WO2011105294A1 - エッジライト型バックライト用白色反射フィルム及びそれを用いたバックライト - Google Patents

エッジライト型バックライト用白色反射フィルム及びそれを用いたバックライト Download PDF

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Publication number
WO2011105294A1
WO2011105294A1 PCT/JP2011/053485 JP2011053485W WO2011105294A1 WO 2011105294 A1 WO2011105294 A1 WO 2011105294A1 JP 2011053485 W JP2011053485 W JP 2011053485W WO 2011105294 A1 WO2011105294 A1 WO 2011105294A1
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Prior art keywords
reflective film
white
film
backlight
white reflective
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Ceased
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PCT/JP2011/053485
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English (en)
French (fr)
Japanese (ja)
Inventor
善彦 坂口
融司 河田
渡邊　修
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2011523235A priority Critical patent/JP5578177B2/ja
Priority to KR1020177026441A priority patent/KR20170109696A/ko
Priority to CN201180005983.2A priority patent/CN102713692B/zh
Priority to KR1020127024657A priority patent/KR101796332B1/ko
Priority to US13/580,188 priority patent/US9817160B2/en
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to EP11747258.9A priority patent/EP2541285B1/en
Priority to KR1020177026442A priority patent/KR20170109697A/ko
Priority to MX2012009190A priority patent/MX2012009190A/es
Publication of WO2011105294A1 publication Critical patent/WO2011105294A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033—Means for improving the coupling-out of light from the light guide
    • G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
    • G02B6/0055—Reflecting element, sheet or layer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133615—Edge-illuminating devices, i.e. illuminating from the side

Definitions

  • the present invention relates to a white reflective film for improving luminance unevenness of a liquid crystal backlight. More specifically, the present invention relates to a white reflective film suitably used for an edge light type liquid crystal display backlight and an illumination surface light source such as a signboard / vending machine.
  • the liquid crystal display uses a backlight that illuminates the liquid crystal cell.
  • a relatively small liquid crystal monitor employs an edge light type backlight
  • a relatively large liquid crystal television employs a direct type backlight.
  • a porous white film formed of bubbles is generally used (Patent Document 1).
  • a white film in which an ultraviolet absorbing layer is laminated in order to prevent yellow discoloration of the film due to ultraviolet rays emitted from a cold cathode tube has been proposed (Patent Documents 2 and 3).
  • a reflection sheet in which a layer containing soft beads is laminated on a base sheet layer has also been developed as being particularly suitable for use with a light guide plate having a prism shape (Patent Documents 4 and 5).
  • LEDs light emitting diodes
  • LCD TVs require high brightness and require a large number of LEDs. Therefore, it was necessary to create a case using aluminum with a high thermal conductivity coefficient and take measures for heat dissipation. However, when aluminum is employed, mechanical strength tends to be poor. Therefore, for example, as shown in FIG. 1, it has been necessary to form irregularities on the back housing 4 by drawing. The unevenness was also intended to save space by arranging a circuit or the like in the recess 7 for thinning.
  • a light guide plate is indispensable as an optical member for an edge light type backlight.
  • the size up to about 25 inches is sufficient for the conventional notebook personal computer and desktop monitor, but 30 to 60 inches are required for the TV.
  • a light guide plate having a convex portion obtained by dot-printing mainly on an acrylic plate (3 to 4 mm thick), a light guide plate having a concave portion by laser processing or UV transfer method, and the like have been developed.
  • (1) to (6) are mainly cited as problems of the reflective sheet.
  • (4) The problem is that the reflection sheet rises due to local convex portions generated due to poor molding of the back housing, and as a result of strong contact with the light guide plate, the light guide plate is scratched and luminance unevenness occurs.
  • the reflection sheets described in Patent Documents 4 and 5 described above also show an effect to some extent.
  • these reflective sheets cannot sufficiently satisfy the rigidity, the maximum height of the convex portions, and the cushioning properties required for the liquid crystal TV applications that are made thinner and larger.
  • the present invention improves brightness unevenness even when it is used by being overlapped with a housing having an uneven portion for arranging a circuit or the like or used with an LED.
  • the present invention is intended to provide a white reflective film that can prevent uneven contact with the light guide plate and damage to the light guide plate.
  • the present invention employs any one of the following means (1) to (7) in order to solve such a problem.
  • a white reflective film for an edge-light type backlight that satisfies the following (i) to (iii):
  • the rigidity is 2 to 10 mN ⁇ m.
  • Projections are formed on at least one surface (A), and the maximum height of the projections is 15 to 60 ⁇ m.
  • the cushion rate on the surface (B) opposite to the surface (A) is 12% or more.
  • the white base film has a coating layer containing spherical particles on at least one side, and the compressive strength of the spherical particles is 0.1 to 2.0 kgf / mm 2 as described in (1) above White reflective film for edge light type backlight.
  • the white reflective film for edge light type backlight according to (2) wherein the spherical particles are nylon.
  • the white reflective film for edge light type backlight according to (3) wherein the nylon is nylon 12 and / or a copolymer of nylon 6 and nylon 12.
