WO2010150577A1 - 偏光板、及び液晶表示装置 - Google Patents

偏光板、及び液晶表示装置 Download PDF

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Publication number
WO2010150577A1
WO2010150577A1 PCT/JP2010/053650 JP2010053650W WO2010150577A1 WO 2010150577 A1 WO2010150577 A1 WO 2010150577A1 JP 2010053650 W JP2010053650 W JP 2010053650W WO 2010150577 A1 WO2010150577 A1 WO 2010150577A1
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Prior art keywords
film
hard coat
polarizing plate
mass
coat layer
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PCT/JP2010/053650
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English (en)
French (fr)
Japanese (ja)
Inventor
岡野　賢
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コニカミノルタオプト株式会社
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Priority to KR1020117030156A priority Critical patent/KR101689912B1/ko
Priority to JP2011519637A priority patent/JP5382118B2/ja
Publication of WO2010150577A1 publication Critical patent/WO2010150577A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • 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
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a polarizing plate and a liquid crystal display device.
  • polarizing plate is a polarizing element in which a polyvinyl alcohol (hereinafter abbreviated as PVA) film adsorbed and dyed with iodine or a dichroic dye is stretched and oriented in a certain direction between two cellulose-based protective films ( It has a three-layer structure with a polarizing film) in between.
  • PVA polyvinyl alcohol
  • the adhesive layer is provided in the cellulose protective film single side
  • the protective film on the outermost surface of the polarizing plate used in the liquid crystal cell is particularly susceptible to physical damage, and when it is damaged, the display image quality is impaired. Therefore, a hard coat layer is formed on the substrate of the cellulose-based protective film. The provided hard coat film is used.
  • a hard coat film is required to be a clear type rather than an anti-glare type that blurs the outline of an image reflected on the surface from the viewpoint of higher contrast and visibility (clearness).
  • the polarizing plate provided with the adhesive layer of the liquid crystal display panel is assumed to be transported and stored under high temperature and high humidity for a long time in a stacked state, it will be partially on the outermost surface of the polarizing plate due to blocking etc. Deformation failures are likely to occur, which is a quality problem.
  • Patent Document 1 discloses a polarizing plate technique for improving durability under high temperature and high humidity conditions. This technique improves the durability of a polarizing plate by treating a polarizing film, which is a hydrophilic polymer film, with an acidic solution and providing a protective film with a layer obtained by curing a polymerizable resin composition. .
  • a polarizing film which is a hydrophilic polymer film
  • an acidic solution and providing a protective film with a layer obtained by curing a polymerizable resin composition.
  • the above technique can improve the discoloration of the polarizing plate to some extent, it cannot prevent the deformation failure that is the subject of the present invention.
  • Patent Document 2 discloses a coating film containing at least one organic component having a polymerizable functional group, inorganic ultrafine particles, and inorganic and / or organic fine particles having a primary particle size larger than the primary particle size of the inorganic ultrafine particles.
  • a technique for preventing blocking of a hard coat film by a hard coat film formed from components is disclosed.
  • fine particles are added in order to sufficiently prevent blocking, haze is likely to increase, and there is still a problem in achieving both the prevention of deformation failure, which is the subject of the present invention, and visibility (clearness). It was.
  • the objective of this invention is providing the polarizing plate which aimed at coexistence suppression of generation
  • the hard coat layer has 500 to 200,000 protrusions / mm 2
  • a polarizing plate characterized in that the arithmetic average roughness Ra (JIS B0601: 2001) of the coat layer is 2 to 20 nm, and the haze value (Hh) of the hard coat film is 0.2 to 0.6%. .
  • the difference (Hh ⁇ Hf) between the haze value (Hh) of the hard coat film and the haze value (Hf) of the base film of the hard coat film is 0.02% to 0.3%, 2.
  • the polarizing plate as described in any one of 1 to 4 above, which is 50:50.
  • the polarizing plate as described in any one of 1 to 5 above, wherein
  • a liquid crystal display device comprising the polarizing plate according to any one of 1 to 6 in at least one of the liquid crystal cells.
  • the polarizing plate which aimed at coexistence suppression of generation
  • the present inventor has provided a specific number of protrusions on the hard coat layer of the hard coat film to be bonded to the polarizing plate.
  • the present invention has been found.
  • the hard coat film according to the present invention has a low haze value and clearness as a liquid crystal display device is not impaired, it is possible to achieve both suppression of partial deformation failure and visibility (clearness). .
  • the hard coat layer according to the present invention is characterized by having 500 to 200000 protrusions / mm 2 , and the number of protrusions present is a value measured by the following method.
  • the number of protrusions can also be measured from a hard coat layer disposed on the viewing side when used in a display device such as a liquid crystal display device.
  • the number of protrusions was measured by measuring the hard coat layer with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO, magnification 50 times). Next, the number of protrusions in this measurement area (100 ⁇ m ⁇ 100 ⁇ m square) was read from the image. This series of measurements was performed 10 times, and the number of protrusions of the hard coat layer of the hard coat film was determined from the average value of 10 times.
  • RST / PLUS optical interference surface roughness meter
  • protrusions having a height of 3 nm or more from the average line of the roughness curve were counted.
