m) can be easily obtained.
• the pH of the liquid crystalline coating solution of the present invention is preferably 5-9.
• a polarizing film having a high degree of orientation can be obtained, and the productivity is excellent because the coater made of metal such as stainless steel is not corroded.
• the liquid crystal coating liquid of the present invention may contain any other liquid, for example, other liquid crystal compounds and additives, as long as it contains the specific azo compound and a solvent.
• the additive include a surfactant, an antioxidant, and an antistatic agent.
• concentration of these additives is usually less than 10% by weight.
• the method for preparing the liquid crystalline coating liquid of the present invention is not particularly limited.
• the above azo compound may be added to the solvent, or conversely, the solvent may be added to the above azo compound.
• the azo compound used in the liquid crystalline coating liquid of the present invention is a compound represented by the above general formula (1).
• the azo compound represented by the general formula (1) exhibits absorption dichroism in the visible light region (wavelength of 380 nm to 780 nm), and suppresses precipitation of fine crystals by having a substituent such as a sulfonic acid group at a specific position. Thus, a polarizing film having a small haze can be obtained.
• Q 1 represents an aryl group which may have a substituent
• Q 2 represents an arylene group which may have a substituent, and adjusts the width of the absorption wavelength. Substituents suitable for are used.
• R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group or a phenyl group (these groups may have a substituent).
• M represents a counter ion, preferably a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a metal ion of the above metal, or a substituted or unsubstituted ammonium ion.
• the metal ions include Li + , Ni 2+ , Fe 3+ , Cu 2+ , Ag + , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Sn 2+ , Co 2+ , Mn 2+ , and Ce 3+ .
• the counter ion M is a multivalent ion, a plurality of azo compounds share one multivalent ion (counter ion).
• the azo compound is preferably one represented by the following general formula (2) or (3).
• R and M are the same as in formula (1).
• X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an —SO 3 M group.
• the azo compounds represented by the above formulas (1) and (2) are, for example, diazotized and coupled with an aniline derivative and a naphthalene derivative by a conventional method to obtain a monoazo compound, which is further diazotized to give 1-amino It can be obtained by coupling reaction with an -8-naphthol derivative.
• the solvent used in the present invention dissolves the above azo compound, and a hydrophilic solvent is preferably used.
• the hydrophilic solvent is preferably water, alcohols, cellosolves or a mixed solvent thereof.
• a water-soluble compound such as glycerin or ethylene glycol may be added to the solvent.
• the polarizing film of the present invention is obtained by casting the liquid crystalline coating liquid of the present invention on the surface of a substrate or a metal drum and drying it.
• the casting means is not particularly limited as long as the liquid crystalline coating solution can be cast uniformly, and an appropriate coater such as a slide coater, slot die coater, bar coater, rod coater, roll coater, curtain coater, spray coater, etc. is used. It is done.
• There is no particular limitation on the drying method and natural drying, reduced pressure drying, heat drying, reduced pressure heat drying and the like are used.
• an arbitrary drying device such as an air circulation drying oven or a hot roll is used.
• the drying temperature in the case of heat drying is preferably 50 ° C. to 120 ° C.
• the polarizing film of the present invention is preferably dried so that the residual solvent amount is 5% by weight or less based on the total weight of the film.
• the polarizing film of the present invention preferably exhibits absorption dichroism in the visible light region (wavelength 380 nm to 780 nm). Such characteristics can be obtained by orienting the azo compound in the polarizing film.
• the above azo compound forms supramolecular aggregates in the liquid crystalline coating solution, and when the liquid crystalline coating solution is cast while applying a shear stress, the major axis direction of the supramolecular aggregate is aligned in the casting direction.
• the orientation means may be combined with orientation treatment such as rubbing treatment or photo-alignment, orientation by magnetic field or electric field in addition to shear stress.
• the thickness of the polarizing film of the present invention is preferably 0.1 ⁇ m to 3 ⁇ m.
• the polarization degree of the polarizing film of the present invention is preferably 90% or more, more preferably 95% or more.
• the haze value of the polarizing film can be preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less.
• the substrate include a glass plate and a resin film.
• the alignment film is preferably subjected to an alignment treatment.
• the base material including the alignment film include a base material in which a polyimide film is coated on a glass plate. This polyimide film is provided with orientation by a known method, for example, mechanical orientation treatment such as rubbing or photo-alignment treatment.
• the glass of the substrate alkali-free glass used for a liquid crystal cell is preferable.
• Resin film base materials are suitable for applications that require flexibility.
• the surface of the resin film may be aligned by rubbing or the like, or an alignment film made of another material may be formed on the surface of the resin film.
• the material of the resin film used for the substrate is not particularly limited as long as it is a film-forming resin, but a styrene resin, a (meth) acrylic acid resin, a polyester resin, a polyolefin resin, a norbornene resin, a polyimide resin Examples thereof include resins, cellulose resins, polyvinyl alcohol resins, and polycarbonate resins.
• the thickness of the substrate is not particularly limited except for the application, but is generally in the range of 1 ⁇ m to 1000 ⁇ m.
• the polarizing film of the present invention is suitably used as a polarizing element.
• Polarizing elements are various liquid crystal panels, for example, OA equipment such as computers and copiers, portable equipment such as mobile phones, watches, digital cameras, personal digital assistants, portable game machines, household equipment such as video cameras, televisions, and microwave ovens Used in LCD panels for medical equipment such as in-vehicle equipment such as back monitors, car navigation, car audio, display equipment such as store monitors, security equipment such as monitoring monitors, nursing monitors, and medical monitors.