  • the white light-reflecting film for edge-light-type backlights according to any one of (1) to (5) above, and a light source including a light-emitting diode, and a backlight size of 76.2 cm (30 inches) This is the LCD backlight.
  • (7) Furthermore, it has a light guide plate with surface irregularities of 10 ⁇ m or more, and the white light reflection film for the edge light type backlight is arranged so that the convex part of the surface (A) faces the light guide plate.
  • the backlight for liquid crystal display as described in said (6).
  • the rigidity of the white reflective film is set to a specific range, and a convex portion having a specific size is formed on at least one surface (A) (the reflective surface side in use, the side facing the light guide plate).
  • a reflective film can be provided.
  • the white reflective film obtained in the present invention was used for an edge light type backlight provided with an LED light source and a surface light source for illumination (especially used for a backlight having a size of 76.2 cm (30 inches) or more). At the same time, the luminance unevenness can be reduced more than ever, which is preferable.
  • the schematic diagram which shows one embodiment of the large sized edge light type backlight which used LED as the light source.
  • the present invention as a result of intensive studies on the above-mentioned problem, that is, the white reflective film with little brightness unevenness and white spot unevenness in the edge light type backlight, results in the rigidity of the white reflective film and the convexity formed on at least one surface (A).
  • the maximum height of the portion and the cushion rate on the surface opposite to the surface (A) are in a specific range, it has been sought to solve the above problems all at once. Means the following unevenness observed visually when the backlight is turned on.
  • white spot unevenness is an ellipsoid having a major axis of less than 5 cm that is visually observed when the backlight is turned on. This means a spot-like unevenness.
  • the white reflective film according to the present invention has a stiffness of 2 to 10 mN ⁇ m, preferably 3 to 10 mN ⁇ m.
  • the rigidity is less than 2 mN ⁇ m, the luminance unevenness in the edge light type backlight increases.
  • the stiffness exceeds 10 mN ⁇ m, the brightness unevenness of the edge light type backlight increases, and the curl remaining on the film when the white reflective film is unwound from the roll body increases, and the backlight is assembled. Workability at times may be worse.
  • the method for measuring the rigidity of the white reflective film is as follows. (I) According to JIS P8125 (2000), TARBER INSTRUMENT corp. In a test environment of 23 ° C. and 50% RH. Measured using “STIFFNESS TESTER” V5. (Ii) The white reflection film is measured three times in both directions on the reflecting surface side and the non-reflecting surface side, and the average value is defined as “rigidity”.
  • the white reflective film according to the present invention has a convex part on at least one surface (the surface on the side serving as the reflective surface, hereinafter referred to as surface (A)).
  • the convex portion needs to have a maximum height of 15 to 60 ⁇ m, preferably 15 to 40 ⁇ m, and most preferably 15 to 25 ⁇ m.
  • the thickness is less than 15 ⁇ m, luminance unevenness in the edge light type backlight increases.
  • it is larger than 60 ⁇ m the light guide plate is likely to be scraped.
  • the measuring method of the maximum height of the convex part formed in at least one side of the white film is as follows.
  • the white reflective film according to the present invention is non-reflective when incorporated into a surface opposite to the surface (A) (hereinafter referred to as surface (B)), that is, a backlight.
  • the cushion rate on the surface side is 12% or more.
  • the upper limit is not particularly limited, but if it exceeds 50%, the rigidity of the white reflective film is also lowered, and uneven brightness tends to occur. If it is less than 12%, the reflection sheet due to the local convex part of the casing caused by the molding failure of the rear casing is in strong contact with the light guide plate, so that it cannot absorb the rising stress of the convex part. Scratches cause uneven brightness.
  • the cushion rate of the white reflective film is a value measured by the following method.
  • the white reflective film according to the present invention as described above can be produced, for example, by any of the following methods.
  • (I) A method of forming a white reflective film having the above characteristics by providing a specific resin layer or coating layer on both sides of a base white film.
  • (II) A method for producing a white reflective film having the above characteristics by using a specific raw material when producing a white film by melt extrusion.
  • (III) A method for obtaining a white reflective film having the above characteristics by a method in which the methods (I) and (II) are mixed.
  • methods for bringing various properties into a desired range include the following methods.
  • the method for controlling the rigidity of the white reflective film to the above range is not limited, but the following methods can be exemplified.
  • the coating method (i) is preferable in that high performance can be achieved economically.
  • the compressive strength of the spherical particles in the coating layer laminated on at least one side of the base white film is not particularly limited as long as no luminance unevenness occurs in the edge light type backlight, To 2.0 kgf / mm 2 (0.98 to 19.6 MPa), more preferably 0.1 to 1.5 kgf / mm 2 (0.98 to 14.7 MPa), and most preferably 0.1 to 1 2 kgf / mm 2 (0.98 to 11.8 MPa).
  • a compressive strength of less than 0.1 kgf / mm 2 (0.98 MPa) is not preferable because the resin particles may collapse due to the kneading share when the spherical particles are stirred to prepare a coating material. Conversely, when the compressive strength exceeds 2 kgf / mm 2 (19.6 MPa), the light guide plate may be scraped.
  • the method for measuring the compressive strength of the spherical particles is as follows.
