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WO2006054695A1 - Affichage à cristaux liquides - Google Patents

Affichage à cristaux liquides Download PDF

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Publication number
WO2006054695A1
WO2006054695A1 PCT/JP2005/021244 JP2005021244W WO2006054695A1 WO 2006054695 A1 WO2006054695 A1 WO 2006054695A1 JP 2005021244 W JP2005021244 W JP 2005021244W WO 2006054695 A1 WO2006054695 A1 WO 2006054695A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
refractive index
crystal display
side polarizer
display device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/021244
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English (en)
Japanese (ja)
Inventor
Masanori Yoshihara
Shuhei Okude
Tetsuya Toyoshima
Kohei Arakawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
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Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2006545164A priority Critical patent/JPWO2006054695A1/ja
Publication of WO2006054695A1 publication Critical patent/WO2006054695A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

Definitions

  • the present invention relates to a liquid crystal display device. More specifically, the present invention relates to a liquid crystal display device that has a wide viewing angle and excellent scratch resistance with no reflection, good black display quality from any direction, and has a uniform and high contrast. Background art
  • liquid crystal display device As a liquid crystal display device (hereinafter sometimes abbreviated as “LCD”), a so-called TN mode in which liquid crystal having positive dielectric anisotropy is horizontally aligned between two substrates is used. It is mainly used. However, in such a TN mode, even if black display is attempted, birefringence occurs due to liquid crystal molecules near the substrate, resulting in light leakage, making it difficult to perform complete black display.
  • LCD liquid crystal display device
  • VA Vertical Alignment
  • MVA Multi-domain Vertical Alignment
  • PVA Plasma Vertical Alignment
  • Patent Document 1 discloses an example using a biaxial retardation plate satisfying n> n> n and having an in-plane retardation of 120 nm or less.
  • Patent Document 2 uses a biaxial retardation plate where n>n> n, and in-plane direction and film An example in which the viewing angle is improved by increasing the retardation ratio in the thickness direction to 2 or more, and the contrast is further improved by laminating an antiglare layer and an antireflection layer on the observation side of the retardation plate.
  • this antireflection layer a desired antireflection effect is obtained by laminating two or more high refractive index layers and low refractive index layers.
  • this multi-layer antireflection layer has a large wavelength dependency of the antireflection effect.
  • Formation of a multilayer film with a large area using a vacuum apparatus for producing this has a problem in practical use due to poor productivity.
  • Patent Document 1 Japanese Patent No. 3330574
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-307735
  • An object of the present invention is to provide a liquid crystal display device having a wide viewing angle, no reflection, excellent scratch resistance, good black display quality from any direction, uniform and high contrast. It is to provide.
  • a vertical alignment (VA) mode liquid crystal display device having at least one optical anisotropic body and a liquid crystal cell between a pair of polarizers,
  • the three main refractive indices in the plane of the optical anisotropic body are different from each other.
  • the letter when the light with a wavelength of 550 nm is vertically incident when no voltage is applied is R, and the light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • R is the letter decision when
  • a liquid crystal display device with a low refractive index layer that satisfies 40 0 I ⁇ 35 nm and has a refractive index of 1.37 or less on the viewing side of the output-side polarizer has a wide viewing angle. It has been found that it has excellent scratch resistance with no reflection, good black display quality from any direction, uniform and high contrast, and based on this finding, the present invention has been completed.
  • the transmission axes are in a substantially vertical positional relationship with each other.
  • Vertical alignment (VA) mode liquid crystal display having at least one biaxial optical anisotropic body and a liquid crystal cell between the output side polarizer including the output side polarizer and the input side polarizer including the input side polarizer A device,
  • the letter retardation is R and the wavelength is 550 ⁇ when light having a wavelength of 550 nm is incident on the normal direction force when no voltage is applied.
  • a liquid crystal display device characterized by satisfying the above relationship is provided.
  • the liquid crystal display device of the present invention includes a normal-direction letter pattern and a pole of a product in which a biaxial optical anisotropic body having a specific refractive index, a liquid crystal cell and a biaxial optical anisotropic body are stacked.
  • the liquid crystal cell is arranged by arranging the slow axis of the superposed liquid crystal cell and the biaxial optical anisotropic body so that the slow axis is substantially parallel or substantially perpendicular to the transmission axis of the polarizer.
  • the liquid crystal display device of the present invention can be suitably used as a large screen flat panel display or the like. Brief Description of Drawings FIG. 1 is an explanatory diagram of a method for measuring Letter Decision R.
  • FIG. 4 shows a state in which the low refractive index layer and the hard coat layer are removed in the liquid crystal display device 1 obtained in Example 1 (Polarizing plate 1C (polarizing plate in which the low refractive index layer and the no coat layer are laminated).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where is replaced with a polarizer P).
  • FIG. 5 shows a state in which the low refractive index layer and the hard coat layer are removed in the liquid crystal display device 2 obtained in Example 2 (Polarizing plate 1C (polarizing plate in which the low refractive index layer and the no coat layer are laminated).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where is replaced with a polarizer P).
  • FIG. 6 shows a state in which the low refractive index layer and the hard coat layer are removed in the liquid crystal display device 3 obtained in Example 3 (Polarizing plate 2C (polarizing plate in which the low refractive index layer and the no coat layer are laminated).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where is replaced with a polarizer P).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where it is replaced by a polarizer P).
  • FIG. 8 shows a state in which the low refractive index layer and the hard coat layer are excluded in the liquid crystal display device 5 obtained in Comparative Example 2 (Polarizing plate 3C (polarizing plate in which the low refractive index layer and the no coat layer are laminated).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where is replaced with a polarizer P).
