[go: up one dir, main page]

WO2011114884A1 - Film de revêtement dur, procédé de production, plaque de polarisation et dispositif d'affichage à cristaux liquides - Google Patents

Film de revêtement dur, procédé de production, plaque de polarisation et dispositif d'affichage à cristaux liquides Download PDF

Info

Publication number
WO2011114884A1
WO2011114884A1 PCT/JP2011/054732 JP2011054732W WO2011114884A1 WO 2011114884 A1 WO2011114884 A1 WO 2011114884A1 JP 2011054732 W JP2011054732 W JP 2011054732W WO 2011114884 A1 WO2011114884 A1 WO 2011114884A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard coat
film
protective film
coat film
coat layer
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/JP2011/054732
Other languages
English (en)
Japanese (ja)
Inventor
賢 岡野
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.)
Konica Minolta Opto Inc
Original Assignee
Konica Minolta Opto Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Konica Minolta Opto Inc filed Critical Konica Minolta Opto Inc
Priority to JP2012505600A priority Critical patent/JP5751249B2/ja
Publication of WO2011114884A1 publication Critical patent/WO2011114884A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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 hard coat film, a manufacturing method thereof, a polarizing plate, and a liquid crystal display device.
  • This polarizing plate comprises a polarizing element (polarizing film) in which a polyvinyl alcohol (hereinafter abbreviated as PVA) film adsorbed and dyed with iodine or a dichroic dye is oriented in a certain direction and is composed of two cellulose ester-based films.
  • PVA polyvinyl alcohol
  • the protective film on the outermost surface of the polarizing plate used in the liquid crystal cell is particularly susceptible to physical damage, and if it is damaged, the display image quality is impaired. Therefore, a hard film provided with a hard coat layer on the protective film. A coat film is used.
  • the hardening shrinkage of the hard coat layer is also a factor that hinders interlayer adhesion.
  • Hard coat layer containing an isocyanurate derivative and an active energy ray-curable compound other than the isocyanurate derivative as a hard coat film having a hard coat layer having a sufficient surface hardness as a surface protective film for an image display device and a small curing shrinkage has been disclosed (for example, see Patent Document 4).
  • Patent Document 5 discloses a hard coat layer cured with a component containing a polyfunctional (meth) acrylic monomer, a (meth) acrylic monomer having a hydroxyl group, a radical photopolymerization initiator, and a fluorine-containing compound having a polymerizable group.
  • the hard coat film has a surface free energy of 20 mN / m or less and a hard coat layer thickness of 5 to 25 ⁇ m.
  • an object of the present invention is to provide a hard coat film with improved interlayer adhesion between the protective film and the hard coat layer after the weather resistance test, a production method thereof, and a polarizing plate and a liquid crystal display device using the same. is there.
  • the present inventors control the balance between the storage elastic modulus and the loss elastic modulus of the cellulose ester-based protective film within a specific range, and contain the active energy ray-curable isocyanurate derivative in the hard coat layer.
  • the inventors have found that the problem can be solved and have reached the present invention.
  • the hard coat layer contains an active energy ray-curable isocyanurate derivative, and tan ⁇ in the film width direction of the protective film has the following relationship: Hard coat film characterized by
  • tan ⁇ peak is the maximum value obtained by measuring tan ⁇ values from 25 ° C. to 210 ° C.
  • tan ⁇ ⁇ 40 is the value of tan ⁇ at a temperature of ⁇ 40 ° C. when tan ⁇ peak is shown.
  • the protective film has cellulose triacetate A having an acetyl group substitution degree of 2.80 to 2.95 and a number average molecular weight of 125,000 or more and less than 155000, and an acetyl group substitution degree of 2.75 to 2.90, and a number average molecular weight. 4.
  • the hard coat film as described in any one of 1 to 3 above, comprising 155,000 or more and less than 180,000 cellulose triacetate B.
  • the hard coat layer contains an active energy ray-curable isocyanurate derivative (A) and an active energy ray-curable resin (B) other than the isocyanurate derivative, and the active energy ray-curable isocyanurate derivative (A) and the isocyanate 7.
  • the hard coat film as described in any one of 1 to 6 above, wherein the mass ratio of the active energy ray-curable resin (B) other than the nurate derivative is 10:90 to 50:50.
  • a polarizing plate comprising the hard coat film according to any one of 1 to 7 on one surface.
  • a liquid crystal display device comprising the polarizing plate according to 9 above in at least one of the liquid crystal cells.
  • a liquid crystal display device with a touch panel wherein the hard coat film according to any one of 1 to 7 is provided as a constituent member of the touch panel.
  • the hard-coat film which aimed at the improvement of the interlayer adhesion of the protective film and hard-coat layer after a weather resistance test, its manufacturing method, and a polarizing plate and a liquid crystal display device using the same can be provided. .
  • the present inventor has controlled the balance between the storage elastic modulus and loss elastic modulus of the protective film to a specific range and contains the active energy ray-curable isocyanurate derivative in the hard coat layer.
  • the interlayer adhesion between the hard coat layer and the protective film is improved, and the present invention has been achieved.
  • the hard coat film of the present invention is composed of at least a protective film and a hard coat layer.
  • active energy ray-curable isocyanurate derivatives and active energy ray-curable resins other than isocyanurate derivatives are simply described as active energy ray-curable resins.
  • the active energy ray curable type refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, and specifically, a resin having an ethylenically unsaturated group.
  • the active energy ray-curable isocyanurate derivative is not particularly limited as long as it is a compound having a structure in which one or more ethylenically unsaturated groups are bonded to an isocyanuric acid skeleton.
  • a compound having three or more ethylenically unsaturated groups and one or more isocyanurate rings in the same molecule shown is preferable from the viewpoint of the object effect of the present invention.
  • the kind of ethylenically unsaturated group is an acryloyl group, a methacryloyl group, a styryl group, and a vinyl ether group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.
  • L 2 is a divalent linking group, preferably a substituted or unsubstituted alkyleneoxy group or polyalkyleneoxy group having 4 or less carbon atoms in which a carbon atom is bonded to the isocyanurate ring, Particularly preferred are alkyleneoxy groups, which may be the same or different.
  • R 2 represents a hydrogen atom or a methyl group, and may be the same or different.
  • Other compounds include isocyanuric acid diacrylate compounds, and isocyanuric acid ethoxy-modified diacrylate represented by the following general formula (2).
  • ⁇ -caprolactone-modified active energy ray-curable isocyanurate derivatives specifically, compounds represented by the following general formula (3).
  • R 1 to R 3 in the chemical structural formula is attached with a functional group represented by the following a, b, and c, and at least one of R 1 to R 3 is a functional group of b.
  • Examples of commercially available isocyanuric acid triacrylate compounds include A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Examples of commercially available isocyanuric acid diacrylate compounds include Aronix M-215 manufactured by Toagosei Co., Ltd.
  • Examples of the mixture of the isocyanuric acid triacrylate compound and the isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd.
  • ⁇ -caprolactone-modified active energy ray-curable isocyanurate derivatives include ⁇ -caprolactone-modified tris- (acryloxyethyl) isocyanurate, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, Toagosei Co., Ltd. Examples include Aronix M-327, but are not limited thereto.
  • Active energy ray-curable resins other than isocyanurate derivatives include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, or UV curable resins. Epoxy resins and the like are preferably 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.
  • Monofunctional acrylates may be used as active energy ray-curable resins other than isocyanurate derivatives.
  • Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate.
  • Monofunctional acrylates can be obtained from Shin Nakamura Chemical Co., Ltd., Osaka Organic Chemical Industry Co., Ltd., and the like. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.