  • Compressive strength (kgf / mm 2 ) 2.8 ⁇ load (kgf) / ⁇ ⁇ (particle radius (mm)) 2 ⁇
  • Compressive strength of spherical particles 2.8 ⁇ load (kgf) / ⁇ ⁇ (particle radius (mm)) 2 ⁇
  • organic solvent used for extracting the binder resin those exemplified as the solvent mixed with the binder resin and the spherical particles constituting the coating layer as described later may be used.
  • the type of spherical particles is not particularly limited, and any of organic and inorganic types can be used.
  • organic spherical particles acrylic resin particles, silicone resin particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, urethane resin particles, and the like can be used.
  • inorganic spherical particles silica, aluminum hydroxide, aluminum oxide, zinc oxide, barium sulfide, magnesium silicate, or a mixture thereof can be used.
  • a binder resin made of a copolymer of an acrylic monomer and an ultraviolet absorber which will be described later, is used as the binder resin for the coating layer
  • the relationship between the refractive index difference between the binder resin and the spherical particles, particle dispersibility, coating From the viewpoint of properties, acrylic resin particles, silicone resin particles, nylon resin particles, and urethane resin particles are preferably used.
  • nylon resin particles are more preferable from the viewpoint of scratching to the light guide plate, and most preferable are nylon 12 resin particles and / or resin particles made of a copolymer of nylon 6 and nylon 12.
  • nylon 12 resin particles nylon fine particles SP500, SP10 (manufactured by Toray Industries, Inc.), “Ganz Pearl” (registered trademark) GPA550 (manufactured by Ganz Kasei Co., Ltd.), and the like can be used.
  • resin particles made of a copolymer of nylon 6 and nylon 12 SP20 (manufactured by Toray Industries, Inc.) can be used.
  • the specific gravity of spherical particles is not particularly limited as long as luminance unevenness does not occur in an edge light type backlight. However, from the viewpoint of dispersibility with a binder resin and an organic solvent described later, 0.8 to 1.10 is preferable, and 0.8 to 1.05 is more preferable. If the specific gravity of the spherical particles exceeds 1.10, the dispersibility of the spherical particles is lowered, coating stripes and coating spots are frequently generated, and the yield may be lowered.
  • the method for measuring the specific gravity of the spherical particles according to the present invention is as follows.
  • (I) The binder resin is extracted from the coating layer of the white reflective film using an organic solvent, and after distilling off the organic solvent, the spherical particles in the coating layer are collected.
  • (Ii) Using a true density measuring instrument (for example, Auto True Densor MAT-7000, manufactured by Seishin Enterprise Co., Ltd.), measurement was performed on five samples collected arbitrarily, and the number average was defined as “specific gravity of spherical particles”. To do.
  • a true density measuring instrument for example, Auto True Densor MAT-7000, manufactured by Seishin Enterprise Co., Ltd.
  • the binder resin constituting the coating layer provided on at least one side of the base white film is not particularly limited, but a resin mainly comprising an organic component is preferable, for example, a polyester resin, a polyurethane resin, an acrylic resin, Examples thereof include methacrylic resin, polyamide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, fluorine resin, and silicone resin. These resins may be used alone or in combination of two or more. Of these, polyester resins, polyurethane resins, acrylic or methacrylic resins are preferably used in terms of heat resistance, particle dispersibility, coatability, and glossiness.
  • the binder resin layer contains an ultraviolet absorber and a light stabilizer.
  • ultraviolet absorbers and light stabilizers are roughly classified into inorganic and organic types.
  • the form to be contained is not particularly limited, and may be a method such as mixing with a resin for forming such a coating layer. If it is desired to prevent bleeding out from such a coating layer, for example, the coating layer is formed. A method such as copolymerization with a resin to be used may be used.
  • titanium oxide, zinc oxide, cerium oxide, etc. are generally known. Among them, at least one selected from the group consisting of zinc oxide, titanium oxide, and cerium oxide is bleed out. It is preferably used from the viewpoints of economy, light resistance, ultraviolet absorption, and photocatalytic activity. Such ultraviolet absorbers may be used in combination of several kinds as required. Of these, zinc oxide or titanium oxide is most preferable from the viewpoints of economy, ultraviolet absorption, and photocatalytic activity.
  • organic ultraviolet absorbers examples include benzotriazole and benzophenone.
  • benzotriazole can be suitably used because it contains nitrogen in the structure and thus has a function as a flame retardant, but is not particularly limited thereto. Since these ultraviolet absorbers only absorb ultraviolet rays and cannot capture organic radicals generated by ultraviolet irradiation, the base thermoplastic resin film may be deteriorated in a chain by these radicals.
  • a light stabilizer is preferably used in combination, and a hindered amine (HALS) compound is preferably used as the light stabilizer.
  • HALS hindered amine
  • vinyl monomers such as acrylic and styrene are highly versatile and economically preferable.
  • copolymerizable monomers since the styrene vinyl monomer has an aromatic ring and is easily yellowed, copolymerization with an acrylic vinyl monomer is most preferably used in terms of light resistance.