  • FIG. 9 shows a state in which the low refractive index layer and the hard coat layer are removed in the liquid crystal display device 6 obtained in Comparative Example 3 (Polarizing plate 4C (polarizing plate in which the low refractive index layer and the no coat layer are laminated).
  • FIG. 6 is a contrast diagram obtained by calculation by simulation in a state where is replaced with a polarizer P).
  • the liquid crystal display device of the present invention includes at least one biaxial optical anisotropic body and at least one biaxial optical anisotropic body between the exit side polarizer and the entrance side polarizer in which the transmission axes are substantially perpendicular to each other.
  • a vertical alignment (VA) mode liquid crystal display device having a liquid crystal cell, a VA mode liquid crystal cell, at least one biaxial optical anisotropic body, an output side polarizer, and an input side polarization Including at least a child.
  • the liquid crystal molecules are aligned substantially perpendicular to the substrate surface when no voltage is applied, and the liquid crystal molecules are aligned horizontally on the substrate surface when a voltage is applied. It is. Specifically, MVA (Multi-domain Vertical Alignment) method, PV A (Patterned Vertical Alignment) method, etc. are known.
  • At least one biaxial optical anisotropic body used in the present invention has ⁇ ⁇ and ⁇ as the main refractive index in the in-plane direction and ⁇ > ⁇ > when the main refractive index in the thickness direction is ⁇ . It shows the relationship of ⁇ .
  • the direction indicating n is called the slow axis ( ⁇ ), and the direction showing n is called the slow axis (y).
  • CR means that the brightness of the LCD display during dark display is Y and the brightness during bright display is Y.
  • the value is represented by ⁇ / ⁇ , and the greater the contrast, the better the visibility.
  • the bright display is the state in which the display screen of the liquid crystal display device is brightest
  • the dark display is the state in which the display screen of the liquid crystal display device is most bright.
  • the biaxial optical anisotropic body used in the present invention is a single stretched film satisfying the relationship of n> n> n, or the whole of two or more stretched films, n> It may satisfy n> n relationship.
  • the biaxial optical anisotropic body used in the present invention stretches a film made of transparent resin. It is obtained from Kotoko.
  • the transparent resin can be used without particular limitation as long as it has a total light transmittance of 80% or more when formed into a 1 mm-thick molded product.
  • the transparent resin include a polymer resin having an alicyclic structure, a chain olefin polymer such as polyethylene and polypropylene, a polycarbonate polymer, a polyester polymer, a polysulfone polymer, and a polyethersulfone polymer. , Polystyrene polymer, polybutyl alcohol polymer, polymetatalylate polymer, and the like. These can be used in combination of two or alone. Among these, polymer resins having an alicyclic structure and chain olefin polymers are preferred, and particularly excellent in transparency, low hygroscopicity, dimensional stability, light weight, etc. I prefer fat.
  • the film made of the transparent resin is not particularly limited by its production method, and examples thereof include films obtained by a conventionally known method such as a solution casting method or a melt extrusion method. Among them, the melt extrusion method without using a solvent can reduce the content of volatile components, and it is easy to produce a film having a large R at 100 ⁇ m or more. In addition, the power of manufacturing costs is also provided.
  • melt extrusion method is preferred.
  • examples of the melt extrusion method include a method using a die and an inflation method, but a method using a T die is preferable because of its excellent productivity and thickness accuracy.
  • R (nm) is the letter direction in the thickness direction.
  • a transparent resin is introduced into an extruder having a T die, and the temperature is usually 80 to 180 ° C higher than the glass transition temperature of the transparent resin to be used.
  • the transparent resin is melted at a temperature 100 to 150 ° C. higher than the glass transition temperature, the molten resin is extruded with a T-die force, and the resin is cooled with a cooling roll or the like to form a film. If the melting temperature of the transparent resin is excessively low, the fluidity of the transparent resin may be insufficient. Conversely, if the melting temperature is excessively high, the transparent resin may be deteriorated.
  • the method and conditions for stretching the film made of the above transparent resin may be determined by the methods and conditions under which n> n> n. Select as appropriate
  • tenter stretching machine examples thereof include a stretching method and a biaxial stretching method.
  • tenter drawing machine examples include a pantograph type tenter drawing machine, a screw type tenter drawing machine, and a linear motor type tenter drawing machine.
  • Examples of the biaxial stretching method include a method of sequentially biaxial stretching in the longitudinal direction and the transverse direction, and a method of simultaneously biaxial stretching in the longitudinal direction and the transverse direction.
  • the simultaneous biaxial stretching method is preferred because it can simplify the process and increase the thickness-direction letter value Rth, which makes the optical anisotropic body difficult to crack.
  • the simultaneous biaxial stretching method includes a step of preheating the raw film (preheating step), a step of simultaneously biaxially stretching the preheated raw film in the machine direction and the transverse direction (stretching step), and stretching.
  • the raw film is usually heated to [stretching temperature 40 ° C] to [stretching temperature + 20 ° C], preferably [stretching temperature 30 ° C] to [stretching temperature + 15 ° C].
  • the raw film is preferably Tg-30 ° C to Tg + 60 ° C, more preferably Tg-10 ° C, where Tg is the glass transition temperature of the transparent resin. Stretched while heated to ⁇ Tg + 50 ° C.
  • the draw ratio is not particularly limited as long as a desired refractive index relationship can be obtained, but is usually 1.3 times or more, preferably 1.3 to 3 times.
  • the stretched film is usually room temperature to stretching temperature + 30 ° C, preferably stretching temperature-40 ° C to stretching temperature + 20 ° C.
  • Examples of the heating means (or temperature adjusting means) in the preheating step, the stretching step, and the heat setting step include an oven-type heating device, a radiation heating device, and a means for immersing in a temperature-adjusted liquid. Of these, an oven-type heating device is preferred. The oven type heating device is preferable because the nozzle force hot air is jetted onto the upper and lower surfaces of the film (raw film or stretched film) and the temperature distribution in the film surface is reduced.