  • the protrusion shape has a height of 1 nm to 5 ⁇ m, preferably 1 nm to 1 ⁇ m, preferably 10 nm to 0.5 ⁇ m.
  • the width is 50 nm to 100 ⁇ m, preferably 50 nm to 50 ⁇ m.
  • FIG. 1 is an explanatory view of the protrusion.
  • the cross-section of the hard coat film was cut in the film width direction at room temperature at an angle of 0 ° using a microtome (manufactured by Japan Microtome Laboratories). Next, this cross section was observed using a transmission electron microscope (TEM, magnification 2000 times). According to the definition of JIS B 0601: 2001, the center line a is drawn on the image from the cross-sectional observed image, and the lines b and c forming the mountain ridge and the center line a are 2 The distance between the two intersections was defined as the protrusion size width t. Further, the distance from the summit to the center line a is obtained as the height h of the protrusion size.
  • the arithmetic average roughness Ra specified in JIS B0601: 2001 of the hard coat layer according to the present invention is 2 to 20 nm, more preferably 4 to 20 nm.
  • the arithmetic average roughness of the hard coat layer can be measured and analyzed using a commercially available surface roughness measuring instrument.
  • it can be determined using a small surface roughness measuring instrument (model number; SJ-401, manufactured by Mitutoyo Corporation). It can also be measured with an optical interference type surface roughness measuring instrument, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.
  • a method for forming the protrusion shape As a method for forming the protrusion shape, a method for adding fine particles, a method for forming a protrusion on the surface by pressing a mold, and a method for forming surface irregularities by mixing resins having different SP values (solubility parameters) ( Examples thereof include the methods described in JP-A-2007-182519 and JP-A-2009-13384.
  • mold rolls used to form protrusions those with fine irregularities and coarse ones can be selected and applied as appropriate, and patterns, mats, lenticular lenses, and spherical irregularities are regularly or randomly arranged. it can.
  • a method of forming protrusions by adding fine particles is preferable from the viewpoint of productivity and reproducibility.
  • the haze value (Hh) of the hard coat film according to the present invention is 0.2 to 0.6%.
  • the haze value (Hh) of the hard coat film is set to 0.2 to 0.6%, the objective effect of the present invention is achieved, and when used outdoors such as an enlarged liquid crystal display device or digital signage. This is also preferable in that sufficient luminance and high contrast can be obtained. If the haze value (Hh) of the hard coat film is less than 0.2%, it is difficult to design from the viewpoint of the handleability of the hard coat film.
  • the effect of the present invention is that the difference (Hh ⁇ Hf) between the haze value (Hh) of the hard coat film and the haze value (Hf) of the base film is 0.02% to 0.3%. Is preferable in achieving the above.
  • Controlling the haze value of the hard coat layer is achieved by adjusting the type and amount of resin, additives, etc. that make up the hard coat layer, and adjusting the type, particle size, and amount of added fine particles. Is done.
  • the roughness of the surface also affects the haze value as the surface haze, it is effective to control the shape and number of the protrusions.
  • the hard coat film according to the present invention is composed of at least a base film and a hard coat layer, and the hard coat layer contains an actinic radiation curable resin, and an actinic ray such as an ultraviolet ray or an electron beam (both active energy rays). It is preferably a layer mainly composed of a resin that cures through a crosslinking reaction upon irradiation.
  • an actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams.
  • Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but the resin that is cured by ultraviolet irradiation is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
  • polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
  • the hard coat layer contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • the hard coat layer according to the present invention preferably contains fine particles of an inorganic compound or an organic compound so as to have 500 to 200,000 protrusions / mm 2 and an arithmetic average roughness Ra of 2 to 20 nm.
  • silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate.
  • silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.
  • These inorganic fine particles are preferably coated with an organic component having a reactive functional group on a part of the surface because the scratch resistance is improved while maintaining the transparency of the hard coat film.
  • a method for coating an organic component having a reactive functional group on a part of the surface for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, and the surface A mode in which an organic component is bonded to a part of the metal particle, a mode in which an organic component is attached to a hydroxyl group present on the surface of a metal oxide fine particle by an interaction such as a hydrogen bond, or one or more inorganic particles in a polymer particle.
  • fine-particles etc. are mentioned.
  • Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin. Powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, or the like can be added.
  • Preferred fine particles include crosslinked polystyrene particles (for example, SX-130H, SX-200H, SX-350H manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150 and MX300 manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles.
  • fluorine-containing acrylic resin fine particles include commercially available products such as FS-701 manufactured by Nippon Paint.
  • acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.
  • the average particle diameter of these fine particle powders is not particularly limited, but is preferably 0.01 to 5 ⁇ m, and more preferably 0.01 to 1.0 ⁇ m. Moreover, you may contain 2 or more types of microparticles
  • the average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring device.
  • the ratio of the ultraviolet curable resin composition and the fine particles is desirably 10 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the resin composition.
  • These hard coat layers are coated using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, and the like. And can be formed by UV curing.
  • the coating amount is suitably 0.1 to 40 ⁇ m, preferably 0.5 to 30 ⁇ m, as the wet film thickness.
  • the dry film thickness is from 0.1 to 30 ⁇ m, preferably from 1 to 20 ⁇ m, particularly preferably from 6 to 15 ⁇ m.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm 2 , preferably 5 to 200 mJ / cm 2 .