  • benzotriazole 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (trade name: RUVA-) is used in which a reactive vinyl monomer is substituted for the benzotriazole. 93); manufactured by Otsuka Chemical Co., Ltd.), and in the case of hindered amine compounds, 4-methacryloyloxy-2,2,6,6 Tetramethylpiperidine (“ADK STAB LA-82”; manufactured by ADEKA Corporation) can be used.
  • ADK STAB LA-82 4-methacryloyloxy-2,2,6,6 Tetramethylpiperidine
  • organic ultraviolet absorbers examples include resins containing organic ultraviolet absorbers such as benzotriazole and benzophenone, resins obtained by copolymerizing benzotriazole and benzophenone reactive monomers, and hindered amines.
  • a resin containing and / or copolymerizing a light stabilizer such as a (HALS) -based reactive monomer can be used within a range that does not impair the effects of the present invention.
  • Organic UV-absorbing resins containing a resin obtained by copolymerizing such benzotriazole-based and benzophenone-based reactive monomers, and further a resin copolymerized with a hindered amine (HALS) -based reactive monomer are thin and have a high UV absorption effect.
  • HALS hindered amine
  • benzotriazole is particularly preferred because it contains nitrogen in the structure and also has a function as a flame retardant.
  • the substrate white film should have a higher visible light reflectance when used as a backlight for a liquid crystal display or a reflective film for illumination. For this reason, a film containing bubbles and / or incompatible particles therein, specifically, a white thermoplastic resin film is preferably used.
  • white thermoplastic resin films include, but are not limited to, polyolefins such as porous unstretched or biaxially stretched polypropylene films and porous unstretched or stretched polyethylene terephthalate films.
  • a polyester film is preferably used. In particular, a polyester film is preferably used from the viewpoint of moldability and productivity.
  • the porous white biaxially stretched polyethylene terephthalate film disclosed in JP-A-2002-90515 can be preferably used as the base white film in the present invention for the reasons described above.
  • a porous white biaxially stretched polyethylene terephthalate film mixed and / or copolymerized with polyethylene naphthalate is preferable, and in particular, the white thermoplastic resin film itself has flame retardancy.
  • a porous white biaxially stretched polyethylene terephthalate film containing inorganic particles is preferable.
  • the content rate of the inorganic particle contained in this white thermoplastic resin film is 2 mass% or more with respect to the total mass of a white thermoplastic resin film, More preferably, it is 7 mass% or more, More preferably Is 10% by mass or more, and most preferably 30% by mass or more.
  • the configuration of the base white film according to the present invention may be appropriately selected depending on the intended use and required characteristics, and is not particularly limited. Specifically, a single layer and / or a composite film of two or more layers having a configuration of at least one layer can be exemplified, and it is preferable that at least one or more layers contain bubbles and / or inorganic particles.
  • a film having a single layer structure is a film composed of only a single layer (hereinafter referred to as A layer), and the A layer contains inorganic particles and / or bubbles.
  • the two-layer film is a film having a structure of A layer / B layer obtained by laminating a B layer on the A layer.
  • inorganic particles and / Or air bubbles are contained.
  • the content of the inorganic particles is preferably 2% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass with respect to the total mass of the base white film, that is, the total mass of the two layers. Above, most preferably 30% by mass or more.
  • the film having a three-layer structure is a film having a structure of A layer / B layer / A layer or A layer / B layer / C layer as described above, and at least one of these layers contains inorganic particles. And / or contains bubbles.
  • the content rate of an inorganic particle is 2 mass% or more with respect to the total mass of a base white film similarly to the film of 2 layer structure, More preferably, it is 7 mass% or more, More preferably, it is 10 It is at least 30% by mass, most preferably at least 30% by mass.
  • the B layer is most preferably a layer containing bubbles from the viewpoint of productivity.
  • the number average particle diameter of the inorganic fine particles contained in such a substrate white film is preferably 0.3 to 2.0 ⁇ m.
  • examples of the inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, silica, alumina, mica, titanium mica, talc, clay, Kaolin, lithium fluoride, calcium fluoride, or the like can be used.
  • the manufacturing method of the white thermoplastic resin film of 3 layer structure among the said base material white films is demonstrated.
  • the present invention is not limited to this example.
  • polymethylpentene is added as an incompatible polymer, and a copolymer of polyethylene glycol, polybutylene terephthalate, and polytetramethylene glycol is added as a low specific gravity agent to polyethylene terephthalate.
  • the mixture is sufficiently mixed and dried, and then supplied to the extruder B heated to a temperature of 270 to 300 ° C.
  • Polyethylene terephthalate containing inorganic and / or organic additives such as BaSO 4 , CaCO 3 , and TiO 2 is supplied to the extruder A by a conventional method.
  • the polymer of the extruder B is arranged on the inner layer (B layer), and the polymer of the extruder A is arranged on both surface layers (A layer), so that A layer / B layer / A layer Laminated in three layers of the structure.
  • the melt-laminated sheet is closely cooled and solidified by electrostatic force on a drum cooled to a drum surface temperature of 10 to 60 ° C. to obtain an unstretched film.