  • the exit side polarizing plate used in the present invention includes an exit side polarizer.
  • the incident side polarizing plate used in the present invention includes an incident side polarizer.
  • the exit side polarizer and the entrance side polarizer can convert natural light into linearly polarized light.
  • these polarizers include polybulal alcohol and partial formalization.
  • examples thereof include polarizers obtained by subjecting a film made of a butyl alcohol polymer such as polybulal alcohol to a dyeing treatment, a stretching treatment, and a crosslinking treatment with a dichroic substance such as iodine or a dichroic dye.
  • polarizers obtained by subjecting a film made of a butyl alcohol polymer such as polybulal alcohol to a dyeing treatment, a stretching treatment, and a crosslinking treatment with a dichroic substance such as iodine or a dichroic dye.
  • the exit side polarizer and the entrance side polarizer are in a positional relationship in which their transmission axes are substantially vertical.
  • the substantially vertical positional relationship is usually 87 to 90 degrees, preferably 89 to 90 degrees, when the angle formed by the two transmission axes is displayed as 0 to 90 degrees (the angle formed by the narrower side). is there. If the angle formed by the two transmission axes of the output side polarizer and the input side polarizer is less than 87 degrees, light may leak and the black display quality of the display screen may be degraded.
  • a protective film is usually adhered to both sides of the exit side polarizer of the exit side polarizer and the entrance side polarizer of the entrance side polarizer! Speak.
  • a film made of a polymer excellent in transparency, mechanical strength, thermal stability, moisture shielding property and the like can be suitably used.
  • polymers having an alicyclic structure and polyethylene terephthalate have good transparency, lightness, dimensional stability, and film thickness control, and triacetyl cellulose has good transparency and lightness. It can be used suitably.
  • Examples of the polymer having an alicyclic structure include a norbornene polymer, a monocyclic olefin polymer, and a polymer of a vinyl monomer and a hydrocarbon monomer having an alicyclic structure.
  • norbornene polymers can be suitably used because of their good transparency and moldability.
  • Examples of norbornene polymers include, for example, ring-opening polymers of norbornene monomers, ring-opening copolymers of norbornene monomers and other monomers, and hydrogenated products of these polymers; norbornene monomers Examples thereof include addition polymers, addition copolymers of norbornene monomers with other monomers, and hydrogenated products of these polymers.
  • the hydrogenation of norbornene monomer ring-opening polymer or ring-opening copolymer. Additives are particularly preferred because of their excellent transparency.
  • the above biaxial optical anisotropic body can be used.
  • the liquid crystal display device can be thinned.
  • an adhesive or a pressure sensitive adhesive is usually used as a means for adhesively bonding the exit side polarizer or the entrance side polarizer and the protective film or the biaxial optical anisotropic body.
  • the adhesive or pressure-sensitive adhesive include acrylic, silicone-based, polyester-based, polyurethane-based, polyether-based, and rubber-based adhesives or pressure-sensitive adhesives.
  • acrylic adhesives or pressure-sensitive adhesives can be suitably used because they have good heat resistance and transparency.
  • the exit-side polarizer or the entrance-side polarizer, and the protective film or the biaxial optical anisotropic body can be cut out to a desired size and bonded to each other. It is preferable that the exit-side polarizer or the entrance-side polarizer and the long protective film or the biaxial optical anisotropic body are adhered to each other by roll-to-roll.
  • the exit-side polarizing plate used in the present invention has a low-refractive index layer having a refractive index of 1.37 or less composed of air-mouth gel on the observation side of the exit-side polarizer.
  • the hard coat layer and the low-refractive index layer are formed in this order from the exit side polarizer toward the viewing side.
  • a method of providing a low refractive index layer and, if necessary, a hard coat layer on the protective film on the observation side of the output side polarizer is usually employed. By providing these layers in this order, the reflection of external light can be reduced.
  • the contrast of the displayed image can be increased, and by providing a hard coat layer, the scratch resistance is increased and the contrast is increased. can do.
  • the hard coat layer is a layer having a high surface hardness. Specifically, it is a layer having a hardness of “HB” or higher in the pencil hardness test specified in JIS K5600-5-4.
  • the average thickness of the hard coat layer is not particularly limited, but is usually 0.5 to 30 / ⁇ ⁇ , preferably 3 to 15 m.
  • the material that forms the hard coat layer is the pencil hardness specified in JIS K 5600-5-4
  • organic hard coat materials such as silicone-based, melamine-based, epoxy-based, acrylic-based, urethane acrylate, etc. are acceptable as long as they can form a layer with a hardness of HB or higher.
  • inorganic hard coat materials such as nickel silicate and the like.
  • urethane acrylate and polyfunctional acrylate hard coat materials can be suitably used because of their high adhesive strength and excellent productivity.
  • the refractive index of the hard coat layer is preferably 1.55 or more, more preferably 1.37 or more, and more preferably 1.60 or more.
  • the rate layer can be easily designed.
  • the refractive index can be measured and determined using, for example, a known spectroscopic ellipsometer.
  • the hard coat layer preferably further contains inorganic oxide particles.
  • the scratch resistance is excellent, and the refractive index of the hard coat layer can be easily increased to 1.55 or more.
  • the inorganic oxide particles used for the hard coat layer are preferably those having a high refractive index. Specifically, inorganic oxide particles having a refractive index of 1.6 or more, particularly 1.6 to 2.3 are preferred.
  • examples of such inorganic oxide particles having a high refractive index include titanium (acid titanium), zirconium oxide (acid zirconium), acid zinc, acid tin, cerium oxide, Antimony pentoxide, tin oxide doped with antimony (ATO), tin oxide doped with phosphorus (PTO), tin oxide doped with fluorine (FTO), indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO) and aluminum-doped zinc oxide (AZO).