  • irradiating active rays it is preferably performed while applying tension in the film transport direction, more preferably while applying tension in the width direction.
  • the tension to be applied is preferably 30 to 300 N / m.
  • the method for applying tension is not particularly limited, and tension may be applied in the conveying direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
  • the hard coat layer according to the present invention may contain a conductive agent in order to impart antistatic properties, and preferred conductive agents include metal oxide particles or ⁇ -conjugated conductive polymers.
  • An ionic liquid is also preferably used as the conductive compound.
  • the hard coat layer has a nonionic surfactant such as a silicone surfactant, a fluorosurfactant or a polyoxyether, an anion, from the viewpoint of coatability and uniform dispersibility of fine particles.
  • a surfactant or the like can also be contained. These enhance the applicability.
  • these components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.
  • FIG. 2 shows a schematic diagram of a hard coat film having a hard coat layer according to the present invention and a polarizing plate.
  • two layers such as the hard coat layers 2a and 2b are laminated, but may be one layer or a plurality of layers.
  • Provided in two or more layers in order to better demonstrate the object effects of the present invention and to make it easier to control the hard coat properties, haze, protrusion shape formed on the surface, and arithmetic surface roughness Ra of the hard coat layer. It is preferable.
  • the thickness of the uppermost layer when two or more layers are provided is preferably in the range of 0.05 to 2 ⁇ m.
  • Two or more layers may be formed by simultaneous multilayers.
  • the simultaneous multi-layering is to form a hard coat layer by applying two or more hard coat layers on a base material without going through a drying step.
  • the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.
  • the hard coat film has a pencil hardness, which is an index of hardness, of H or more, more preferably 3H or more. If it is 3H or more, it is not only difficult to be scratched in the polarizing plate forming step of the liquid crystal display device, but also used for outdoor applications, and is a surface protective film for large liquid crystal display devices and liquid crystal display devices for digital signage. When used as an excellent film strength.
  • the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more, and then the pencil hardness evaluation specified by JIS K5400 is performed using a test pencil specified by JIS S 6006. It is the value measured according to the method.
  • the base film is easy to manufacture, easily adheres to the hard coat layer, and is optically isotropic. Moreover, a base film can also be used as a protective film according to the present invention as it is.
  • cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate Polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic Tick polystyrene film, norbornene resin film, polymethylpentene film Polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, cycloolefin polymer films, and polymethyl methacrylate film or an acrylic film or the like.
  • cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, cellulose
  • cellulose ester films for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UE, KC4UE, and KC12UR (above, Konica Minolta Opto Co., Ltd., Polycarbonate Film)
  • Olefin polymer films and polyester films are preferred, and in the present invention, the cellulose ester film is particularly advantageous in terms of production, cost, isotropy, adhesiveness (saponification suitability), and the object effects of the present invention. preferable.
  • the refractive index of the base film according to the present invention is preferably 1.30 to 1.70, more preferably 1.40 to 1.65.
  • the refractive index is measured by the method of JIS K7142 using an upe refractometer 2T manufactured by Atago Co., Ltd.
  • the cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose.
  • the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms, such as cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A-10-45804 and 08-231761.
  • Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used.
  • the lower fatty acid esters of cellulose that are particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.
  • cellulose triacetate those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%.
  • acetylation bound acetic acid amount
  • Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester including a cellulose ester that simultaneously satisfies I) and (II).
  • cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9.
  • the portion that is not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods. The method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.
  • the molecular weight of the cellulose ester is preferably a number average molecular weight (Mn) of 60,000 to 300,000, more preferably 70,000 to 200,000, particularly preferably 100,000 to 200,000.
  • the cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, more preferably 1.4 to 2.3.
  • the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.
  • the measurement conditions are as follows.
  • Thermoplastic acrylic resin includes methacrylic resin.
  • the thermoplastic acrylic resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.
  • Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
  • Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like, and these can be used alone or in combination of two or more monomers.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferably used.
  • the weight average molecular weight (Mw) is preferably 80,000 to 500,000, and more preferably 110,000 to 500,000.
  • the weight average molecular weight of the thermoplastic acrylic resin can be measured by the gel permeation chromatography described above, including the measurement conditions.
  • thermoplastic acrylic resin there is no restriction
  • a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
  • the polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent. Commercial products can also be used.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Denki Kagaku Kogyo Co., Ltd.) and the like can be mentioned.
  • Two or more thermoplastic acrylic resins can be used in combination.
  • the thermoplastic acrylic resin a graft copolymer obtained by grafting a (meth) acrylic resin to a copolymer of (meth) acrylic rubber and an aromatic vinyl compound described in JP-A-2009-84574 is used. May be.
  • graft copolymer a copolymer of (meth) acrylic rubber and an aromatic vinyl compound forms a core, and the (meth) acrylic resin forms a shell around the copolymer.
  • -A shell-type graft copolymer is preferred.
  • the total mass of the thermoplastic acrylic resin and the cellulose ester resin in the base film is preferably 55% by mass or more of the base film, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. is there.
  • the base film may contain a resin other than thermoplastic acrylic resin and cellulose ester resin and additives.
  • the base film preferably contains acrylic particles from the viewpoint of improving brittleness and obtaining excellent pencil hardness.