  • the unstretched film is guided to a roll group heated to 80 to 120 ° C., longitudinally stretched 2.0 to 5.0 times in the longitudinal direction, and cooled with a roll group of 20 to 50 ° C. Subsequently, the film is stretched in the direction perpendicular to the longitudinal direction in an atmosphere heated to 90 to 140 ° C. while being guided to a tenter while holding both ends of the longitudinally stretched film with clips.
  • the stretching ratio is 2.5 to 4.5 times in the longitudinal and lateral directions, and the area ratio (longitudinal stretching ratio ⁇ lateral stretching ratio) is preferably 9 to 16 times. That is, when the area magnification is less than 9, the whiteness of the obtained film tends to be poor. On the other hand, if the area magnification exceeds 16 times, the film tends to be broken during stretching and the film forming property tends to be poor.
  • the film is heat-set at 150 to 230 ° C. in a tenter, uniformly cooled, and further cooled to room temperature. To obtain a substrate thermoplastic resin film.
  • the thickness of the base white film is designed in the range of 200 to 450 ⁇ m, for example.
  • examples of the base white film having a single layer structure include “Lumirror” (registered trademark) E20 (manufactured by Toray Industries, Inc.), SY64, SY74 (manufactured by SKC), and the like.
  • surface of a base white film arbitrary methods are employable. For example, gravure coat, roll coat, spin coat, reverse coat, reverse kiss coat, bar coat, screen coat, blade coat, air knife coat, slit die coat, Examples include various coating methods such as lip coating and dipping, which are applied during production of a white substrate film (in-line coating) or applied onto a white substrate film after completion of crystal orientation (off-line coating). When there is little restriction on the effective coating width and the product width is flexible, reverse kiss coating can be most preferably used.
  • the solvent used for mixing with the binder resin and spherical particles constituting the coating layer is an organic compound having the property of dissolving the binder resin, and is applied to the surface of the base white film. After being applied, it is dried.
  • aromatic hydrocarbons such as toluene, xylene and styrene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as methanol, isopropyl alcohol and isobutyl alcohol, chlorobenzene and orthodichloro Chlorinated aromatic hydrocarbons such as benzene, methane derivatives such as monochloromethane, chlorinated aliphatic hydrocarbons containing ethane derivatives such as monochloroethane, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl ether, 1 Ethers such as 1,4-dioxane, glycol ethers such as ethylene glycol monomethyl ether, alicyclic hydrocarbons such as cyclohexane, and aliphatic hydrocarbons such as normal hexane.
  • methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, and butyl acetate are preferable.
  • additives that can be used for the base white film and the coating layer
  • Various additives can be added to the base white film and the coating layer as long as the effects of the present invention are not impaired.
  • additives include organic and / or inorganic fine particles, fluorescent brighteners, crosslinking agents, heat stabilizers, oxidation stabilizers, organic lubricants, antistatic agents, nucleating agents, dyes, fillers, and dispersions.
  • An agent, a flame retardant, a coupling agent and the like can be added and blended.
  • the white reflective film of the present invention is used for edge light type backlights, and among them, it can be suitably used for edge light type liquid crystal display backlights and surface light sources for lighting such as signboards and vending machines. it can.
  • paper substitutes, ie cards, labels, stickers, home delivery slips, video printer paper, inkjet, barcode printer paper, posters, maps, dust-free paper, display boards, white boards, thermal transfer, offset printing, telephones
  • Receiving sheet base materials used for various printing records such as cards and IC cards, building materials such as wallpaper, lighting equipment and indirect lighting equipment used indoors and outdoors, members mounted on automobiles, railways, aircraft, etc., circuit materials, etc. It can also be used as an electronic component.
  • the white reflective film of this invention is used suitably for an edge light type backlight.
  • the edge light type backlight is formed by, for example, incorporating a white reflective film of the present invention and a light guide plate in this order into a housing having unevenness, and the white film has the surface (A) side facing the light guide plate. Incorporated.
  • a light source such as an LED is installed at the edge portion of the light guide plate.
  • a diffusion plate, a prism, or the like may be installed on the front surface of the light guide plate (on the side opposite to the white reflective film).
  • the white reflective film of the present invention for such an edge light type backlight, it is possible to produce a high quality backlight that is free from uneven brightness and that is less damaged by the light guide plate.
  • the backlight area becomes large.
  • the white reflective film of the present invention when used, it is wavy due to curling during assembly or heat generation of the LED light source. There are few, and a high-quality backlight can be manufactured with a good yield.
  • the size (rectangular diagonal length) of a backlight for a liquid crystal display using a light emitting diode as a light source that exhibits the effect of the present invention more effectively is 76.2 cm (30 inches) or more, preferably 88. It is 9 cm (35 inches) or more, more preferably 101.6 cm (40 inches) or more, and most preferably 127 cm (50 inches) or more.
  • a concave or convex portion of 3 um or more is provided on the surface of the light guide plate in the edge light type backlight. Furthermore, it is preferable that a concave or convex portion of 10 ⁇ m or more is provided.
  • the irregularities on the surface of the light guide plate are defined as follows.
  • (I) Take out the light guide plate arranged above the white reflective film from the liquid crystal television.
  • (Ii) The light guide plate is cut into a 5 cm square, and any five sheets are taken out.