  • antimony pentoxide is suitable as a component for adjusting the refractive index because it has a high refractive index and an excellent balance between conductivity and transparency.
  • the hard coat layer is formed by coating the protective film with the hard coat material and, if necessary, the composition containing the inorganic oxide particles, and if necessary, drying and curing. can get.
  • the surface of the protective film can be subjected to plasma treatment, primer treatment, etc. to increase the peel strength between the hard coat layer and the protective film.
  • the curing method includes a thermal curing method and an ultraviolet curing method. In the present invention, the ultraviolet curing method is preferred.
  • a coextruded film in which the protective film resin and the hard coat material are laminated is formed. That is, a structure in which a hard coat layer is laminated on a protective film can be obtained.
  • the hard coat layer may have a fine uneven shape formed on its surface to give antiglare properties!
  • the uneven shape is not particularly limited as long as it is a shape effective for imparting a known antiglare property.
  • the low refractive index layer is a layer having a refractive index of 1.37 or less.
  • the refractive index of the low-refractive index layer is low or lower, and the preferred strength S is preferably 1.25-1.37, more preferably 1.32-1.36.
  • the thickness of the low refractive index layer is preferably 10 to 1, and more preferably 30 to 500 nm.
  • the low refractive index layer also has an air-mouth gel force.
  • the air mouth gel is a transparent porous body in which minute bubbles are dispersed in a matrix, and the diameter of the bubbles is mostly 200 nm or less.
  • the matrix refers to a component that can form a film on the observation side of the output side polarizer.
  • the bubble content of the air mouth gel is preferably 20 to 40% by volume, more preferably 20 to 40% by volume.
  • Examples of the air mouth gel include silica air mouth gel and a porous body in which hollow fine particles are dispersed in a matrix.
  • the silica air-mouthed gel can be produced by supercritical drying of a wet gel material having a silica skeleton obtained by hydrolysis polymerization reaction of alkoxysilane.
  • supercritical drying for example, a gel-like substance is immersed in liquefied carbon dioxide, and all or part of the solvent contained in the gel-like substance is replaced with liquid oxalate-carbon having a lower critical point than this solvent. Thereafter, drying can be performed under supercritical conditions of a single system of carbon dioxide or a mixed system of carbon dioxide and a solvent.
  • Silica air gel can also be produced in the same manner as described above using sodium silicate as a raw material.
  • the refractive index of the silica air mouth gel can be freely changed depending on the raw material mixing ratio of the silica air mouth gel.
  • Examples of the porous body in which the hollow fine particles are dispersed in the matrix include a porous body in which hollow fine particles having voids inside the fine particles are dispersed in the matrix.
  • the material constituting the matrix is not particularly limited, but the dispersion of hollow fine particles Polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, Raw resin, silicone resin, petital resin, phenol resin, butyl acetate resin, ultraviolet curable resin, electron beam curable resin, emulsion resin, water-soluble resin, hydrophilic resin, these Examples thereof include a mixture of resin, a resin resin for coating such as a copolymer or a modified product of these resins, a hydrolyzable organosilicon compound such as alkoxysilane, and a hydrolyzate thereof.
  • hydrolyzable organosilicon compounds such as acrylic resin, epoxy resin, urethane resin, silicone resin, alkoxysilane, and hydrolysates thereof have good fine particle dispersibility and are porous. Since the body is strong, it can be used properly.
  • the hydrolyzable organosilicon compound such as alkoxysilane and the hydrolyzate thereof are formed from one or more compounds selected from the following (a) to (c) group forces, and have molecular It has a — (0—Si) —O— (where m represents a natural number) bond.
  • the hollow fine particles may have an inorganic compound or an organic compound as a material constituting the outer shell, but from the viewpoint of strength, a cavity is formed inside the outer shell made of inorganic compound.
  • Silica-based hollow fine particles that are preferred are inorganic hollow fine particles.
  • the inorganic fine particles include (A) a single layer of an inorganic oxide, (B) a single layer of a composite oxide consisting of several kinds of inorganic oxides, and (C) the above (A) and (B). Those including a double layer can be used.
  • the outer shell may be formed of a porous body having finer pores than the cavity. When the outer shell has pores, it is preferable that the pores are closed and the cavity is sealed against the outside of the outer shell.
  • the outer shell is preferably a plurality of inorganic oxide coating layers such as an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outside, the outer shell is filled and the outer shell is finely packed. The strength can be increased and the cavity can be sealed.
  • fluorine-containing organosilicon compound for forming the second inorganic oxide coating layer is preferable because the refractive index can be lowered, the dispersibility of the hollow fine particles is improved, and the antifouling property is further improved.
  • fluorine-containing organic silicon compounds include 3, 3, 3-trifluoropropyltrimethoxysilane, methyl 3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, Examples include heptadecafluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and the like.
  • the thickness of the outer shell is preferably 1 nm to 50 nm and the average particle diameter of the hollow fine particles is 1Z50 to 1Z5.
  • the size of the inorganic hollow fine particles is not particularly limited, but the average particle size is preferably 5 to 2, and more preferably 20 to LOONm. If the average particle size is too small, the volume of the cavity portion may be reduced and the refractive index may be increased. If the average particle size is too large, the transparency may be lowered due to light diffusion and reflection.
  • the average particle diameter can be determined as a number average particle diameter by observation with a transmission electron microscope.
  • the low refractive index layer can be obtained by applying the air-mouth gel material to a protective film or a protective film laminated with a hard coat layer and drying it.