• the polarizing film of the present invention may be used after being peeled off from the substrate, or may be used while being laminated with the substrate. When used for optical purposes while being laminated with a substrate, the substrate is preferably transparent to visible light. When peeled from the base material, it is preferably used by being laminated on another support or optical element.
• Example 1 4-azoaniline and 8-amino-2-naphthalenesulfonic acid are diazotized by the conventional method (Toyo Hosoda, “Theoretical Manufacturing, Dye Chemistry, 5th Edition”, published on July 15, 1968, Technique Hall, pages 135-152). And a coupling reaction to obtain a monoazo compound.
• the resulting monoazo compound is similarly diazotized by a conventional method, and is further subjected to a coupling reaction with 1-amino-8-naphthol-2,4-disulfonic acid lithium salt to produce a crude product containing an azo compound of the following structural formula (4)
• an azo compound of the following structural formula (4) was obtained by salting out with lithium chloride.
• the azo compound of the above structural formula (4) was dissolved in ion-exchanged water to prepare a 20% by weight liquid crystalline coating solution.
• the liquid crystalline coating solution had a pH of 7.8.
• This liquid crystalline coating solution was collected with a poly dropper, and was sandwiched between two slide glasses and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• Example 2 A compound of the following structural formula (5) was obtained in the same manner as in Example 1 except that 4-nitroaniline was changed to p-anisidine.
• the azo compound of the above structural formula (5) was dissolved in ion exchange water to prepare a 20 wt% liquid crystalline coating solution.
• the pH of this liquid crystalline coating solution was 7.5.
• This liquid crystalline coating solution was collected with a poly dropper, sandwiched between two slide glasses, and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• the liquid crystalline coating solution was further diluted with ion-exchanged water to prepare 10% by weight.
• a polarizing film having a thickness of 0.6 ⁇ m was produced in the same manner as in Example 1 using this liquid crystalline coating solution. Table 1 shows the optical characteristics of the obtained polarizing film.
• Example 3 A compound of the following structural formula (6) was obtained in the same manner as in Example 1 except that 4-nitroaniline was changed to p-toluidine.
• the azo compound of the above structural formula (6) was dissolved in ion exchange water to prepare a 20 wt% liquid crystalline coating solution.
• the pH of this liquid crystalline coating solution was 7.5.
• This liquid crystalline coating solution was collected with a poly dropper, sandwiched between two slide glasses, and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• the liquid crystalline coating solution was further diluted with ion-exchanged water to prepare 10% by weight.
• a polarizing film having a thickness of 0.6 ⁇ m was produced in the same manner as in Example 1 using this liquid crystalline coating solution. Table 1 shows the optical characteristics of the obtained polarizing film.
• Example 4 A compound of the following structural formula (7) was obtained in the same manner as in Example 1 except that 8-amino-2-naphthalenesulfonic acid was changed to 5-amino-1-naphthol-3-sulfonic acid hydrate.
• the azo compound of the above structural formula (7) was dissolved in ion exchange water to prepare a 20% by weight liquid crystalline coating solution.
• the liquid crystalline coating solution had a pH of 8.3.
• This liquid crystalline coating solution was collected with a poly dropper, sandwiched between two slide glasses, and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• the liquid crystalline coating solution was further diluted with ion-exchanged water to prepare 5% by weight.
• a polarizing film having a thickness of 0.6 ⁇ m was produced in the same manner as in Example 1 except that a bar coater (trade name “Mayer rot HS9” manufactured by BUSCHMAN Co., Ltd.) was used using this liquid crystalline coating solution.
• Table 1 shows the optical characteristics of the obtained polarizing film.
• the azo compound of the above structural formula (8) was dissolved in ion-exchanged water to prepare a 20% by weight liquid crystalline coating solution.
• the liquid crystalline coating solution had a pH of 6.7.
• This liquid crystalline coating solution was collected with a poly dropper, and was sandwiched between two slide glasses and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• a polarizing film having a thickness of 0.8 ⁇ m was produced in the same manner as in Example 1 using the above liquid crystalline coating solution. Table 1 shows the optical characteristics of the obtained polarizing film.
• the azo compound of the above structural formula (9) was dissolved in ion exchange water to prepare a 20 wt% liquid crystalline coating solution.
• the liquid crystalline coating solution had a pH of 6.0.
• This liquid crystalline coating solution was collected with a poly dropper, sandwiched between two slide glasses, and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• the liquid crystalline coating solution was further diluted with ion-exchanged water to prepare 10% by weight.
• a polarizing film having a thickness of 0.6 ⁇ m was produced in the same manner as in Example 1 using this liquid crystalline coating solution. Table 1 shows the optical characteristics of the obtained polarizing film.
• [Comparative Example 3] A compound of the following structural formula (10) was obtained in the same manner as in Comparative Example 1 except that 4-nitroaniline was changed to p-toluidine.
• the azo compound of the above structural formula (10) was dissolved in ion exchange water to prepare a 20 wt% liquid crystalline coating solution.
• the liquid crystalline coating solution had a pH of 6.0.
• This liquid crystalline coating solution was collected with a poly dropper, sandwiched between two slide glasses, and observed with a polarizing microscope at room temperature (23 ° C.). As a result, a nematic liquid crystal phase was observed.
• the liquid crystalline coating solution was further diluted with ion-exchanged water to prepare 10% by weight.
• a polarizing film having a thickness of 0.6 ⁇ m was produced in the same manner as in Example 1 using this liquid crystalline coating solution. Table 1 shows the optical characteristics of the obtained polarizing film.

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• 2008
  • 2008-04-22 JP JP2008110902A patent/JP4915699B2/ja not_active Expired - Fee Related
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