  • the viscosity of the polyfunctional acrylate is preferably 3000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less, at 25 ° C.
  • the viscosity is a value measured using a B-type viscometer at 25 ° C.
  • the active energy ray-curable isocyanurate derivative (A) and the isocyanurate derivative are used in combination in the hard coat layer.
  • the hard coat layer preferably contains a photopolymerization initiator in order to accelerate the curing of the active energy ray-curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. .
  • 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.
  • the organic fine 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, 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 organic fine particles include cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H manufactured by Soken Chemical), polymethyl methacrylate particles (for example, MX150, MX300 manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. It is done.
  • fluorine-containing acrylic resin fine particles include commercially available products such as FS-701 manufactured by Nippon Paint.
  • the 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.
  • the hard coat layer according to the present invention may be provided by applying a hard coat layer coating composition diluted with a solvent on a film substrate by the following method, drying, and curing. It is preferable from the viewpoint that interlayer adhesion is easily obtained.
  • a solvent such as acetone, cyclohexanone, and methyl isobutyl ketone.
  • ketones include methyl ethyl ketone, acetone, cyclohexanone, and methyl isobutyl ketone.
  • esters include methyl acetate, ethyl acetate, butyl acetate, and propyl acetate. It is not limited.
  • solvents include alcohols (ethanol, methanol, butanol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol), hydrocarbons (toluene, xylene, benzene, cyclohexane), glycol ethers (propylene glycol monomethyl ether, Propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc.) can be preferably used.
  • solvents are excellent in stability as a coating composition when used in the range of 20 to 200 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin.
  • 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 4 to 15 ⁇ m.
  • the hard coat layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die (extrusion) coater, a hard coat coating composition that forms a hard coat layer is applied using a known coating method such as an inkjet method, After the application, it can be formed by drying, UV-curing treatment, and if necessary, heat-treating to UV curing.
  • the heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. By performing the heat treatment after UV curing at such a high temperature, the mechanical film strength (abrasion resistance, pencil hardness) of the hard coat layer is excellent.
  • the drying is preferably performed at a high temperature treatment of 90 ° C. or more at the temperature of the reduced rate drying section.
  • the temperature in the decreasing rate drying section is preferably 95 ° C. or higher and 130 ° C. or lower because the effect is easily obtained.
  • the drying process changes from a constant state to a gradually decreasing state when drying starts.
  • the decreasing section is called the decreasing rate drying section.
  • the constant rate drying section the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section.
  • the temperature of the coating surface rises and approaches the hot air temperature, so the temperature of the hard coat layer coating composition rises and the viscosity of the active energy ray curable resin in the hard coat layer coating composition decreases.
  • the liquidity is thought to increase.
  • 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 50 to 1000 mJ / cm 2 , preferably 50 to 300 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 transport 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 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 anionic surfactant, from the viewpoint of coating properties and the uniform dispersibility of fine particles.
  • a fluorine-siloxane graft polymer is graft polymer.
  • the fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine resin.
  • Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. 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.
  • the hard coat layer may be a single layer or a plurality of layers.
  • the hard coat layer may be divided into two or more layers. Moreover, you may provide a hard-coat layer on both surfaces of a protective film.
  • 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 as a simultaneous multilayer.
  • 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 pencil hardness, which is an index of hardness, of the hard coat film in the present invention is H or more, more preferably 4H or more. If it is 4H or more, it is not only difficult to be scratched in the polarizing plate forming step of the liquid crystal display device, but is 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 arithmetic average roughness Ra of the hard coat layer according to the present invention is preferably 2 to 20 nm from the viewpoint that the objective effect of the present invention can be easily obtained after a more severe weather resistance test.
  • Arithmetic average roughness Ra is a value measured with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO) based on JIS B0601: 2001.
  • the average length RSm of the contour curve element is preferably 3 to 80 ⁇ m.
  • RSm can be measured with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO) based on the provisions of JIS B0601: 2001, similarly to the arithmetic average roughness Ra.
  • Arithmetic average roughness Ra is a method of forming protrusions on the surface by pressing a mold, or a method of forming surface irregularities by mixing resins having different SP values (solubility parameters) (for example, JP-A-2007-182519, The method may be formed by a method described in JP2009-13384A.
  • 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.
  • the haze value of the hard coat film of the present invention is preferably 1% or less.
  • the haze value is 1% or less, sufficient brightness and high contrast can be obtained when used outdoors such as a large liquid crystal display device or digital signage.
  • the haze value can be measured according to JIS K7105 and JIS K7136.
  • the hard coat film of the present invention may have antiglare properties.
  • Anti-glare is a function that blurs the outline of the image and external light reflected on the hard coat layer of the hard coat film, which reduces the visibility of the reflected image and reflects when the hard coat film is used for liquid crystal displays. It is to avoid the reflection of the image.
  • the total haze value is preferably 3% to 40%.
  • the surface haze value (haze due to film surface scattering) is preferably 3 to 40%, and the internal haze value (haze due to internal scattering) is preferably 35% or less.
  • the protective film which is another feature of the present invention will be described.
  • the protective film is characterized in that tan ⁇ measured by changing the temperature from 25 ° C. to 210 ° C. at a humidity of 55% RH in the width direction of the film has the following relationship.
  • tan ⁇ peak is the maximum value obtained by measuring the tan ⁇ value by changing the temperature from 25 ° C. to 210 ° C.
  • tan ⁇ ⁇ 40 is the value of tan ⁇ at a temperature of ⁇ 40 ° C. when tan ⁇ peak is indicated.
  • Hard coat layer and protective film containing active energy ray-curable isocyanurate derivative by controlling tan ⁇ in width direction of protective film, that is, temperature change of ratio of storage elastic modulus and loss elastic modulus to the above range
  • the active energy ray-curable isocyanurate derivative easily penetrates into the protective film and hardens, and the anchor effect works to improve the adhesion. It is assumed that the objective effect can be obtained.
  • Tan ⁇ can be measured, for example, by using a sample that has been conditioned for 24 hours in an atmosphere of 23 ° C. and 55% RH in advance and increasing the temperature under the following conditions at a humidity of 55% RH or by setting the temperature.
  • Measuring device RSA III manufactured by TI Instruments Sample: width 5 mm, length 50 mm (gap set to 20 mm) Measurement conditions: Tensile mode Measurement temperature: 25-210 ° C or -40 ° C Temperature rising condition: 5 ° C / min Frequency: 1Hz
  • the tan ⁇ - 40 / tan ⁇ peak is controlled by the type of cellulose ester (substitution degree, molecular weight, combination, etc.), the type of ester compound (difference in acid value), and the film forming conditions (film thickness and stretching conditions) described later. Can do. When the acid value of the ester compound is high, tan ⁇ ⁇ 40 / tan ⁇ peak decreases.
  • cellulose such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, cellulose acetate butyrate film, etc.
  • An ester film is preferred.