  • (Iii) Using a laser microscope VK-9700 manufactured by Keyence Corporation, observation is performed with the magnification of the objective lens set to 20 times, and a portion detected with a height or depth of 1 ⁇ m or more is defined as surface irregularities.
  • a light guide plate having a recess formed by laser processing is preferable in that the backlight luminance is high and the possibility of the light guide plate being scraped by a white reflective film is low.
  • the maximum height of the convex portion formed on at least one side of the white reflective film is larger than the unevenness of the light guide plate surface. By doing so, it is possible to further reduce luminance unevenness in the backlight. This is presumed to be due to the fact that there is a correlation in luminance unevenness due to the adhesion between the light guide plate and the white reflective film, and the convex portions formed on at least one side of the base white film play a role of a spacer to suppress the luminance unevenness. It is estimated that
  • corrugation of the surface of a light-guide plate is as follows. (I) When taking a sample from a liquid crystal television product, the light guide plate disposed on the white reflective film is taken out and used as a measurement sample. (Ii) Cut the light guide plate into 5 cm square.
  • Specific gravity of spherical particles The method for measuring the specific gravity of spherical particles according to the present invention is as follows.
  • (I) The binder resin was extracted from the coating layer of the white reflective film using an organic solvent, and after the organic solvent was distilled off, spherical particles in the coating layer were collected.
  • (Ii) Using a true density measuring device (manufactured by Seishin Co., Ltd., Auto True Densor MAT-7000), measurements were performed on 5 samples collected arbitrarily, and the number average was defined as “specific gravity of spherical particles”. .
  • Surface irregularity of light guide plate (i) The light guide plate placed on the white reflective film was taken out from the liquid crystal television. (Ii) The light guide plate was cut into 5 cm square.
  • a 40-inch liquid crystal television (Samsung, PAVV UN40B7000WF) was disassembled, and an edge-light type backlight (referred to as backlight B) using an LED as a light source was taken out.
  • the size of the light emitting surface of the backlight B was 89.0 cm ⁇ 50.2 cm, and the diagonal length was 102.2 cm.
  • three optical films, a light guide plate (acrylic plate, 4 mm thickness, convex 15 ⁇ m) and a reflective film are taken out from the backlight B, and the same shape as the reflective film on which the reflective films of the examples and comparative examples of the present invention are mounted. Cut to size.
  • the reflective film of each Example and Comparative Example that was cut instead of the mounted reflective film was placed so that the surface provided with the convex portion faces the light guide plate side, and the light guide plate and the three optical films were separated. Installed in the same order and direction.
  • Class B Scratches are observed under a load of 200 gf / cm 2 , but no scratches are observed under a load of 100 gf / cm 2 and a load of 50 gf / cm 2 .
  • Class C 200gf / cm 2, although scratches is observed under a load of 100 gf / cm 2, not seen scratches under a load of 50 gf / cm 2.
  • Class D Scratches are observed under a load of 50 gf / cm 2 .
  • the cut reflective film was installed so that the surface provided with the convex part was facing the light guide plate, and the light guide plate and the three optical films were installed in the same direction and direction as before disassembly. .
  • Class A No white spots are seen.
  • Class B White spots are observed.
  • Example 1 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3.85 g, acrylic Resin particles (“TECHPOLYMER” (registered trademark) BM30X-8 manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 8.0 ⁇ m, coefficient of variation 35%): 0.9 g added with stirring A coating liquid was prepared.
  • TECHPOLYMER registered trademark
  • BM30X-8 manufactured by Sekisui Plastics Co., Ltd.
  • Metabar # 16 is used on one side of a 300 ⁇ m thick porous biaxially oriented polyethylene terephthalate containing polymethylpentene (base white film, “Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) Then, this coating solution was applied, and a coating layer was provided under drying conditions at 120 ° C. for 1 minute.
  • Example 2 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3.85 g, acrylic Resin particles (“TECHPOLYMER” (registered trademark) BM30X-15 manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 15 ⁇ m, coefficient of variation 35%): 0.9 g was added with stirring. A coating solution was prepared.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 3 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 4.50 g, ethyl acetate: 4.30 g, acrylic Resin particles (“TECHPOLYMER” (registered trademark) BM30X-30 manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 30 ⁇ m, variation coefficient 35%): 1.20 g was added with stirring. A coating solution was prepared.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 4 The type of spherical particles in the coating liquid for forming the coating layer is acrylic resin particles (“TECHPOLYMER” (registered trademark “) MBX-30 manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 40 ⁇ m, A white reflective film was obtained by providing a coating layer in the same manner as in Example 3 except that the variation coefficient was 35%.
  • TECHPOLYMER registered trademark “) MBX-30 manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 40 ⁇ m
  • a white reflective film was obtained by providing a coating layer in the same manner as in Example 3 except that the variation coefficient was 35%.