  • the acrylic particle represents an acrylic component present in a particle state (also referred to as an incompatible state) in a base film containing the thermoplastic acrylic resin and the cellulose ester resin in a compatible state.
  • the acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably a multilayer structure acrylic granular composite.
  • acrylic granular composites that are multi-layer structured polymers
  • examples of commercially available acrylic granular composites that are multi-layer structured polymers include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kaneace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and “Acryloid” manufactured by Haas, “Staffyroid” manufactured by Ganz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used.
  • acrylic particles that are graft copolymers suitably used as acrylic particles include unsaturated carboxylic acid ester monomers, unsaturated carboxylic acid monomers in the presence of rubbery polymers. And a graft copolymer obtained by copolymerizing a mixture of a monomer, an aromatic vinyl monomer, and, if necessary, a monomer composed of other vinyl monomers copolymerizable therewith.
  • the rubbery polymer used for the acrylic particles that are the graft copolymer but diene rubber, acrylic rubber, ethylene rubber, and the like can be used.
  • Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, and ethylene-methyl acrylate copolymer A polymer etc. are mentioned. These rubbery polymers can be used alone or in a mixture of two or more.
  • the refractive index of the mixture of the thermoplastic acrylic resin and the cellulose ester resin is close to the refractive index of the acrylic particles in order to obtain a highly transparent film.
  • the refractive index difference between the acrylic particles and the thermoplastic acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
  • the method of blending the acrylic particles with the thermoplastic acrylic resin is not particularly limited, and after blending the thermoplastic acrylic resin and other optional components in advance, usually at 200 to 350 ° C. while adding the acrylic particles, uniaxially or A method of uniformly melt-kneading with a twin-screw extruder is preferably used.
  • a solution in which acrylic particles are dispersed in advance is added to and mixed with a solution (dope solution) in which a thermoplastic acrylic resin and a cellulose ester resin are dissolved, and acrylic particles and other optional additives are dissolved and mixed.
  • a method such as in-line addition of the prepared solution can be used.
  • acrylic particles can also be used.
  • metabrene W-341 (manufactured by Mitsubishi Rayon Co., Ltd.)
  • Chemisnow MR-2G (C3)
  • MS-300X (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.
  • the acrylic fine particles are contained in a mass ratio with respect to the total mass of the thermoplastic acrylic resin and the cellulose ester resin constituting the film.
  • a plasticizer can be used in combination with the base film.
  • the plasticizer include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy. Of these, polyester and phthalate plasticizers are preferably used. Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate, but are slightly inferior in plasticizing effect and compatibility.
  • the polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol.
  • Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
  • glycol examples include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene, and dipropylene. These divalent carboxylic acids and glycols may be used alone or in combination.
  • the ester plasticizer may be any of ester, oligoester, and polyester types, and the molecular weight is preferably in the range of 100 to 10,000, and preferably in the range of 600 to 3000, which has a large plasticizing effect.
  • the viscosity of the plasticizer has a correlation with the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, the range of 200 to 5000 MPa ⁇ s (25 ° C.) is preferable because of compatibility and plasticization efficiency. Furthermore, some polyester plasticizers may be used in combination.
  • the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the base film. If the added amount of the plasticizer exceeds 30 parts by mass, the surface becomes sticky, which is not preferable for practical use.
  • the base film preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone And benzophenones.
  • ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high-temperature molding, so that the weather resistance is effectively improved with a relatively small amount of addition. be able to.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
  • antioxidants can be added to the base film in order to improve the thermal decomposability and thermal colorability during the molding process. It is also possible to add an antistatic agent to give the optical film antistatic performance.
  • a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
  • Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
  • triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
  • the base film according to the present invention is preferably a “film that does not cause ductile fracture”.
  • the ductile fracture is a fracture caused by applying a stress larger than the strength of a certain material, and is defined as a fracture accompanied by significant elongation or drawing of the material until the final fracture.
  • the fracture surface is characterized by numerous indentations called dimples.
  • the base film according to the present invention is required to withstand use in a high-temperature environment, and if the tension softening point is 105 ° C. to 145 ° C., it can be determined that it exhibits sufficient heat resistance. In particular, it is preferable to control at 110 to 130 ° C.
  • a Tensilon tester (ORIENTEC Co., RTC-1225A) is used to cut out the optical film at 120 mm (length) ⁇ 10 mm (width) and pull it with a tension of 10 N.
  • the temperature can be continuously increased at a temperature increase rate of 30 ° C./min, and the temperature at 9 N can be measured three times, and the average value can be obtained.
  • the substrate film preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
  • Tg glass transition temperature
  • the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min. Point glass transition temperature (Tmg).
  • the dimensional change rate (%) is preferably less than 0.5%, and more preferably less than 0.3%.
  • the substrate film has a defect with a diameter of 5 ⁇ m or more in the film plane of 1 piece / 10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
  • the diameter of the defect indicates the diameter when the defect is circular, and when it is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
  • the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
  • the defect is a change in the surface shape, such as transfer of a roll flaw or an abrasion
  • the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
  • the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
  • the coating agent may not be formed uniformly, resulting in defects (coating defects).
  • the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to the foreign matter (foreign matter defect) in the film.
  • the base film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more in the measurement based on JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the thickness of the base film is preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more.