  • polyester films such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate films, polyarylate films, polysulfone (including polyethersulfone) films, polyethylene films, polypropylene films, cellophane, polyvinylidene chloride films, polyvinyl Alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, norbornene resin film, polymethylpentene film, polyether ketone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film, cycloolefin polymer film Polymethylmethacrylate film or acrylic fill It can be cited used in the protective film and the like. You may use together the resin which comprises an above described film.
  • the refractive index of the protective film 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 film preferably has an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5%, and more preferably an average degree of acetylation of 58.0 to A 62.5% cellulose triacetate film is preferred.
  • the degree of acetyl group substitution of cellulose triacetate is 2.80 to 2.95 and the number average molecular weight (Mn) is 125000. As mentioned above, it is preferable to contain the cellulose triacetate A which is less than 155000.
  • the cellulose triacetate A preferably has a weight average molecular weight (Mw) of 265,000 to less than 310,000 and Mw / Mn of 1.9 to 2.1.
  • Mw weight average molecular weight
  • the degree of acetyl group substitution is 2.75 to 2.90
  • the number average molecular weight (Mn) is 155,000 or more and less than 180,000
  • Mw is 290000 or more and less than 360,000 because pencil hardness is improved.
  • the cellulose triacetate B having a Mw / Mn of 1.8 to 2.0 is preferably used in combination with the cellulose triacetate A.
  • the weight ratio of cellulose triacetate A: cellulose triacetate B is preferably in the range of 100: 0 to 20:80.
  • cellulose triacetate when an acyl group having 2 to 4 carbon atoms is used as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the propionyl group or butyryl group is Y, the following formula (I) and Cellulose esters that simultaneously satisfy (II) can be used, Formula (I) 2.6 ⁇ X + Y ⁇ 3.0 Formula (II) 0 ⁇ X ⁇ 2.5 Among them, cellulose acetate propionate is preferable, and 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9 are particularly preferable.
  • the degree of acyl group substitution can be measured according to ASTM D817-96. Cellulose diacetate can also be preferably used.
  • the number average molecular weight (Mn) and molecular weight distribution (Mw) of the cellulose ester can be measured using high performance liquid chromatography.
  • the measurement conditions are as follows.
  • the cellulose ester-based film preferably contains an ester compound from the viewpoint of excellent moisture permeation resistance and easy control of tan ⁇ - 40 / tan ⁇ peak of the protective film in the width direction of the film.
  • an ester compound having a structure obtained by reacting phthalic acid, adipic acid, at least one benzene monocarboxylic acid and at least one alkylene glycol having 2 to 12 carbon atoms is preferable.
  • benzene monocarboxylic acid component examples include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid.
  • an acid etc. there exists an acid etc., and these can be used as a 1 type, or 2 or more types of mixture, respectively. Most preferred is benzoic acid.
  • alkylene glycol component having 2 to 12 carbon atoms examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1, 3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1 , 6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexan
  • the ester compound can be produced by mixing in the presence of an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours, and performing an esterification reaction.
  • an aromatic terminal ester compound can also be used as the ester compound.
  • the exemplary compound of an aromatic terminal ester compound is shown below, it is not limited to these.
  • sugar ester compounds can be mentioned.
  • the sugar ester compound is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide.
  • a general formula (4 ) And the like As a more specific example, a general formula (4 ) And the like.
  • R 1 to R 8 represent a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms, and R 1 to R 8 May be the same or different.
  • the compounds represented by the general formula (4) are shown below in more detail (compounds 4-1 to 4-23), but are not limited thereto.
  • the number average molecular weight of the ester compound is preferably 300 to 2000, more preferably 400 to 1500.
  • the acid value is preferably 0.08 to 0.50 mg KOH / g.
  • the hydroxyl value is preferably 25 mgKOH / g or less, more preferably 15 mgKOH / g or less.
  • the ester compound is preferably contained in the protective film in an amount of 1 to 35% by mass, particularly 5 to 30% by mass. Within this range, there is no bleeding out and excellent transparency.
  • the cellulose ester film may contain a thermoplastic acrylic resin and a cellulose ester resin.
  • Acrylic resin includes methacrylic resin.
  • the 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 acrylic resin can be measured by gel permeation chromatography including the measurement conditions.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd. product), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd. product), KT75 (Electrochemical Industry Co., Ltd. product) Etc.
  • Two or more acrylic resins can be used in combination.
  • Acrylic particles may be contained for the purpose of improving the brittleness of the protective film.
  • examples of commercially available acrylic particles include, for example, Metablen W-341 (C2) (Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G (C3), MS-300X (C4) (Soken Chemical Co., Ltd.) And the like.
  • the acrylic fine particles are preferably contained in the range of 0.5% to 30% with respect to the total mass of the resin forming the protective film.
  • Fine particles other than acrylic fine particles may be contained.
  • fine particles other than acrylic fine particles silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silica from the viewpoint of slipperiness and storage stability.
  • Inorganic particles such as calcium acid, aluminum silicate, magnesium silicate and calcium phosphate are preferred.
  • silicon dioxide is preferable in terms of low turbidity. Silicon dioxide that has been subjected to a hydrophobization treatment is preferable in terms of achieving both slipperiness and haze.
  • the hydrophobic substituent is preferably a methyl group.
  • the primary particle size of silicon dioxide is preferably 20 nm or less, and more preferably 10 nm or less. Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferable because they have a large effect of reducing the friction coefficient while keeping the haze of the protective film low, and Aerosil R812 is most preferably used.
  • the dynamic friction coefficient of at least one surface is 0.2 to 1.0.
  • a plasticizer can also be added to the protective film in order to improve the fluidity and flexibility of the composition.
  • the plasticizer include phthalic acid compounds, fatty acid compounds, trimellitic acid compounds, phosphoric acid compounds, acrylic polymers, and epoxy compounds.
  • the acrylic polymer is preferably a homopolymer or copolymer of acrylic acid or alkyl methacrylate.
  • the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate ( n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic Acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxy
  • the acrylic polymer is a homopolymer or copolymer of the above-mentioned monomer, but it is preferable that the acrylic acid methyl ester monomer unit has 30% by mass or more, and the methacrylic acid methyl ester monomer unit has 40% by mass or more. preferable. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.
  • plasticizers can be selected or used in combination depending on the application.
  • 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 protective film.
  • the protective 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
  • 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 also be added to the protective film in order to improve the thermal decomposability and thermal coloring during molding. It is also possible to add an antistatic agent to give the protective 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.
  • Protective films are required to be able to withstand use in higher temperature environments due to the demand for higher brightness due to use in outdoor applications such as digital signage. However, if it is 105 ° C. to 145 ° C., it can be judged that sufficient heat resistance is exhibited, and it is particularly preferable to control the temperature to 110 ° C. 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 protective 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 (%) of the protective film is preferably less than 0.5%, and more preferably less than 0.3%. .