  • Example 5 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 3.0 g, ethyl acetate: 5.2 g, acrylic Resin particles (“TECHPOLYMER” (registered trademark) MBX-40, manufactured by Sekisui Plastics Co., Ltd., refractive index 1.49, volume average particle size 40 ⁇ m, variation coefficient 35%): 1.8 g was added with stirring. A coating solution was prepared.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 6 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 6.0 g, ethyl acetate: 3.4 g, nylon 6 resin particles (TR-1, manufactured by Toray Industries, Inc., refractive index 1.53, volume average particle size 13 ⁇ m, coefficient of variation 48%): A coating solution was prepared by adding 0.6 g with stirring.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 7 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3.85 g, nylon 12 resin particles (SP10 manufactured by Toray Industries, Inc., refractive index 1.53, volume average particle size 10 ⁇ m, coefficient of variation 48%): A coating liquid prepared by adding 0.9 g with stirring was prepared.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 8 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3.85 g, nylon Resin particles made of a copolymer of 6 and nylon 12 (SP20 manufactured by Toray Industries, Inc., refractive index 1.52, volume average particle size 40 ⁇ m, coefficient of variation 29%): 0.9 g added with stirring Prepared.
  • HALS HYBRID registered trademark
  • UV-G720T acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • Example 9 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 3.0 g, ethyl acetate: 5.2 g, nylon Resin particles made of a copolymer of nylon 6 and nylon 12 (SP20 manufactured by Toray Industries, Inc., refractive index 1.52, volume average particle size 40 ⁇ m, coefficient of variation 29%): 0.18 g, acrylic resin particles (Sekisui Plastics Industry ( Co., Ltd.
  • TECHPOLYMER (registered trademark) MBX5, refractive index 1.49, volume average particle size 5 ⁇ m, coefficient of variation 35%): 1.62 g was added while stirring. This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16. The coating layer was provided under drying conditions for 1 minute.
  • Example 10 “HALS HYBRID” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3.85 g, nylon 12 resin particles (SP10 manufactured by Toray Industries, Inc., refractive index 1.53, volume average particle size 10 ⁇ m, coefficient of variation 48%): A coating liquid prepared by adding 0.9 g with stirring was prepared.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 250 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16, 120 ° C., The coating layer was provided under drying conditions for 1 minute.
  • Example 11 The base white film was the same as Example 10 except that a white film made of porous biaxially stretched polyethylene terephthalate with a thickness of 300 ⁇ m containing cyclic polyolefin (“Lumirror” (registered trademark) E80B manufactured by Toray Industries, Inc.) was used. A coating layer was provided to obtain a white reflective film.
  • a white film made of porous biaxially stretched polyethylene terephthalate with a thickness of 300 ⁇ m containing cyclic polyolefin (“Lumirror” (registered trademark) E80B manufactured by Toray Industries, Inc.) was used.
  • a coating layer was provided to obtain a white reflective film.
  • Example 12 Example except that the base white film was a white film made of 225 ⁇ m-thick porous biaxially stretched polyethylene terephthalate containing barium sulfate (“Tetron” (registered trademark) film UXSP manufactured by Teijin DuPont Films Ltd.) In the same manner as in Example 10, a coating layer was provided to obtain a white reflective film.
  • Tetron registered trademark
  • Example 13 Example 10 except that the base white film is a white film made of 400 ⁇ m-thick porous biaxially stretched polyethylene terephthalate containing polymethylpentene (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.). Then, a coating layer was provided to obtain a white reflective film.
  • the base white film is a white film made of 400 ⁇ m-thick porous biaxially stretched polyethylene terephthalate containing polymethylpentene (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.). Then, a coating layer was provided to obtain a white reflective film.
  • Example 14 (I) “Hals Hybrid” (registered trademark) UV-G720T (acrylic copolymer, 40% concentration solution, refractive index 1.58, manufactured by Nippon Shokubai Co., Ltd.): 5.25 g, ethyl acetate: 3. 85 g, nylon 12 resin particles (SP10 manufactured by Toray Industries, Inc., refractive index 1.53, volume average particle size 10 ⁇ m, coefficient of variation 48%): A coating liquid prepared by adding 0.9 g with stirring was prepared.
  • a metabar # 16 on one side of a white film (“Tetron” (registered trademark) film UX manufactured by Teijin DuPont Films Ltd.) made of 188 ⁇ m-thick porous biaxially stretched polyethylene terephthalate containing barium sulfate.
  • the coating liquid was applied, a coating layer was provided under drying conditions at 120 ° C. for 1 minute, and a white reflective film having a convex surface was obtained.
  • a white film (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) containing 188 ⁇ m thick porous biaxially stretched polyethylene terephthalate containing polymethylpentene
  • an adhesive layer for dry lamination was provided under drying conditions at 120 ° C. for 1 minute.
  • a white film (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m was prepared as a base white film.
  • the white film was not provided with a convex portion, and was directly evaluated as a reflective film.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 300 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16.
  • the coating layer was provided under drying conditions for 1 minute.
  • This coating solution was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 188 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16, The coating layer was provided under drying conditions for 1 minute.
  • This adhesive was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 188 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16, An adhesive layer for dry lamination was provided under drying conditions for 1 minute, and dry-laminated with the opposite surface of the convex surface of the white reflective film obtained in Example 7 to obtain a white reflective film.
