JP2016068556A - Laminate film, backlight unit, liquid crystal display device, and production method of laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate film capable of enhancing luminance, a backlight unit and a liquid crystal display device including the laminate film, and a production method of the laminate film.SOLUTION: A laminate film 7, 8 includes an optical functional layer 4 and a barrier layer 6 stacked on at least one surface of the optical functional layer 4, and the laminate film 7, 8 includes a film 5 having a refractive index larger than a refractive index of the optical functional layer 4, on a lateral surface of the optical functional layer 4. The optical functional layer 4 preferably contains at least one of a quantum dot and a quantum rod.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film, a backlight unit, a liquid crystal display device, and a method for producing a laminated film, and more particularly to a laminated film capable of improving luminance and a method for producing the laminated film. Further, the present invention relates to a backlight unit including the laminated film and a liquid crystal display device including the backlight unit.

  A flat panel display such as a liquid crystal display (LCD) (hereinafter also referred to as an LCD) has a low power consumption, and its use is expanding year by year as a space-saving image display device. The liquid crystal display device is composed of at least a backlight and a liquid crystal cell, and usually further includes members such as a backlight side polarizing plate and a viewing side polarizing plate.

  In the flat panel display market, color reproducibility is improving as LCD performance improvement. In this regard, in recent years, quantum dots (also referred to as Quantum Dot, QD, quantum dots) have attracted attention as light emitting materials. For example, when excitation light enters a light conversion member including quantum dots from a backlight, the quantum dots are excited and emit fluorescence. Here, by using quantum dots having different light emission characteristics, it is possible to realize white light by emitting light having a narrow half-value width of red light, green light, and blue light. Since the half-value width of the fluorescence due to quantum dots is narrow, it is possible to design white light obtained by appropriately selecting the wavelength to have high luminance or excellent color reproducibility. With the progress of the three-wavelength light source technology using such quantum dots, the color gamut has been expanded from 72% to 100% compared to the current TV (television) standard (FHD, NTSC (National Television System Committee)). ing.

  However, since QD particles are deteriorated in quantum yield due to oxygen, it is necessary to protect the QD particles with a barrier film. Although the surface of the resin layer can be protected by protecting the resin layer containing the QD particles with a barrier film, oxygen has entered from the end portion, and the performance has been a problem. Moreover, there existed a subject that a brightness | luminance fell by the leak light from a film edge part.

  In response to such a problem, the following Patent Document 1 discloses a quantum dot film including a barrier layer on the side surface of the QD phosphor material layer. Patent Document 2 describes that a barrier layer is disposed on a composition containing a plurality of light-emitting nanocrystals to hermetically seal and protect against deterioration factors such as oxygen and moisture.

Special table 2013-544018 gazette Special table 2010-528118

  However, in Patent Document 1, although the luminance improvement in the normal direction of the quantum dot film is described, light leakage from the side surface of the quantum dot film has not been studied, and the problem of luminance reduction due to light leakage from the end surface is not It was not improved. Also in Patent Document 2, a barrier layer is disposed on the composition, light leakage from the side surface has not been studied, and the light reflectivity is insufficient, resulting in a decrease in luminance.

  The present invention has been made in view of such circumstances, and when used in a backlight, a laminated film capable of improving luminance, a backlight unit including the laminated film, a liquid crystal display device, and this It aims at providing the manufacturing method of a laminated | multilayer film.

  In order to achieve the above object, the present invention is a laminated film formed by laminating an optical functional layer and a barrier layer on at least one surface of the optical functional layer. Provided is a laminated film having a film having a refractive index greater than the refractive index of the layer.

  According to the present invention, since the side surface of the optical functional layer has a film having a refractive index larger than that of the optical functional layer, light can be reflected by the side surface, and the optical path length can be increased. it can. Therefore, the luminance can be improved.

  In another aspect of the present invention, the optical functional layer preferably includes at least one of quantum dots and quantum rods.

  According to this aspect, since at least one of quantum dots and quantum rods is included in the optical functional layer, it can be used as a wavelength conversion member, and luminance unevenness and chromaticity unevenness can be improved.

  In another aspect of the present invention, the film is preferably a film having gas barrier properties.

  According to this aspect, since the film provided on the side surface of the optical functional layer has gas barrier properties, oxygen, water vapor, and the like can be prevented from entering from the side surface of the optical functional layer. Therefore, it is possible to prevent performance deterioration of the optical functional layer.

  In another aspect of the present invention, the membrane is preferably an inorganic membrane.

  According to this aspect, gas barrier properties can be imparted by forming the film with an inorganic film.

  In another aspect of the invention, the film is an oxide, nitride and oxynitride of one or more metals selected from silicon, aluminum, indium, tin, zinc, titanium, chromium, nickel, copper, silver and gold. Preferably it comprises at least one of the objects.