  • the protective film preferably 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. If the defect is a change in 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 hard coat layer coating composition may not be applied uniformly, resulting in a defect (missing coating).
  • 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 protective 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 protective 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 thickness of the protective film according to the present invention is preferably 20 to 250 ⁇ m from the viewpoint of controlling the tan ⁇ , more preferably 30 to 100 ⁇ m, and from the viewpoint of thinning the optical member, 30 to 70 ⁇ m. It is particularly preferred that
  • the protective 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.
  • the retardation of the protective film is preferably such that the in-plane retardation Ro at a wavelength of 590 nm is from 0 to 50 nm and the retardation Rth in the thickness direction is from ⁇ 10 to 50 nm.
  • Ro and Rth are values defined by the following formulas (I) and (II).
  • Formula (I) Ro (nx ⁇ ny) ⁇ d
  • Formula (II) Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (Where nx is the refractive index in the slow axis direction in the base film surface, ny is the refractive index in the direction perpendicular to the slow axis in the base film surface, and nz is the refractive index in the thickness direction of the base film)
  • D represents the thickness (nm) of the base film.
  • the retardation can be determined at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments).
  • Retardation can be adjusted by the types of ester compounds and plasticizers described above, the amount added, and the film thickness and stretching conditions of the base 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, or a hot press method can be used.
  • melt casting film forming method From the viewpoint of suppressing the residual solvent in which the cellulose ester resin is used 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 molding method that can obtain a film having excellent mechanical strength and surface accuracy is preferable. 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 An organic solvent useful for forming a dope when a protective film is produced by a solution casting method can be used without limitation as long as it dissolves a cellulose ester resin and other additives simultaneously.
  • 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 dope composition is dissolved in%.
  • 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.
  • the protective film can be produced by a solution casting method.
  • a step of preparing a dope by dissolving a resin and an additive in a solvent a step of casting the dope on a belt-like or drum-like metal support, and 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, a step of further drying, and a step of winding up the finished film.
  • the concentration of the cellulose ester resin in the dope is preferably higher because the drying load after casting on the metal support can be reduced, but if the concentration of the cellulose ester resin is too high, the load during filtration increases. Thus, the filtration accuracy is deteriorated.
  • 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 preferably 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 during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0. 0.1 mass% or less, particularly preferably 0 to 0.01 mass% or less.
  • a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
  • the film can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the lateral direction (TD direction).
  • the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively. It is preferably performed in the range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction.
  • a method in which a difference in peripheral speed is applied to a plurality of rolls and the roll peripheral speed difference is used to stretch the roll in the MD direction.
  • a tenter it may be a pin tenter or a clip tenter.
  • the film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 N / m to 200 N / m, and more preferably 140 N / m to 200 N / m. 140 N / m to 160 N / m is most preferable.
  • the glass transition temperature of the protective film is Tg, (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (Tg + 20). ) ° C.
  • the Tg of the protective film can be controlled by the material type constituting the film and the ratio of the constituting materials.
  • the Tg when the protective film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower.
  • the Tg of the film can be determined by the method described in JIS K7121.
  • the surface is preferably roughened. It is preferable to appropriately roughen the film surface because not only the slipperiness is improved but also the surface processability, particularly the adhesion of the hard coat layer is improved.
  • the arithmetic average roughness Ra is preferably 2.0 nm to 4.0 nm, more preferably 2.5 nm to 3.5 nm.
  • the protective film may be formed by a melt film forming method.
  • the melt film-forming method refers to heating and melting a composition containing an additive such as a resin and a plasticizer to a temperature exhibiting fluidity, and then casting a melt containing a fluid cellulose ester.
  • 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 preferable from the viewpoint of mechanical strength and surface accuracy. It is preferable that a plurality of raw materials used for melt extrusion are usually kneaded in advance and pelletized.
  • 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.
  • the stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated.
  • the density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.
  • 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 Japanese Patent No. 3194904, Japanese Patent No. 3422798, Japanese Patent Laid-Open No. 2002-36332, Japanese Patent 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 of the present invention can be provided with functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, and a barrier layer.
  • a back coat layer may be provided on the surface of the protective 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 oxide. 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 composed of a low refractive index layer having a lower refractive index than the protective film as the support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as the support.
  • it is.
  • 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 low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm.
  • 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. Further, it may contain a compound having a thermosetting property and / or a photocuring property mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used.
  • fluorine-containing polymer examples include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], and fluorine-containing monomers. Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units.
  • the refractive index of the high refractive index layer is preferably adjusted to a range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm.
  • the thickness of the high refractive index layer is preferably 5 nm to 1 ⁇ m, more preferably 10 nm to 0.2 ⁇ m, and most preferably 30 nm to 0.1 ⁇ m.
  • the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
  • Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
  • the kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S
  • a metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta, and a small amount of atoms may be doped. May be. A mixture of these may also be used.
  • at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as a main component. In particular, it is preferable to contain zinc antimonate particles.
  • the average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm.
  • the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze increases remarkably, which is not preferable.
  • the shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.
  • the metal oxide fine particles may be surface-treated with an organic compound.
  • an organic compound By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . Therefore, the amount of surface modification with a preferable organic compound is 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass with respect to the metal oxide particles.
  • the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.
  • the high refractive index layer may contain a ⁇ -conjugated conductive polymer.
  • the ⁇ -conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a ⁇ -conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.
  • the ⁇ -conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group.
  • a functional group such as a group, a hydroxy group, or a cyano group may be introduced.
  • the ionic compound include imidazolium-based, pyridium-based, alicyclic amine-based, aliphatic amine-based, aliphatic phosphonium-based cations and inorganic ion-based compounds such as BF 4 ⁇ and PF 6 ⁇ , CF 3 SO 2 ⁇ , and the like. , (CF 3 SO 2 ) 2 N ⁇ , CF 3 CO 2 —, etc.