  • a white film made of porous biaxially stretched polyethylene terephthalate having a thickness of 188 ⁇ m (“Lumirror” (registered trademark) E6SQ manufactured by Toray Industries, Inc.) using Metabar # 16,
  • An adhesive layer for dry lamination was provided under drying conditions for 1 minute, and dry-laminated with the opposite surface of the convex surface of the white reflective film obtained in Example 7 to obtain a white reflective film.
  • This adhesive was applied to one side of a white film made of porous biaxially stretched polyethylene terephthalate with a thickness of 188 ⁇ m (“Tetron” (registered trademark) film UX manufactured by Teijin DuPont Films Ltd.) using Metabar # 16, An adhesive layer for dry lamination was provided under drying conditions at 120 ° C. for 1 minute, and dry-laminated with the opposite surface of the white reflective film obtained in Comparative Example 5 to obtain a white reflective film.
  • Tetron registered trademark
  • the luminance unevenness evaluation was “pass”. However, in Examples 10, 11, and 12 in which the rigidity of the white film is less than 3, the luminance unevenness in the 40-inch edge light type backlight is slightly inferior to those in Examples 1 to 9. In Example 13, the luminance unevenness in the edge light type backlight is good, but the curl characteristics are lower than those in Examples 1-7.
  • Examples 6 to 14 using nylon resin particles as spherical particles are better in terms of shaving of the light guide plate than Examples 1 to 5 using acrylic resin particles.
  • Examples 7 to 14 using resin particles made of nylon 12 or a copolymer of nylon 6 and nylon 12 are particularly excellent in terms of shaving of the light guide plate.
  • the acrylic resin particles the smaller the maximum convex portion of the white reflective film, the less the light guide plate is scraped (Examples 1 to 3), and the smaller the compressive strength of the spherical particles at the same convex portion height, the smaller the light guide plate. Scraping is reduced (Examples 3 and 4).
  • acrylic particles having a relatively small particle size are added to resin particles made of a copolymer of nylon 6 and nylon 12 having a relatively large particle size.
  • resin particles made of the nylon copolymer are mainly in contact with the light guide plate, and the light guide plate is less likely to be scraped, and white spots can be prevented with acrylic particles hidden in the shadow of nylon. That is, both prevention of shaving of the light guide plate and prevention of white spots can be achieved.
  • Example 9 In terms of dispersibility of the spherical particles, Examples 6 to 8 and 10 to 13 having a particle composition of nylon resin particles alone are better than Examples 1 to 5 and 9 using acrylic resin particles, and are solvents. The resin particles made of nylon 12 having a specific gravity close to that of ethyl acetate and a copolymer of nylon 6 and nylon 12 were the best.

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PCT/JP2011/053485 2010-02-24 2011-02-18 エッジライト型バックライト用白色反射フィルム及びそれを用いたバックライト Ceased WO2011105294A1 (ja)

Priority Applications (8)

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MX2012009190A MX2012009190A (es) 2010-02-24 2011-02-18 Pelicula reflectora blanca para luz posterior de bordes iluminados y luz posterior que usa la misma.
KR1020177026441A KR20170109696A (ko) 2010-02-24 2011-02-18 엣지 라이트형 백라이트용 백색 반사 필름 및 그것을 이용한 백라이트
CN201180005983.2A CN102713692B (zh) 2010-02-24 2011-02-18 侧光型背光源用白色反射膜和使用该白色反射膜的背光源
KR1020127024657A KR101796332B1 (ko) 2010-02-24 2011-02-18 엣지 라이트형 백라이트용 백색 반사 필름 및 그것을 이용한 백라이트
US13/580,188 US9817160B2 (en) 2010-02-24 2011-02-18 White reflective film for edge-lit backlight and backlight using the same
JP2011523235A JP5578177B2 (ja) 2010-02-24 2011-02-18 エッジライト型バックライト用白色反射フィルム及びそれを用いたバックライト
EP11747258.9A EP2541285B1 (en) 2010-02-24 2011-02-18 White reflective film for edge-lit backlight and backlight using the aforementioned
KR1020177026442A KR20170109697A (ko) 2010-02-24 2011-02-18 엣지 라이트형 백라이트용 백색 반사 필름 및 그것을 이용한 백라이트

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JP2014112251A (ja) 2014-06-19
KR20120121411A (ko) 2012-11-05
KR101796332B1 (ko) 2017-11-09
JP5578177B2 (ja) 2014-08-27
EP2541285A1 (en) 2013-01-02
MX2012009190A (es) 2012-08-31
TWI499793B (zh) 2015-09-11
JP2015163986A (ja) 2015-09-10
JP2018018085A (ja) 2018-02-01
JP6017475B2 (ja) 2016-11-02
JPWO2011105294A1 (ja) 2013-06-20
CN102713692A (zh) 2012-10-03
KR20170109696A (ko) 2017-09-29
CN102713692B (zh) 2014-12-10
JP6485758B2 (ja) 2019-03-20
US9817160B2 (en) 2017-11-14
TW201131195A (en) 2011-09-16
US20120314450A1 (en) 2012-12-13
EP2541285A4 (en) 2014-04-30
JP6355204B2 (ja) 2018-07-11
KR20170109697A (ko) 2017-09-29

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