  • the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying, and the like.
  • the thickness of the film can be appropriately selected depending on the application.
  • the base film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film.
  • a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, a hot press method, or the like can be used.
  • melt casting film forming method From the viewpoint of suppressing residual solvent using a cellulose ester resin or a thermoplastic acrylic resin for dissolution, a method of producing by a melt casting film forming method is preferable. Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method is preferable, in which a film having excellent mechanical strength and surface accuracy can be obtained. From the viewpoints of suppressing coloring, suppressing defects of foreign matters, and suppressing optical defects such as die lines, solution casting by casting is preferred.
  • a method of extruding a film forming material onto a drum or an endless belt after the film forming material is heated to develop its fluidity is also included as a melt casting film forming method.
  • Organic solvent useful for forming the dope when the base film is produced by the solution casting method is not limited as long as it can dissolve thermoplastic acrylic resin, cellulose ester resin, and other additives at the same time. I can do it.
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
  • the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • the proportion of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
  • the proportion of alcohol is small, thermoplastic acrylic resins and cellulose ester resins in non-chlorine organic solvent systems There is also a role of promoting dissolution of the.
  • thermoplastic acrylic resin in particular, cellulose ester resin, and acrylic particles are used.
  • a dope composition in which 45% by mass is dissolved is preferable.
  • linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
  • Cellulose ester film and cellulose ester resin / thermoplastic acrylic resin film are prepared by solution casting, and a dope is prepared by dissolving cellulose ester or cellulose ester resin / thermoplastic acrylic resin and additives in a solvent.
  • a step of casting the dope on a belt-shaped or drum-shaped metal support a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, and a step of further drying. It is performed by a process of winding up the finished film.
  • the concentration of the cellulose ester in the dope, and the concentration of the cellulose ester resin / thermoplastic acrylic resin is preferably higher because the drying load after casting on the metal support can be reduced, but the concentration of the cellulose ester is too high.
  • the load at the time of filtration increases, resulting in poor filtration accuracy.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 ⁇ 4m.
  • the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected at any time during or after production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is preferably peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less. Is 0.1% by mass or less, particularly preferably 0 to 0.01% by mass.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while transporting the web is employed.
  • the cellulose ester film and the cellulose ester resin / thermoplastic acrylic resin film are also preferably formed by a melt film forming method.
  • a melt film forming method a composition containing cellulose ester and an additive such as a cellulose ester resin / thermoplastic acrylic resin and a plasticizer is heated and melted to a temperature showing fluidity, and then contains a fluid cellulose ester. It refers to casting a melt.
  • the molding method for heating and melting can be further classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like.
  • the melt extrusion method is excellent.
  • a plurality of raw materials used for melt extrusion are usually kneaded and pelletized in advance.
  • Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and formed into a strand from a die. It can be done by extrusion, water cooling or air cooling and cutting.
  • Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
  • a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
  • the extruder is preferably processed at as low a temperature as possible so that it can be pelletized so as to suppress the shearing force and prevent the resin from deteriorating (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • Film formation is performed using the pellets obtained as described above.
  • the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
  • the melting temperature at the time of extrusion is about 200 to 300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, and then formed into a film from the T die.
  • the film is nipped by a cooling roll and an elastic touch roll, and solidified on the cooling roll.
  • the extrusion flow rate is preferably carried out stably by introducing a gear pump. Further, a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
  • Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
  • the film temperature on the touch roll side when the film is nipped by the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film.
  • a well-known roll can be used for the roll which has the elastic body surface used for such a purpose.
  • the elastic touch roll is also called a pinching rotator.
  • a touch roll disclosed in registered patent 3194904, registered patent 3422798, Japanese Patent Application Laid-Open No. 2002-36332, Japanese Patent Application Laid-Open No. 2002-36333, or the like can be preferably used. These can also use what is marketed.
  • the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roll.
  • the stretching method a known roll stretching machine or tenter can be preferably used.
  • the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking or scratching during winding.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
  • grip part of the clip of both ends of a film is cut out and reused.
  • the hard coat film according to the present invention may be provided with functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer.
  • functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer.
  • a back coat layer may be provided on the surface of the base film opposite to the side on which the hard coat layer is provided to prevent curling and sticking.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.
  • the particles contained in the backcoat layer are preferably 0.1 to 50% by mass with respect to the binder.
  • the increase in haze is preferably 1.5% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less.
  • the binder is preferably a cellulose ester resin such as diacetylcellulose.
  • the hard coat film according to the present invention can be used as an antireflection film having an external light antireflection function by coating an antireflection layer on the hard coat layer.
  • the antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflection layer is preferably composed of a low refractive index layer having a refractive index lower than that of the support, or a combination of a high refractive index layer having a refractive index higher than that of the support and a low refractive index layer. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support).
  • an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
  • the layer structure of the antireflection film the following structure can be considered, but it is not limited to this.
  • the refractive index layer preferably contains silica-based fine particles, and the refractive index thereof is lower than the refractive index of the base film as a support, and is in the range of 1.30 to 1.45 at 23 ° C. and wavelength of 550 nm. Preferably there is.
  • the film thickness of the low refractive index layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and most preferably 30 nm to 0.2 ⁇ m.
  • the composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles.
  • the particles having the outer shell layer and having a porous or hollow interior are preferably hollow silica-based fine particles.
  • composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.
  • OSi-1 organosilicon compound represented by the following general formula (OSi-1)
  • hydrolyzate thereof a hydrolyzate thereof
  • polycondensate thereof a polycondensate thereof.
  • R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.
  • a solvent and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added.
  • the polarizing plate of the present invention using the hard coat film according to the present invention will be described.
  • the polarizing plate can be produced by a general method.
  • the back surface side of the hard coat film according to the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated hard coat film in an iodine solution. It is preferable to stick them together.
  • the hard coat film may be used on the other surface, or another polarizing plate protective film may be used.
  • an optical compensation film (retardation film) having a retardation of in-plane retardation Ro of 590 nm, 20 to 70 nm, and Rt of 70 to 400 nm may be used to obtain a polarizing plate capable of widening the viewing angle. it can.
  • These can be produced, for example, by the method of JP-A-2002-71957.
  • the optically anisotropic layer can be formed by the method described in JP-A-2003-98348.
  • polarizing plate protective films preferably used include KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-2, KC4FR-2, KC4FR-2, KC8FR-2 KC4UE (Konica Minolta Opto Co., Ltd.) etc. are mentioned.
  • the polarizing film which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction.
  • a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film.
  • polarizing film a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.
  • a polarizing film having a thickness of 5 to 30 ⁇ m, preferably 8 to 15 ⁇ m is preferably used.
  • one side of the hard coat film according to the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
  • the pressure-sensitive adhesive layer used on one side of the protective film to be bonded to the substrate of the liquid crystal cell is preferably optically transparent and exhibits moderate viscoelasticity and adhesive properties.
  • the adhesive layer include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethane, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers.
  • a film such as a drying method, a chemical curing method, a thermal curing method, a thermal melting method, a photocuring method, or the like can be formed and cured using a polymer such as the above.
  • the acrylic copolymer can be preferably used because it is most easy to control the physical properties of the adhesive and is excellent in transparency, weather resistance, durability and the like.
  • the hard coat film according to the present invention is incorporated in a polarizing plate, and is a reflective type, transmissive type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS. It is preferably used in liquid crystal display devices of various driving systems such as a type and OCB type.
  • Example 1 ⁇ Preparation of base film 1> (Preparation of dope solution)
  • the following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. .
  • the silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester.
  • This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution A.
  • the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.
  • the web is transported while being dried with a drying air of 90 ° C. in a transport and drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped with a tenter, and then the web 1 is stretched in the width direction at 130 ° C. The film was stretched so as to be 1 time. After stretching with a tenter, the web was dried with 130 ° C. drying air in a transport drying process using a plurality of rolls arranged vertically.
  • the film After heat treatment for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying process, the film was subjected to a knurling process with a width of 10 mm and a height of 10 ⁇ m at both ends of the film, cooled to room temperature and wound on a core.
  • a base film 1 having a thickness of 0.5 m, a thickness of 40 ⁇ m, and a length of 4000 m was produced.
  • the following hard coat layer coating composition 1-1 is filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to prepare a hard coat layer coating solution, which is applied using a micro gravure coater. and, after drying at 80 ° C., using an ultraviolet lamp, irradiance 80 mW / cm 2 irradiation unit to cure the coating layer the amount of irradiation as 80 mJ / cm 2, forming a hard coat layer 1 dry film thickness 8 ⁇ m did.
  • the hard coat layer coating composition 1-2 is applied onto the hard coat layer 1 by an extrusion coater, dried at 80 ° C., and nitrogen is added so that the oxygen concentration becomes 1.0 vol% or less. while purging, the illuminance of the irradiation unit using a UV lamp 150 mW / cm 2, thereby curing the coated layer irradiation amount as 250 mJ / cm 2, to form a hard coat layer 2 of a dry film thickness of 0.6 .mu.m. Further, after forming the hard coat layer 2, the following back coat layer coating composition 1 was applied to the surface opposite to the surface on which the hard coat layer was applied with a coater so as to have a wet film thickness of 10 ⁇ m. Then, a back coat layer 1 was provided, wound up, and a roll-shaped hard coat film 1 was produced.
  • Hard Coat Layer Coating Composition 1-1) The following materials were stirred and mixed to obtain hard coat layer coating composition 1.
  • NK ester A-TMM-3LM-N a solution composed of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate made by Shin-Nakamura Chemical Co. was added dropwise at 30 ° C. over 1 hour.
  • the specific organic compound (S1) was obtained by heating and stirring at 3 ° C. for 3 hours.
  • the average particle size of the silica particles was 35 nm. Here, the average particle diameter was measured with a transmission electron microscope. Next, the following materials were stirred and mixed to obtain a hard coat layer coating composition 3-1.
  • the silica particles of the hard coat layer coating composition 1-2 were changed to silica particles having an average particle diameter of 1 ⁇ m (KE-P100, manufactured by Nippon Shokubai Co., Ltd.), and the addition amount of the silica particle dispersion was 110.
  • a hard coat film 5 was produced in the same manner except that the mass part was changed and the film thickness of the hard coat layer 2 was changed to 1.1 ⁇ m.
  • Hardcoat layer coating composition 8-1 The following materials were stirred and mixed to obtain a hard coat layer coating composition 8-1.