  • the ratio of the polymer to the binder is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polymer, and particularly preferably 100 to 200 parts by mass of the binder with respect to 100 parts by mass of the polymer.
  • the polarizing plate can be produced by a general method.
  • the back surface side of the hard coat film of the present invention is subjected to alkali saponification treatment, and a completely hardened 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 bond them together.
  • the hard coat film may be used on the other surface, or the protective film described above 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 of the present invention is incorporated in a polarizing plate, and is a reflection type, transmission type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type. It is preferably used in liquid crystal display devices of various driving systems such as OCB type.
  • the hard coat film of the present invention is used for a touch panel member of a liquid crystal display device with a touch panel, it is preferable in terms of excellent visibility and durability against pen input (scratches due to sliding, etc.).
  • FIG. 1 shows a schematic diagram of a hard coat film 10 with a conductive film for a touch panel.
  • the transparent conductive thin film 5 is formed on at least one hard coat layer of the hard coat film 3 provided with the hard coat layers 2 and 4 on both surfaces of the protective film 1.
  • a resistive film type touch panel is formed by making the hard coat film 10 with a conductive film for a touch panel and the glass substrate 13 on which the transparent conductive thin film 14 is formed face each other with a certain interval so that the transparent conductive thin films face each other. 11 can be configured. Electrodes (not shown) are arranged at the end portions of the hard coat film 10 with the conductive film for touch panel and the glass substrate 13. In the resistive film type touch panel, the transparent conductive thin film of the hard coat film 10 with a conductive film for a touch panel becomes a glass substrate 13 when the user presses the hard coat film 10 with the conductive film for a touch panel with a finger or a pen.
  • the resistive touch panel liquid crystal display device 20 can be configured by mounting the touch panel 11 on an LCD (liquid crystal display panel) 12.
  • ester compound 1 251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with a thermometer, stirrer, and slow cooling tube The flask is charged and gradually heated with stirring until it reaches 230 ° C. in a nitrogen stream. The ester compound 1 was obtained by carrying out a dehydration condensation reaction for 15 hours, and distilling off unreacted 1,2-propylene glycol under reduced pressure at 200 ° C. after completion of the reaction. The acid value was 0.10 mg KOH / g, and the number average molecular weight was 450.
  • the belt was cast evenly on a stainless steel band support using a belt casting apparatus.
  • the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off.
  • Cellulose ester film web was evaporated at 35 ° C, slit to 1.65m width and dried at 160 ° C drying temperature while stretching 1.3 times in TD direction (film width direction) with tenter. I let you. At this time, the residual solvent amount when starting stretching with a tenter was 20%.
  • the protective film 1 was obtained.
  • the residual solvent amount of the protective film was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 6000 m.
  • the storage elastic modulus at 30 ° C. was 4.1 GPa in the MD direction, and the draw ratio in the MD direction calculated from the rotational speed of the 5.5 GPa stainless steel band support and the operating speed of the tenter in the TD direction was 1.01 times. It was.
  • the cellulose triacetate and ester compounds listed in Table 2 are as follows.
  • the number average molecular weight of cellulose triacetate was measured by the method described above.
  • ester compound 2 In the synthesis of the ester compound 1, the same reaction was carried out using 182 g of phthalic anhydride and 273 g of adipic acid to obtain an ester compound 2. The acid value was 0.15 mg KOH / g and the number average molecular weight was 600.
  • the ester compound 5 was obtained by performing dehydration condensation reaction for 15 hours, and distilling off unreacted 1,2-propylene glycol under reduced pressure at 200 ° C. after completion of the reaction.
  • the acid value was 0.90 mg KOH / g and the number average molecular weight was 500.
  • the mixture was charged into a liter four-necked flask, heated stepwise to 220 ° C. with stirring under a nitrogen stream, and then reacted at 220 ° C. for a total of 15 hours for dehydration condensation.
  • ester compound 5 was obtained by distilling off unreacted 1,2-propylene glycol at 200 ° C. under reduced pressure.
  • ⁇ Ester compound 6 > 125 g of 1,2-propylene glycol, 97 g of dimethyl terephthalate, 244 g of benzoic acid, 0.028 g of tetraisopropyl titanate as an esterification catalyst, 1 liter in volume with thermometer, stirrer and reflux condenser The mixture was charged into a four-necked flask, heated stepwise to 220 ° C. while stirring under a nitrogen stream, and then reacted at 220 ° C. for a dehydration condensation reaction for a total of 11 hours. After the reaction, ester compound 6 was obtained by distilling off unreacted 1,2-propylene glycol at 190 ° C. under reduced pressure. The acid value was 0.07 mg KOH / g and the number average molecular weight was 700.
  • the illuminance of the irradiated part is 100 mW / cm 2 using an ultraviolet lamp and the irradiation amount is 0
  • the coating layer was cured as .23 J / cm 2 , and the hard coat layer 1 having a dry film thickness of 8 ⁇ m was formed and wound up to produce a roll-shaped hard coat film 1.
  • Radical polymerizable fluororesin (A): Cephalal coated CF-803 (hydroxyl value 60, number average molecular weight 15,000; manufactured by Central Glass Co., Ltd.)
  • One-end radically polymerizable polysiloxane (B): Silaplane FM-0721 (number average molecular weight 5,000; manufactured by Chisso Corporation)
  • Radical polymerization initiator Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
  • Curing agent Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.) (Synthesis of radical polymerizable fluororesin)
  • a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet was added to cefal coat CF-803 (1554 parts by mass), xylene
  • Hard Coat Layer Coating Composition 2 >> 100 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.) 5 parts by mass Fluorine-siloxane graft polymer (35% by mass) 2 parts by mass Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 20 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 3] On the protective film 1 produced above, a hard coat film 3 was produced in the same manner except that it was changed to the following hard coat layer coating composition 3.
  • Hardcoat layer coating composition 3 >> 65 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass of tris (2-acryloyloxyethyl) isocyanurate (Aronix M-315, manufactured by Toagosei Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.) 5 parts by mass Fluorine-siloxane graft polymer (35% by mass) 2 parts by mass Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 20 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 4] On the protective film 1 produced above, a hard coat film 4 was produced in the same manner except that it was changed to the following hard coat layer coating composition 4.
  • NK ester A-TMM-3L manufactured by Shin-Nakamura
  • Hard Coat Layer Coating Composition 4 65 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) Isocyanuric acid ethoxy-modified diacrylate 35 parts by mass (Aronix M-215, manufactured by Toagosei Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.) 5 parts by mass Fluorine-siloxane graft polymer (35% by mass) 2 parts by mass Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 20 parts by mass Methyl ethyl ketone 70 parts by mass [of hard coat films 5-12 Production] Hard coat films 5 to 12 were prepared in the same manner except that the hard coat layer coating composition and the protective film were changed as shown in Table 2 in the preparation of the hard coat film 1.
  • a hard coat film 13 was prepared with reference to Preparation Example 1 of Example 1 of JP-A-2008-173856, except that the dry thickness of the hard coat layer was adjusted to 8 ⁇ m.
  • T40UZ described in Table 2 is a 40 ⁇ m triacetyl cellulose film (manufactured by FUJIFILM Corporation).
  • Hard coat films 14 to 16 were produced in the same manner as in the production of the hard coat film 1 except that the protective film 1 was changed as described in Table 2.
  • Measuring device RSA III manufactured by TI Instruments Sample: width 5 mm, length 50 mm (gap set to 20 mm) Measurement conditions: Tensile mode Measurement temperature: 25-210 ° C or -40 ° C Temperature rising condition: 5 ° C / min Frequency: 1Hz 2. Evaluation of hard coat film a. Measurement of Arithmetic Average Roughness Ra The hardcoat layers of the hardcoat films 1 to 16 produced above were measured 10 times using an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO). From the average, the arithmetic average roughness Ra of each hard coat film was determined.