  • a porous body in which hollow fine particles are dispersed in a matrix is prepared by applying a coating liquid (composition) containing the hollow fine particles and a material constituting the matrix to other layers such as an output-side polarizer and a hard coat layer. It can be obtained by coating in a film and then drying and curing by ionizing radiation and Z or heating.
  • the hollow fine particles can be produced, for example, based on the method described in JP-A-2001-233611.
  • the low refractive index layer has a wavelength of 430 ⁇ at an incident angle of 5 degrees!
  • the maximum value of reflectance at ⁇ 700 nm is usually 1.4% or less, and preferably 1.3% or less.
  • the reflectance at an incident angle of 5 ° and a wavelength of 550 nm is usually 0.7% or less, and preferably 0.6% or less.
  • Maximum power of reflectance at ⁇ 700nm Usually 1.5% or less, preferably 1.4% or less.
  • Reflectance power at a wavelength of 550 nm at an incident angle of 20 degrees is usually 0.9% or less, preferably 0.8% or less.
  • the reflectivity is in the above range, so that reflection of external light and glare are eliminated.
  • a liquid crystal display device with excellent visibility can be obtained.
  • the reflectance is measured using a spectrophotometer (for example, an ultraviolet-visible near-infrared spectrophotometer V-550, manufactured by JASCO Corporation).
  • the reflectance of the low refractive index layer before and after the steel wool test is usually 10% or less, preferably 8% or less. If the variation in reflectivity exceeds 10%, the screen of the liquid crystal display device may be blurred or glaring.
  • the steel wool test is obtained by reciprocating the protective film surface of the output side polarizer 10 times in a state where a load of 0.025 MPa is applied to steel wool # 0000 and measuring the change in reflectance before and after the test. Reflectance is measured five times at five locations on the surface and is calculated from the arithmetic average value of these measurements.
  • the change in reflectance before and after the steel wool test was determined by the following formula (i).
  • R b represents the reflectance before the steel wool test
  • R a represents the reflectance after the steel wool test.
  • the liquid crystal display device of the present invention has a retardation when all of the biaxial optical anisotropic bodies and the liquid crystal cell are overlapped, and light having a wavelength of 550 nm is incident on a normal force when no voltage is applied. A letter when light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • R I exceeds 35 nm, the black display quality will deteriorate when the display screen is viewed from an oblique direction.
  • letter decision R is the position of A (normal direction) as shown in FIG.
  • the direction force of the in-plane slow axis (X) of the optical anisotropic body is inclined in the direction inclined by 45 degrees in the plane (that is, the direction inclined by 45 degrees in the direction of the fast axis (y)) and the normal force is 40
  • This is a letter decision when light with a wavelength of 550 nm is incident from the position B, which is the direction of inclination (polar angle).
  • the letter determination is a value measured using a high-speed spectroscopic ellipsometer, A. Woolam, M-2000U, with a 550 nm wavelength light incident on the A or B position force.
  • a preferred liquid crystal display device of the present invention includes a transmission axis of an output-side polarizer or a transmission axis of an incident-side polarizer, a liquid crystal cell in a state in which no voltage is applied, and at least one biaxial optical anisotropic body.
  • Heavy The slow axis of the sludge is substantially parallel or substantially perpendicular. “Substantially parallel” means that when the angle is displayed at 0 to 90 degrees, the angle between the two axes is 0 to 3 degrees, more preferably 0 to 1 degree. Means an angle of 87 to 90 degrees, more preferably 89 to 90 degrees.
  • the liquid crystal cell without voltage applied and at least one biaxial optical anisotropic body are the same as those used when R and R are measured. Output side deviation
  • the angle formed by the slow axis of an object in which the transmission axis of the photon or the transmission axis of the polarizer on the incident side, the liquid crystal cell in the state where no voltage is applied, and at least one biaxial optical anisotropic body are overlapped is 3 degrees. If it is over and below 87 degrees, light may leak and the black display quality may deteriorate.
  • the direction of the slow axis of an object in which the liquid crystal cell without voltage application and at least one biaxial optical anisotropic body are stacked can be obtained when R is measured.
  • the layer structure is particularly limited as long as it is an array having at least one optical anisotropic body and a liquid crystal cell between the exit side polarizer and the entrance side polarizer. Not.
  • the incident side polarizer 11, the biaxial optical anisotropic body 12, the liquid crystal cell 13, the output side polarizer 14, the low refractive index layer, and the no coat layer 15 are stacked in this order. ing .
  • the arrows in the figure represent the transmission axis for the polarizers 11 and 14 and the in-plane slow axis for the biaxial optical anisotropic body 12.
  • the slow axis in the plane of the biaxial optical anisotropic body 12 is in a positional relationship parallel to the transmission axis of the incident side polarizer 11.
  • the optical anisotropic body, the liquid crystal cell, the optical anisotropic body, and the optical anisotropic body from the incident side polarizer to the output side polarizer Any arrangement of a rectangular liquid crystal cell or a liquid crystal cell, an optical anisotropic body, and an optical anisotropic body can be used.
  • FIG. 3 shows an example of the layer arrangement. As shown in FIG. 3, the incident side polarizer 1, the first optical anisotropic body 2, the liquid crystal cell 3, the second optical anisotropic body 4, the output side polarizer 5, the low refractive index layer and the no coat layer 6 are stacked in this order.
  • the slow axis in the plane of the optical anisotropic body 4 is parallel to the transmission axis of the incident side polarizer, and the slow axis in the plane of the optical anisotropic body 2 is the transmission axis of the output side polarizer. And a parallel positional relationship.
  • films or layers may be provided, for example, a prism array sheet, a lens array sheet, a light diffusion plate, a light guide plate, a diffusion sheet, a brightness enhancement film, etc., in an appropriate position, one layer Or two or more layers can be arranged.