  • Pentaerythritol triacrylate 5.0 parts by mass Pentaerythritol tetraacrylate 13 parts by mass Dipentaerythritol hexaacrylate 7.0 parts by mass Dipentaerythritol pentaacrylate 7.0 parts by mass Irgacure 184 (manufactured by Ciba Japan) 1.6 parts by mass Reactive silica particle dispersion (Reactive silica particles (Xa) 36%) 58 parts by mass Polyether-modified polydimethylsiloxane (BYK-UV3510, manufactured by Big Chemie Japan) 1.0 part by mass Propylene glycol monomethyl ether 5 parts by mass Methyl ethyl ketone 25 parts by mass ⁇ Preparation of hard coat film 9> In the production of the hard coat film 5, the hard coat film 9 was produced in the same manner except that the addition amount of the silica particle dispersion was 125 parts by mass and the film thickness of the hard coat layer 2 was changed
  • the hard coat layer 2 was irradiated with ultraviolet rays without purging with nitrogen. Further, the hard coat layer coating composition 1-1 was applied onto the hard coat layer 2 by an extrusion coater and heated at 80 ° C. The coating layer is cured by drying and purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, using an ultraviolet lamp and setting the illuminance of the irradiated part to 150 mW / cm 2 and the irradiation amount to 250 mJ / cm 2.
  • a hard coat film 10 was produced in the same manner except that the hard coat layer 3 having a dry film thickness of 0.1 ⁇ m was formed to have a three-layer structure.
  • the silica particles of the hard coat layer coating composition 1-2 were changed to silica particles having an average particle diameter of 1 ⁇ m (KE-P100, manufactured by Nippon Shokubai Co., Ltd.), and the addition amount of the silica particle dispersion was 10
  • a hard coat film 11 was produced in the same manner except that the mass part was changed and the film thickness of the hard coat layer 2 was changed to 1.15 ⁇ m.
  • Reactive silica particles (Xb) were produced in the same manner as in the production of reactive silica particles (Xa) except that the silica particle dispersion was changed to particles having different particle diameters.
  • the particle diameter of the reactive silica particles (Xb) was 15 nm, and the solid content was 36%.
  • the mold roll used was an array of the molds regularly
  • the irradiance of the irradiated part using an ultraviolet lamp while purging with nitrogen so that the oxygen concentration was 1.0% by volume or less.
  • the hard coat film 13 was produced in the same manner except that the coating layer was cured at 150 mW / cm 2 and the irradiation amount was 250 mJ / cm 2 to form the hard coat layer 1 having a dry film thickness of 10 ⁇ m.
  • ⁇ Preparation of hard coat film 14> In the production of the hard coat film 13, a hard coat film 14 was produced in the same manner except that the shape of the mold roll was changed.
  • ⁇ Preparation of hard coat film 15> In the production of the hard coat film 13, a hard coat film 15 was produced in the same manner except that the shape of the mold roll was changed.
  • a polarizing plate 101 was prepared using one each of the hard coat film 1 and the base film 1 as a protective film for the polarizing plate.
  • the obtained PVA film had an average thickness of 25 ⁇ m, a moisture content of 4.4%, and a film width of 3 m.
  • the obtained PVA film was continuously processed in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to produce a polarizing film. That is, the PVA film was preliminarily swollen in water at a temperature of 30 ° C. for 30 seconds, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes.
  • the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under the condition that the tension applied to the film was 700 N / m, and the potassium iodide concentration was 40 g / liter and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes.
  • the obtained polarizing film had an average thickness of 13 ⁇ m, a polarizing performance of a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
  • a polarizing plate 101 was produced by bonding the polarizing film, the base film 1 and the hard coat film 1 in accordance with the following steps 1 to 4.
  • Step 1 The polarizing film described above was immersed in a storage tank of a polyvinyl alcohol adhesive solution having a solid content of 2% by mass for 1 to 2 seconds.
  • Process 2 Alkali saponification treatment was performed on the hard coat film 1 in which a peelable protective film (made of PET) was attached to the base film 1 and the hard coat layer under the following conditions. Next, the excess adhesive adhered to the polarizing film immersed in the polyvinyl alcohol adhesive solution in Step 1 is lightly removed, and the base film 1 and the hard coat film 1 are sandwiched between the polarizing films as shown in FIG. Laminated.
  • Step 3 The laminate was laminated with two rotating rollers at a pressure of 20 to 30 N / cm 2 and a speed of about 2 m / min. At this time, it was carried out with care to prevent bubbles from entering.
  • Step 4 The sample prepared in Step 3 was dried in a dryer at a temperature of 100 ° C. for 5 minutes to prepare a polarizing plate.
  • Step 5 Apply a commercially available acrylic adhesive to the base film 1 of the polarizing plate prepared in Step 4 so that the thickness after drying is 25 ⁇ m, and dry it in an oven at 110 ° C. for 5 minutes to form an adhesive layer Then, a peelable protective film was attached to the adhesive layer. This polarized light was cut (punched) into a size of 576 ⁇ 324 mm, and the polarizing plate 101 was produced.
  • Polarizers 102 to 115 were produced in the same manner as in the production of the polarizing plate 101 except that the hard coat film 1 was changed to the hard coat films 2 to 15, respectively.