  • RST / PLUS optical interference surface roughness meter
  • ⁇ Weather resistance test> The above-prepared roll-shaped hard coat films 1 to 16 are cut out in a size of 10 cm ⁇ 10 cm, and cycle thermostats ( ⁇ 40 ° C., 30 minutes, and then left at 85 ° C., 30 minutes are alternately assumed assuming outdoor use. After 500 cycles, the sample was irradiated with light for 150 hours using a light resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.).
  • the apparatus which reciprocated steel wool used the Shinto Scientific Co., Ltd. friction-wear tester (Tribo station TYPE: 32, moving speed 4000mm / min).
  • Abrasion resistance evaluation criteria A 1 / cm or less ⁇ : 10 / cm or less ⁇ : 20 / cm or less ⁇ : 20 / cm or more c.
  • Adhesion evaluation Each hard coat film 1 to 16 after the weather resistance test was conditioned for 12 hours in an atmosphere of 23 ° C. and 55% RH, and then a distance of 1 mm between the hard coat layers of each hard coat film by a method according to JIS K5400. Then, 11 cuts were made vertically and horizontally, 1 mm square, 100 grids were prepared, cellophane tape was applied and peeled off at an angle of 90 degrees, and the number of grids remaining without peeling was counted. Evaluation was made according to the following criteria.
  • a hard coat layer containing an active energy ray-curable isocyanurate derivative is provided on a protective film having a tan ⁇ in the width direction of 0.5 ⁇ tan ⁇ ⁇ 40 / tan ⁇ peak ⁇ 0.24.
  • the hard coat film of the present invention is excellent in interlayer adhesion between the protective film and the hard coat layer, and also has good film strength (scratch resistance).
  • Example 2 In the production of the hard coat film 1 of Example 1, the active energy ray-curable isocyanurate derivative of the hard coat layer coating composition 1 is not tris (2-acryloyloxyethyl) isocyanurate (A) or an isocyanurate derivative. Except that the mass ratio of the active energy ray-curable resin (pentaerythritol tri / tetraacrylate) (B) was changed to hard coat layer coating compositions 5 to 8 changed as shown in Table 3, Examples In the same manner as in Example 1, hard coat films 17 to 20 were produced.
  • Example 3 the obtained hard coat films 17 to 20 and the hard coat film 1 produced in Example 1 were evaluated in the same manner as in Example 1 except that the cycle thermocondition of the weather resistance test was changed to the following. .
  • the obtained results are shown in Table 3.
  • ⁇ Weather resistance test> The roll-like hard coat film 1 produced in Example 1 and the roll-like hard coat films 17 to 20 produced in Example 2 were cut out in a size of 10 cm ⁇ 10 cm, cycle thermostatic ( ⁇ 40 ° C., 30 minutes, then 85 C. and 30 minutes standing were alternately put in 1000 cycles, and then irradiated with light for 150 hours with a light resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.).
  • a light resistance tester eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.
  • Example 3 Hard coat films 21 to 26 were produced in the same manner as in Example 1 except that the hard coat film 1 of Example 1 was changed to the conditions described in Table 4 except that the temperature in the decreasing rate drying section was changed. Next, the hard coat films 21 to 26 obtained and the hard coat film 1 produced in Example 1 were evaluated in the same manner as in Example 1, except that the conditions of the weather resistance test were changed more severely. The results obtained are shown in Table 4.
  • ⁇ Weather resistance test> The roll-shaped hard coat film 1 prepared in Example 1 and the roll-shaped hard coat films 21 to 26 prepared in Example 3 were cut out in a size of 10 cm ⁇ 10 cm, respectively, and cycle thermostatic ( ⁇ 40 ° C., 30 minutes, then 85 C. and 30 minutes standing were alternately put in 1000 cycles, and then irradiated with light for 250 hours with a light resistance tester (Isuper UV tester, manufactured by Iwasaki Electric Co., Ltd.).
  • a light resistance tester Isuper UV tester, manufactured by Iwasaki Electric Co., Ltd.
  • the temperature of the decreasing rate drying section in the drying step when forming the hard coat layer of the present invention is controlled to 95 ° C. or higher and 130 ° C. or lower, and the arithmetic average roughness of the hard coat layer of the present invention
  • Ra By controlling Ra within the range of 2 to 20 nm, it is particularly preferable because the objective effect of the present invention can be exhibited better even after a more severe weather resistance test.
  • Example 4 Preparation of Polarizing Plate 101> (Alkaline saponification treatment) A polarizing plate 101 was prepared using one each of the hard coat film 1 and the protective 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 immersed in water at a temperature of 30 ° C. for 30 seconds to be pre-swelled, 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. Subsequently, the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under a tension of 700 N / m.
  • 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 treatment. 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 protective film 1 and the hard coat film 1 according to 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.
  • Step 2 Alkali saponification treatment was performed on the hard coat film 1 obtained by attaching a peelable protective film (PET) to the protective film and the hard coat layer under the following conditions. After the alkali saponification treatment, the protective film of the hard coat layer was peeled off. Next, in Step 1, the polarizing film was immersed in the polyvinyl alcohol adhesive solution. Excess adhesive adhered to the immersed polarizing film was lightly removed, and the polarizing film was sandwiched between the protective film 1 and the hard coat film 1 as shown in FIG.
  • PET peelable protective film
  • 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 protective film 1 of the polarizing plate prepared in Step 4 so that the thickness after drying is 25 ⁇ m, and dry in an oven at 110 ° C. for 5 minutes to form an adhesive layer. A peelable protective film was attached to the adhesive layer. This polarizing plate was cut (punched) to produce a polarizing plate 101.
  • Polarizers 102 to 116 were produced in the same manner except that the hard coat film 1 was changed to the hard coat films 2 to 16 in the production of the polarizer 101.
  • ⁇ Production of Liquid Crystal Display Device 401> Remove the polarizing plate of the NEC notebook PC LaVie G type liquid crystal panel and use the adhesive layer and the liquid crystal cell glass so that the hard coat layer is on the viewing side of the polarizing plate 101 prepared as the viewing side polarizing plate. Pasted. Further, on the backlight side, a polarizing plate 201 laminated and bonded so as to sandwich the polarizing film with the protective film 1 subjected to alkali saponification treatment in the same manner as in the above procedure is used with an acrylic adhesive having a thickness of 25 ⁇ m. The liquid crystal panel 301 was produced by bonding to a 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 416 were similarly manufactured except that the polarizing plate 101 was changed to the polarizing plates 102 to 116 in manufacturing the liquid crystal display device 401, respectively.
  • Example 5 Preparation of hard coat film 1 with conductive film>
  • a double-sided hard coat film 1 was produced in the same manner except that the hard coat layer coating composition 1 was coated on both sides.
  • a transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 200 ⁇ is provided on one side of the hard coat layer using a sputtering method, and the hard coat film with a conductive film for a touch panel shown in FIG. 1 was produced.
  • ITO indium tin oxide
  • a transparent conductive thin film of ITO having a surface resistivity of about 200 ⁇ is provided on one side of the hard coat layers of the double-sided hard coat films 2 to 16 using a sputtering method, and the hard coat film 2 with a conductive film for a touch panel is provided. To 16 were produced.
  • a straight line 40 mm was reciprocated 150,000 times at a load of 500 g and a pen sliding speed of 100 mm / second.
  • the hard coat layer was scratched and peeled visually.
  • the hard coat film with a conductive film of the present invention was excellent in pen sliding resistance. Further, as a result of evaluating the visibility of the resistive film type touch panel liquid crystal display devices 501 to 516 in the same manner as in Example 4, those using the hard coat film with the conductive film of the comparative example had a visibility of ⁇ to ⁇ . However, what used the hard coat film with an electroconductive film of this invention was favorable, and visibility was (circle).