  • liquid crystal display device of the present invention as a backlight, a cold cathode tube, a mercury flat lamp, a light emitting diode, electret luminescence, or the like can be used.
  • the in-plane slow axis direction of the optical anisotropy is obtained at a wavelength of 550 nm, the refractive index n in the in-plane slow axis direction, and the surface
  • the refractive index n in the direction perpendicular to the slow axis and the refractive index n in the thickness direction were measured.
  • the display was darkened and the display characteristics from the front direction and the oblique direction within a polar angle of 80 degrees were visually observed.
  • a spectrophotometer manufactured by JASCO Corporation: “UV-visible near-infrared spectrophotometer V-570”, the reflection spectrum was measured at an incident angle of 5 degrees, and the reflectance at a wavelength of 550 nm was determined.
  • the surface was reciprocated 10 times in a state where a load of 0.025 MPa was applied to steel wool # 0000, and the surface state after the test was visually observed and evaluated in the following two stages.
  • the panel with black display was visually observed and evaluated according to the following three levels.
  • the liquid crystal display panel was installed in an environment with an ambient brightness of 100 lux, and the reflected color was visually observed.
  • a liquid crystal display panel is installed in an environment with an ambient brightness of 100 lux, and the luminance at a position of 5 degrees from the front during dark display and bright display is measured with a color luminance meter (Topcon's color luminance meter BM).
  • liquid crystal display devices of Examples and Comparative Examples were in a state where the low refractive index layer and the hard coat layer were removed (polarizing plate C (polarized light having a low refractive index layer and a hard coat layer laminated).
  • Fig. 4 to Fig. 9 show the simulation results of the luminance simulation at a position where the plane force at the time of dark display and bright display of the liquid crystal display panel is 40 degrees when the plate is replaced with the polarizer P). Showing It was.
  • An optical anisotropic body 2 having a thickness of 100 m was obtained by the same operation as in Production Example 2, except that the oven temperature was set to 134 ° C in Production Example 2.
  • Hexafunctional urethane atallylate oligomer (trade name: NK Oligo U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts, butyl acrylate, 40 parts, isoboronyl metatalylate (trade name: NK ester IB, Shin-Nakamura Chemical Co., Ltd.) 30 parts, 2, 2-diphenol-l-one 10 parts mixed with a homogenizer, 40% methyl isobutyl ketone solution of antimony pentoxide fine particles (average particle size 20nm: hydroxyl group is pyrochlore structure) Is bonded to the antimony atoms appearing on the surface of the coating layer at a ratio of 50% of the total solid content of the hard coat layer forming coating solution. Hard coat layer forming coating solution was prepared.
  • a hollow silica isopropanol dispersion sol (solid content 20%, average primary particle diameter of about 35 nm, outer shell thickness of about 8 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.), hollow fine particle Z silicone resin (condensed compound equivalent) ) Is added to the silicone resin solution so that the weight ratio is 70Z30 based on the solid content, and then diluted with methanol so that the total solid content is 1%.
  • a hollow silica isopropanol dispersion sol solid content 20%, average primary particle diameter of about 35 nm, outer shell thickness of about 8 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.
  • hollow fine particle Z silicone resin condensed compound equivalent
  • Liquid A was prepared by mixing an oligomer of tetraethoxysilane (“methyl silicate 51”, manufactured by Colcoat Co., Ltd.) and methanol in a weight ratio of 47:79.
  • Liquid B was prepared by mixing water, aqueous ammonia (28 wt%), and methanol in a weight ratio of 60: 1.2: 97.2. The liquid A and the liquid B were mixed at a weight ratio of 16:17 to prepare a coating solution 2 for forming a low refractive index layer.
  • a 75 m thick PVA film (Kurarene clay, Vinylon # 7500) was attached to the chuck and immersed in an aqueous solution of 0.2 g of silicon / 60 g of potassium iodide at 30 ° C. for 240 seconds. Next, it was uniaxially stretched 6.0 times in an aqueous solution having a composition of boric acid 70 gZl and potassium iodide 30 gZl, and boric acid treatment was performed for 5 minutes. Finally, by drying at room temperature for 24 hours, a polarizer having an average thickness of 30 m and a degree of polarization of 99.993% was obtained.
  • the original film 1 obtained in Production Example 1 was coated with acrylic on one side of the polarizer obtained in Production Example 8.
  • a polarizer P was obtained by laminating the original film 1 on the incident side of the polarizer through a roll-to-roll method through a PMMA-based adhesive (manufactured by Sumitomo 3EM, DP-8005 clear).
  • Corona discharge treatment was performed on both sides of the original film obtained in Production Example 1 using a high-frequency transmitter (Corona Generator HV 05-2, manufactured by Tamtec) to obtain a base film with a surface tension of 0.72 NZm. It was.
  • HV 05-2 Corona Generator
  • the coating solution for forming the node coat layer obtained in Production Example 4 is applied to one side of the base film using a die coater, and dried in a drying oven at 80 ° C. for 5 minutes. A coating was obtained. Thereafter, ultraviolet rays were irradiated (accumulated dose of 300 miZcm 2 ) to obtain a laminated film 1A in which a hard coat layer having a thickness of 5 m was laminated.
  • the hard coat layer had a refractive index of 1.62 and a pencil hardness of H.
  • the low refractive index layer-forming coating solution 1 obtained in Production Example 5 was applied with a wire bar coater, and allowed to stand for 1 hour to dry, The obtained coating film was heat-treated at 120 ° C. for 10 minutes in an oxygen atmosphere to obtain a laminated film 1B in which a low refractive index layer having a thickness of lOOnm was laminated.
  • the laminated film 1B is rolled to a surface through an acrylic adhesive (DP-8005 clear, manufactured by Sumitomo 3EM), on which the protective film of the polarizer P obtained in Production Example 8 is pasted.