  • ⁇ Production of Liquid Crystal Display Device 401> Remove the polarizing plate of NEC notebook PC LaVie G type liquid crystal panel, and make the above-prepared polarizing plate 101 (see FIG. 2 for the configuration) as the polarizing plate on the viewing side so that the hard coat layer is on the viewing side, Layer 5 and liquid crystal cell glass were bonded together. Further, on the backlight side, an acrylic adhesive having a thickness of 25 ⁇ m is used for the polarizing plate 201 that is laminated and bonded so as to sandwich the polarizing film with the base film 1 that has been subjected to alkali saponification treatment in the same manner as described above. A liquid crystal panel 301 was prepared by pasting the liquid crystal cell glass. Next, the liquid crystal panel 301 was set on a liquid crystal television, and a liquid crystal display device 401 was manufactured.
  • Liquid crystal display devices 402 to 415 were similarly manufactured except that the polarizing plate 101 was changed to the polarizing plates 102 to 115 in the preparation of the liquid crystal display device 401.
  • protrusions having a height of 3 nm or more from the average line of the roughness curve were counted.
  • Haze Measurement The haze (Hf) of the base film was measured using a haze meter (NDH2000; manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS-K7136. Next, the haze of each prepared hard coat film (Hh) was measured in the same manner as the base film.
  • the haze value (Hf) of the base film was 0.26%.
  • the number of protrusions of the hard coat layer of the hard coat film is 500 to 200,000 pieces / mm 2
  • the arithmetic average roughness Ra of the hard coat layer is 2 nm to 20 nm
  • the haze value of the hard coat film The polarizing plate of the present invention having (Hh) of 0.2 to 0.6% prevents deformation failure when stored under high temperature and high humidity, and visibility (clearness) when used in a liquid crystal display device. Excellent performance in both.
  • the polarizing plate of the present invention having an arithmetic average roughness Ra of the hard coat layer of 4 nm to 20 nm or a hard coat layer having a two-layer structure exhibits a particularly excellent deformation failure prevention effect.
  • the hard coat film and polarizing plate according to the present invention after humidity conditioning at 23 ° C. and 55% RH for 24 hours, using a test pencil specified by JIS-S6006, the pencil hardness evaluation method specified by JIS-K5400 is used. The pencil hardness was tested using a 500 g weight. The pencil hardness of the hard coat film and the polarizing plate according to the present invention was 3H or more.
  • Hard coat films 16 to 20 were produced in the same manner except that the base film 1 was changed to the following base film 2 to 6 in the production of the hard coat film 1. Using these prepared hard coat films 16 to 20, polarizing plates 116 to 120 and liquid crystal display devices 416 to 420 were prepared.
  • thermoplastic acrylic resin Dyanal BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) Mw 280000
  • Cellulose ester cellulose acetate propionate acyl group total substitution degree: 2.75, acetyl group substitution degree 0.19, propionyl
  • Group substitution degree 2.56, Mw 200000
  • the produced dope solution B was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support.
  • the peeled thermoplastic acrylic resin / cellulose ester resin web was evaporated at 35 ° C., slit to 1.6 m width, and then stretched 1.1 times in the width direction with a tenter, followed by a drying temperature of 130 ° C. And dried. At this time, the residual solvent amount when starting stretching with a tenter was 10%. After stretching with a tenter, relaxation was performed at 130 ° C.
  • a drying zone at 120 ° C. and 140 ° C. with many rolls, slitting to a width of 1.5 m, and a width of 10 mm at both ends of the film
  • a knurling process having a height of 10 ⁇ m was performed and wound around a core to obtain a base film 2.
  • the film thickness was 40 ⁇ m and the winding length was 4000 m.
  • Polarizers 116 to 120 were produced in the same manner except that the hard coat film 1 was changed to the hard coat films 16 to 20 in the production of the polarizer 101.
  • Liquid crystal display devices 416 to 420 were similarly manufactured except that the polarizing plate 101 was changed to the polarizing plates 116 to 120 in manufacturing the liquid crystal display device 401, respectively.
  • the base film contains a thermoplastic acrylic resin and a cellulose ester resin, and the contained mass ratio of the thermoplastic acrylic resin and the cellulose ester resin is determined as follows:
  • Example 3 Polarizers 121 to 125 were produced except that the protective film was changed to the base films 2 to 6 in the production of the polarizing plate 101 of Example 1. Liquid crystal display devices 421 to 425 were produced using these produced polarizing plates.
  • the protective film contains a thermoplastic acrylic resin and a cellulose ester resin, and the contained mass ratio of the thermoplastic acrylic resin and the cellulose ester resin is determined as follows: thermoplastic acrylic resin: cellulose
  • ester resin 95: 5 to 50:50

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JP2014081413A (ja) * 2012-10-12 2014-05-08 Fujifilm Corp 偏光板及び液晶表示装置
JP2019174760A (ja) * 2018-03-29 2019-10-10 三菱ケミカル株式会社 液晶セル積層体
CN110873916A (zh) * 2018-08-29 2020-03-10 日东电工株式会社 相位差膜、带相位差层的偏振片及相位差膜的制造方法
US12000979B2 (en) 2017-06-29 2024-06-04 Lg Chem, Ltd. Polarizer protective film and manufacturing method thereof

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