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

L'invention concerne un film de revêtement dur comportant une adhérence intercouche améliorée entre un film protecteur et une couche de revêtement dure après test de résistance aux intempéries. L'invention concerne également un procédé de production de celui-ci, une plaque de polarisation le comprenant, et un dispositif d'affichage à cristaux liquides. Le film de revêtement dur comprend la couche de revêtement dure sur le film protecteur, et se caractérise en ce que la couche de revêtement dure comprend un dérivé d'isocyanurate solidifiable par rayons d'énergie active, et en ce que la tand dudit film protecteur dans le sens de la largeur du film répond à la relation suivante : 0,5 ? tand-40/tandpeak ? 0,24 (où, tandpeak est la valeur maximale de tand telle que mesurée à une température de 25°C à 210°C, et tand-40 est la valeur de tand à 40°C en dessous de la température lorsque tandpeak est indiquée.)
PCT/JP2011/054732 2010-03-15 2011-03-02 Film de revêtement dur, procédé de production, plaque de polarisation et dispositif d'affichage à cristaux liquides Ceased WO2011114884A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012505600A JP5751249B2 (ja) 2010-03-15 2011-03-02 ハードコートフィルム、その製造方法、偏光板、及び液晶表示装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-057248 2010-03-15
JP2010057248 2010-03-15

Publications (1)

Publication Number Publication Date
WO2011114884A1 true WO2011114884A1 (fr) 2011-09-22

Family

ID=44648987

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/054732 Ceased WO2011114884A1 (fr) 2010-03-15 2011-03-02 Film de revêtement dur, procédé de production, plaque de polarisation et dispositif d'affichage à cristaux liquides

Country Status (2)

Country Link
JP (1) JP5751249B2 (fr)
WO (1) WO2011114884A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013088438A (ja) * 2011-10-13 2013-05-13 Konica Minolta Advanced Layers Inc 光学フィルム、その製造方法及び画像表示装置
JP2013161404A (ja) * 2012-02-08 2013-08-19 Konica Minolta Inc 導電性フィルム及びタッチパネル
WO2013147028A1 (fr) * 2012-03-30 2013-10-03 大日本印刷株式会社 Composition de résine, film transparent pour capteurs d'écran tactile l'utilisant, et écran tactile
WO2014034850A1 (fr) * 2012-08-31 2014-03-06 王子ホールディングス株式会社 Feuille pour impression, feuille décorative, et feuille décorative adhésive
JP2014044387A (ja) * 2011-12-28 2014-03-13 Toyobo Co Ltd 液晶表示装置、偏光板及び偏光子保護フィルム
JP2014133393A (ja) * 2013-01-11 2014-07-24 Dainippon Printing Co Ltd タッチパネル用前面基板
JP2014178519A (ja) * 2013-03-15 2014-09-25 Fujifilm Corp セルロースアシレートフィルム、偏光板および液晶表示装置
JP2014178518A (ja) * 2013-03-15 2014-09-25 Fujifilm Corp セルロースアセテートブチレートフィルム、偏光板および液晶表示装置
US9798189B2 (en) 2010-06-22 2017-10-24 Toyobo Co., Ltd. Liquid crystal display device, polarizer and protective film
US10054816B2 (en) 2009-11-12 2018-08-21 Toyo Boseki Kabushiki Kaisha Method for improving visibility of liquid crystal display device, and liquid crystal display device using same
US10175494B2 (en) 2011-05-18 2019-01-08 Toyobo Co., Ltd. Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device
US10180597B2 (en) 2011-05-18 2019-01-15 Toyobo Co., Ltd. Liquid crystal display device, polarizing plate, and polarizer protection film
JP2019116048A (ja) * 2017-12-27 2019-07-18 東山フイルム株式会社 インサート成形用ハードコートフィルム、インサート成形物および車載用ディスプレイ
WO2022125668A1 (fr) * 2020-12-10 2022-06-16 3D Systems, Inc. Matériaux de construction résistants à la flamme et articles associés imprimés en 3d
JP2022092403A (ja) * 2020-12-10 2022-06-22 三菱ケミカル株式会社 塗布型偏光素子形成用積層フィルム
JP2023107107A (ja) * 2022-01-21 2023-08-02 日本ゼオン株式会社 積層体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241446A (ja) * 2000-12-11 2002-08-28 Asahi Glass Co Ltd 硬化性組成物、硬化被膜および被覆基材
JP2005239977A (ja) * 2004-02-27 2005-09-08 Jsr Corp 表面保護フィルム
JP2005288214A (ja) * 2004-03-31 2005-10-20 Dainippon Ink & Chem Inc 硬化膜製造方法
JP2009300506A (ja) * 2008-06-10 2009-12-24 Hitachi Chem Co Ltd ディスプレイ用耐衝撃フィルム
JP2010009027A (ja) * 2008-05-27 2010-01-14 Nitto Denko Corp 粘着型偏光板、画像表示装置およびそれらの製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006117908A (ja) * 2004-09-22 2006-05-11 Fuji Photo Film Co Ltd 透明フィルム、光学補償フィルム、偏光板、及び液晶表示装置
JP2006225434A (ja) * 2005-02-15 2006-08-31 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物及びハードコート層を有するプラスチックフィルム
JP2009063983A (ja) * 2006-12-21 2009-03-26 Fujifilm Corp 光学フィルム、及びそれを有する偏光板
JP5309677B2 (ja) * 2007-09-21 2013-10-09 コニカミノルタ株式会社 ハードコートフィルムの製造方法
JP2009210777A (ja) * 2008-03-04 2009-09-17 Konica Minolta Opto Inc 光学フィルム、及びそれを用いた偏光板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241446A (ja) * 2000-12-11 2002-08-28 Asahi Glass Co Ltd 硬化性組成物、硬化被膜および被覆基材
JP2005239977A (ja) * 2004-02-27 2005-09-08 Jsr Corp 表面保護フィルム
JP2005288214A (ja) * 2004-03-31 2005-10-20 Dainippon Ink & Chem Inc 硬化膜製造方法
JP2010009027A (ja) * 2008-05-27 2010-01-14 Nitto Denko Corp 粘着型偏光板、画像表示装置およびそれらの製造方法
JP2009300506A (ja) * 2008-06-10 2009-12-24 Hitachi Chem Co Ltd ディスプレイ用耐衝撃フィルム