  • a polarizing plate 1C was obtained by laminating by a roll method.
  • the optical laminate 1 was fabricated by laminating in this order so that the slow axis of lb was perpendicular.
  • the resulting optical laminate 1 has a letter R of 2 nm when light with a wavelength of 550 nm is perpendicularly incident, and a letter R when light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • the polarizer P obtained in Production Example 9 was combined with the retardation axis of the polarizer P and the optical anisotropic body la.
  • the layers were laminated so that the phase axis was perpendicular and the surface on which the protective film was not laminated was in contact with the optical anisotropic body la.
  • the polarizing plate 1C obtained in Production Example 10 is formed by laminating the slow axis of the optical anisotropic body lb and the absorption axis of the polarizing plate 1C, and the low refractive index layer of the polarizing plate 1C is not laminated.
  • the liquid crystal display device 1 was produced by laminating so that the surface was in contact with the optical anisotropic body 1b.
  • An optical laminated body 2 was produced in the same manner as in Example 1 except that the optical anisotropic body 2 obtained in 1 was used.
  • the resulting optical laminate 2 has a letter R of 65 nm when light with a wavelength of 550 nm is vertically incident, and letter letter when light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • R was 49 nm.
  • was 16 nm.
  • a liquid crystal display device 2 was produced in the same manner as in Example 1 except that the optical laminate 2 was used in place of the optical laminate 1.
  • Example 10 in place of Low Refractive Index Layer Forming Coating Liquid 1, the same method as in Production Example 10 was used for polarizing except that Low Refractive Index Layer Forming Coating Liquid 3 obtained in Production Example 7 was used. Plate 2C was obtained. Next, in Example 1, a liquid crystal display device 3 was obtained in the same manner as in Example 1 except that this polarizing plate 2C was used instead of the polarizing plate 1C.
  • the evaluation results of the obtained liquid crystal display device 3 are shown in Table 1.
  • polarizing plate 2C polarized light having the low refractive index layer and the hard coat layer laminated
  • Fig. 6 shows the figure obtained by the simulation calculation under the condition that the plate is replaced with the polarizer P).
  • Optical laminated body 4 was produced in the same manner as in Example 1.
  • the resulting optical laminate 4 has a letter R of 3 nm when light with a wavelength of 550 nm is perpendicularly incident, and a letter R when light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • 40 0 I was 38 nm.
  • a liquid crystal display device 4 was produced in the same manner as in Example 1 except that the optical laminate 4 was used in place of the optical laminate 1.
  • the evaluation results of the obtained liquid crystal display device 4 are shown in Table 1.
  • the state in which the low refractive index layer and the hard coat layer are removed (Polarizing plate 1C (polarization layered with the low refractive index layer and the hard coat layer)
  • Fig. 7 shows the contrast diagram obtained by the simulation calculation with the plate) replaced by the polarizer P).
  • a polarizing plate 3C was prepared by attaching the base film side of the laminated film 1A obtained in Production Example 10 and the protective film of the polarizer P so that the surface side was in contact.
  • Example 1 an optical laminate 5 was obtained in the same manner as in Example 1 except that this polarizing plate 3C was used instead of the polarizing plate 1C.
  • the resulting optical laminate 5 has a letter R of 65 nm when light with a wavelength of 550 nm is perpendicularly incident and letter letter when light with a wavelength of 550 nm is incident at a polar angle of 40 degrees.
  • R was 49 nm.
  • was 16 nm.
  • Liquid crystal was produced in the same manner as in Example 1 except that optical laminate 5 was used instead of optical laminate 1. Display device 5 was produced.
  • the evaluation results of the obtained liquid crystal display device 5 are shown in Table 1.
  • the state in which the low refractive index layer and the hard coat layer are removed (Polarizing plate 3C (polarization layered with the low refractive index layer and the hard coat layer)
  • Fig. 8 shows the contrast diagram obtained by the simulation calculation with the plate) replaced by the polarizer P).
  • the polarizing solution was polarized in the same manner as in Production Example 10 except that the coating solution 2 for forming the low refractive index layer obtained in Production Example 6 was used. Plate 4C was obtained.
  • the refractive index of the low refractive index layer provided on the polarizing plate 4C was 1.40.
  • Example 1 a liquid crystal display device 6 was obtained in the same manner as in Example 1 except that this polarizing plate 4C was used instead of the polarizing plate 1C.
  • the evaluation results of the obtained liquid crystal display device 6 are shown in Table 1.
  • polarizing plate 4C polarized light in which the low refractive index layer and the hard coat layer are laminated
  • Fig. 8 shows the contrast diagram obtained by the simulation calculation with the plate) replaced by the polarizer P).
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Optical anisotropic body Biaxial stretching Biaxial stretching Biaxial stretching TAC Biaxial stretching Biaxial stretching
  • a biaxial optical anisotropic body and a VA mode liquid crystal cell are provided between the exit-side polarizer and the entrance-side polarizer, satisfying the relationship of n> n> n, and optically different.
  • the relationship IR — RI ⁇ 35 nm is satisfied, and the air side is
  • a liquid crystal display device with a low refractive index layer composed of a mouth gel with a refractive index of 1.37 or less has a display screen whether viewed from the front or from an oblique direction within a polar angle of 80 degrees. It turns out to be good and homogeneous.
  • the display screen in this case has good power. When viewed from an oblique direction with an azimuth angle of 45 degrees, the black display quality is poor. is there.
  • the liquid crystal display device of Comparative Example 2 and Comparative Example 3 whose refractive index of the low refractive index layer is 1.40 can suppress the deterioration of the display quality due to the change of the viewing angle, but has a high reflectance and the screen is glaring.
  • the display quality is poor, such as reflections.
  • the liquid crystal display device of the present invention has a wide viewing angle, no reflection, excellent scratch resistance, good black display quality from any direction, and a uniform and high contrast.
  • the liquid crystal cell in the liquid crystal cell is arranged so that the slow axis of the layered product of the liquid crystal cell and the biaxial optical anisotropic body is in a position substantially parallel or substantially perpendicular to the transmission axis of the polarizer.
  • the viewing angle compensation of the polarizer can also be performed.
  • the liquid crystal display device of the present invention can be suitably used as a large-screen flat panel display or the like.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L’invention concerne un affichage à cristaux liquides en mode d’alignement vertical (VA) disposé de manière séquentielle avec une couche à faible indice de réfraction, un polariseur côté sortie, au moins une feuille de corps anisotrope optiquement biaxial, une cellule à cristaux liquides et un polariseur côté incident où (1) une relation nx>ny>nz (nx, ny: indice de réfraction principal dans le plan de tout le corps anisotrope optiquement, nz : indice de réfraction principal dans le sens de l’épaisseur) est satisfaite, (2) la couche à faible indice de réfraction est composée d’un aérogel ayant un indice de réfraction inférieur ou égal à 1,37, et (3) une relation |R40-R0|≤35 nm est satisfaite entre le retard R0 obtenu lorsqu’une lumière de longueur d’onde de 550 nm pénètre depuis le sens normal lorsqu’une tension n’est pas appliquée, et le retard R40 obtenu lorsqu’une lumière de longueur d’onde de 550 nm pénètre depuis la direction de 40° d’angle polaire dans un état dans lequel le corps anisotrope optiquement biaxial et la cellule à cristaux liquides sont empilés en excluant le polariseur côté sortie et le polariseur côté incident.
PCT/JP2005/021244 2004-11-19 2005-11-18 Affichage à cristaux liquides Ceased WO2006054695A1 (fr)

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JP2007334134A (ja) * 2006-06-16 2007-12-27 Riken Technos Corp 反射防止フィルム
JP2008139581A (ja) * 2006-12-01 2008-06-19 Asahi Glass Co Ltd 反射防止膜付き基体
JP2008224843A (ja) * 2007-03-09 2008-09-25 Stanley Electric Co Ltd 液晶表示装置
CN102854660A (zh) * 2012-09-24 2013-01-02 深圳市华星光电技术有限公司 一种光学补偿膜及减弱va液晶显示器暗态漏光的方法
CN102854659A (zh) * 2012-09-24 2013-01-02 深圳市华星光电技术有限公司 一种光学补偿膜及减弱va液晶显示器暗态漏光的方法
CN103033986A (zh) * 2013-01-09 2013-04-10 深圳市华星光电技术有限公司 用于液晶面板的补偿系统及液晶显示装置
CN103091902A (zh) * 2013-01-18 2013-05-08 深圳市华星光电技术有限公司 液晶显示器
JP2013205500A (ja) * 2012-03-27 2013-10-07 Nippon Zeon Co Ltd 位相差板の製造方法
US11150503B2 (en) 2015-12-17 2021-10-19 Zeon Corporation Liquid crystal display device

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JP2002071954A (ja) * 2000-09-05 2002-03-12 Fuji Photo Film Co Ltd 光学補償シート、偏光板および液晶表示装置
JP2003207783A (ja) * 2001-11-30 2003-07-25 Eastman Kodak Co 画像形成素子
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JP2007334134A (ja) * 2006-06-16 2007-12-27 Riken Technos Corp 反射防止フィルム
JP2008139581A (ja) * 2006-12-01 2008-06-19 Asahi Glass Co Ltd 反射防止膜付き基体
JP2008224843A (ja) * 2007-03-09 2008-09-25 Stanley Electric Co Ltd 液晶表示装置
JP2013205500A (ja) * 2012-03-27 2013-10-07 Nippon Zeon Co Ltd 位相差板の製造方法
WO2014043942A1 (fr) * 2012-09-24 2014-03-27 深圳市华星光电技术有限公司 Film de compensation optique et procédé pour atténuer les fuites de lumière à l'état foncé d'un dispositif d'affichage à cristaux liquides à alignement vertical (va)
CN102854659A (zh) * 2012-09-24 2013-01-02 深圳市华星光电技术有限公司 一种光学补偿膜及减弱va液晶显示器暗态漏光的方法
WO2014043943A1 (fr) * 2012-09-24 2014-03-27 深圳市华星光电技术有限公司 Film de compensation optique et procédé pour atténuer les fuites de lumière à l'état foncé d'un dispositif d'affichage à cristaux liquides à alignement vertical (va)
CN102854660A (zh) * 2012-09-24 2013-01-02 深圳市华星光电技术有限公司 一种光学补偿膜及减弱va液晶显示器暗态漏光的方法
CN103033986A (zh) * 2013-01-09 2013-04-10 深圳市华星光电技术有限公司 用于液晶面板的补偿系统及液晶显示装置
WO2014107886A1 (fr) * 2013-01-09 2014-07-17 深圳市华星光电技术有限公司 Système de compensation pour écran à cristaux liquides et dispositif d'affichage à cristaux liquides
CN103091902A (zh) * 2013-01-18 2013-05-08 深圳市华星光电技术有限公司 液晶显示器
WO2014110839A1 (fr) * 2013-01-18 2014-07-24 深圳市华星光电技术有限公司 Dispositif d'affichage à cristaux liquides
CN103091902B (zh) * 2013-01-18 2015-09-09 深圳市华星光电技术有限公司 液晶显示器
US9645445B2 (en) 2013-01-18 2017-05-09 Shenzhen China Star Optoelectronics Technology Co., Ltd. Liquid crystal display
US11150503B2 (en) 2015-12-17 2021-10-19 Zeon Corporation Liquid crystal display device

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