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10948764B2 (en) 2009-11-12 2021-03-16 Keio University Method for improving visibility of liquid crystal display device, and liquid crystal display device using the same
US10054816B2 (en) 2009-11-12 2018-08-21 Toyo Boseki Kabushiki Kaisha Method for improving visibility of liquid crystal display device, and liquid crystal display device using same
US9897857B2 (en) 2010-06-22 2018-02-20 Toyobo Co., Ltd. Liquid crystal display device, polarizer and protective film
US9798189B2 (en) 2010-06-22 2017-10-24 Toyobo Co., Ltd. Liquid crystal display device, polarizer and protective film
US10503016B2 (en) 2010-06-22 2019-12-10 Toyobo Co., Ltd. Liquid crystal display device, polarizer and protective film
US10180597B2 (en) 2011-05-18 2019-01-15 Toyobo Co., Ltd. Liquid crystal display device, polarizing plate, and polarizer protection film
US10175494B2 (en) 2011-05-18 2019-01-08 Toyobo Co., Ltd. Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device
JP2013088438A (ja) * 2011-10-13 2013-05-13 Konica Minolta Advanced Layers Inc 光学フィルム、その製造方法及び画像表示装置
JP2017062503A (ja) * 2011-12-28 2017-03-30 東洋紡株式会社 液晶表示装置、偏光板及び偏光子保護フィルム
JP2014044387A (ja) * 2011-12-28 2014-03-13 Toyobo Co Ltd 液晶表示装置、偏光板及び偏光子保護フィルム
JP2013161404A (ja) * 2012-02-08 2013-08-19 Konica Minolta Inc 導電性フィルム及びタッチパネル
KR20140138815A (ko) * 2012-03-30 2014-12-04 가부시키가이샤 디엔피 파인 케미칼 수지 조성물, 그것을 사용한 터치 패널 센서용 투명막 및 터치 패널
CN104204010A (zh) * 2012-03-30 2014-12-10 Dnp精细化工股份有限公司 树脂组合物、使用其的触摸面板传感器用透明膜以及触摸面板
US9430071B2 (en) 2012-03-30 2016-08-30 Dnp Fine Chemicals Co., Ltd. Resin composition, and transparent membrane for touch panel sensors and touch panel using same
KR101679137B1 (ko) * 2012-03-30 2016-11-23 가부시키가이샤 디엔피 파인 케미칼 수지 조성물, 그것을 사용한 터치 패널 센서용 투명막 및 터치 패널
CN104204010B (zh) * 2012-03-30 2017-02-22 Dnp精细化工股份有限公司 树脂组合物、使用其的触摸面板传感器用透明膜以及触摸面板
JP2013213864A (ja) * 2012-03-30 2013-10-17 Dainippon Printing Co Ltd 樹脂組成物、それを用いたタッチパネルセンサ用透明膜およびタッチパネル
WO2013147028A1 (fr) * 2012-03-30 2013-10-03 大日本印刷株式会社 Composition de résine, film transparent pour capteurs d'écran tactile l'utilisant, et écran tactile
JP5850165B2 (ja) * 2012-08-31 2016-02-03 王子ホールディングス株式会社 印刷用シート、加飾シート、および粘着性加飾シート
WO2014034850A1 (fr) * 2012-08-31 2014-03-06 王子ホールディングス株式会社 Feuille pour impression, feuille décorative, et feuille décorative adhésive
JP2014133393A (ja) * 2013-01-11 2014-07-24 Dainippon Printing Co Ltd タッチパネル用前面基板
JP2014178519A (ja) * 2013-03-15 2014-09-25 Fujifilm Corp セルロースアシレートフィルム、偏光板および液晶表示装置
JP2014178518A (ja) * 2013-03-15 2014-09-25 Fujifilm Corp セルロースアセテートブチレートフィルム、偏光板および液晶表示装置
JP2019116048A (ja) * 2017-12-27 2019-07-18 東山フイルム株式会社 インサート成形用ハードコートフィルム、インサート成形物および車載用ディスプレイ
WO2022125668A1 (fr) * 2020-12-10 2022-06-16 3D Systems, Inc. Matériaux de construction résistants à la flamme et articles associés imprimés en 3d
JP2022092403A (ja) * 2020-12-10 2022-06-22 三菱ケミカル株式会社 塗布型偏光素子形成用積層フィルム
US11905355B2 (en) 2020-12-10 2024-02-20 3D Systems, Inc. Flame resistant build materials and associated printed 3D articles
JP7600658B2 (ja) 2020-12-10 2024-12-17 三菱ケミカル株式会社 塗布型偏光素子形成用積層フィルム
US12247094B2 (en) 2020-12-10 2025-03-11 3D Systems, Inc. Flame resistant build materials and associated printed 3D articles
JP2023107107A (ja) * 2022-01-21 2023-08-02 日本ゼオン株式会社 積層体

Also Published As

Publication number Publication date
JPWO2011114884A1 (ja) 2013-06-27
JP5751249B2 (ja) 2015-07-22

Similar Documents

Publication Publication Date Title
JP5751249B2 (ja) ハードコートフィルム、その製造方法、偏光板、及び液晶表示装置
JP5799954B2 (ja) 防眩性フィルム、防眩性フィルムの製造方法、偏光板及び液晶表示装置
KR101618423B1 (ko) 방현성 필름, 그 제조 방법, 편광판, 화상 표시 장치 및 터치 패널용 부재
KR101342183B1 (ko) 편광판 및 액정 표시 장치
JP5423382B2 (ja) ハードコートフィルムの製造方法
JP5479258B2 (ja) セルロースアシレートフィルム及びその製造方法、並びにそれを用いた偏光板及び液晶表示装置
JP6048506B2 (ja) 光学フィルム
WO2012026192A1 (fr) Film de revêtement dur, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP5971121B2 (ja) 光学フィルムの製造方法
JPWO2016111316A1 (ja) 偏光板保護フィルムとその製造方法、偏光板及び液晶表示装置
JP2013064821A (ja) ハードコートフィルム、偏光板及び画像表示装置
JP5382118B2 (ja) 偏光板、及び液晶表示装置
JP5948750B2 (ja) 防眩性フィルム、防眩性フィルムの製造方法、偏光板及び立体画像表示装置
JP5980465B2 (ja) 偏光板及びそれを用いた液晶表示装置
CN104755972B (zh) 光学膜及光学膜的制造方法、偏振片及液晶显示装置
JP2012128064A (ja) 反射防止フィルム、偏光板、及び画像表示装置
JP2011118088A (ja) 長尺状偏光板、及び液晶表示装置
JP2012068562A (ja) 画像表示装置
JP2013088438A (ja) 光学フィルム、その製造方法及び画像表示装置
JP2006251163A (ja) 反射防止フィルム、偏光板及びこれらを用いた画像表示装置
JP2013064813A (ja) 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置
JP2014061643A (ja) 光学フィルムの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11756073

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012505600

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11756073

Country of ref document: EP

Kind code of ref document: A1