  In this embodiment, the material of the refractive index film is limited, and gas barrier properties can be imparted by using the above materials.

  In another aspect of the present invention, the film comprises a first metal layer made of one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper and silver, and aluminum, titanium, chromium, nickel, A laminated film in which a laminated structure of a metal oxide layer made of an oxide of one or more metals selected from tin, copper and silver is repeated one or more times is preferable.

  According to this aspect, since pinholes and cracks in the first metal layer can be filled with the metal oxide layer, it is possible to prevent light from leaking from the film end face.

  In another aspect of the present invention, it is preferable to further have a second metal layer made of one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper and silver on the laminated film. .

  According to this aspect, the second metal layer can be mirror-finished by forming the second metal layer on the metal oxide layer of the laminated film. Therefore, the light leaking from the film end face can be reused with high reflectivity on the mirror surface, and the luminance can be improved.

  In another aspect of the present invention, the thickness of the first metal layer is preferably 5 nm or more and 50 nm or less, and the thickness of the metal oxide layer is preferably 0.1 nm or more and 5 nm or less.

  In another aspect of the present invention, the thickness of the film is preferably 5 to 500 nm, and more preferably 20 to 200 nm.

  In another aspect of the present invention, the thickness of the second metal layer is preferably 10 nm or more and 200 nm or less.

  In this aspect, the thickness of the film is limited, and by setting the film thickness within the above range, the luminance can be improved and deterioration of the optical functional layer with time can be prevented. Moreover, the light reflection efficiency of the end surface of a laminated film can be improved and the brightness | luminance can be improved by making the thickness of each layer at the time of setting it as a laminated film into the said range.

  In another aspect of the present invention, the refractive index of the optical functional layer is preferably in the range of 1.3 to 1.6, and the refractive index of the film is preferably 1.5 or more.

  This aspect defines the refractive index of the optical functional layer and the refractive index of the film on the side surface of the optical functional layer, and the luminance can be improved by setting the refractive index within the above range.

  In another aspect of the present invention, the difference between the refractive index of the optical functional layer and the refractive index of the film is preferably 0.2 or more.

  In this embodiment, the difference between the refractive index of the optical functional layer and the refractive index of the film on the side surface of the optical functional layer is defined, and the luminance is improved by setting the difference in refractive index within the above range. Can do.

  In order to achieve the above object, the present invention provides a backlight unit including at least the laminated film described above and a light source.

  Since the laminated film has a film having a refractive index larger than the refractive index of the optical functional layer on the side surface, the optical path length inside the film can be extended and the luminance can be improved. It can be used suitably for a unit.

  In order to achieve the above object, the present invention provides a liquid crystal display device including at least the backlight unit described above and a liquid crystal cell.

  The above backlight unit can be suitably used by being incorporated in a liquid crystal display device.

  In order to achieve the above object, the present invention provides an optical functional layer comprising an optical functional layer and a plurality of laminated films formed by laminating both surfaces of the optical functional layer with a barrier layer, and a plurality of laminated films laminated. A method for producing a laminated film for forming a film having a refractive index larger than the refractive index of the optical functional layer on the side surface is provided.

  According to the method for producing a laminated film of the present invention, after forming a laminated film composed of an optical functional layer and a barrier layer, a plurality of the laminated films are overlapped, and the refractive index of the optical functional layer is determined on the side of the optical functional layer. By forming a film having a large refractive index, a laminated film with improved luminance can be manufactured. Moreover, a film can be formed at a time on the side surfaces of a plurality of laminated films, and the film can be formed efficiently.

  In another embodiment of the present invention, the film is preferably formed by sputtering, vacuum deposition, ion plating, or plasma CVD.

  In this embodiment, a method for forming a film to be formed on the side surface of the optical functional layer is defined. By forming the film by the above method, a plurality of laminated films can be formed at a time.

  According to the laminated film of the present invention and the method for producing the laminated film, the side surface of the optical functional layer has a film having a refractive index larger than the refractive index of the optical functional layer. The luminance can be improved. Further, according to the backlight and the liquid crystal display device including the laminated film, the optical path length can be extended and the luminance can be improved.

It is sectional drawing which shows the structure of a laminated film. It is the schematic of an example of the manufacturing equipment used for formation of an organic layer. It is the schematic of an example of the manufacturing equipment used for formation of an inorganic layer. It is the schematic of an example of the manufacturing equipment used for formation of a laminated | multilayer film. It is the schematic of an example of the manufacturing equipment which forms a film | membrane in the side surface of an optical function layer. It is a figure explaining an example of the backlight unit containing a laminated film. It is a figure explaining an example of a liquid crystal display device.

  Hereinafter, a laminated film according to the present invention, a backlight unit including the laminated film, a liquid crystal display device including the backlight unit, and a method for producing the laminated film will be described with reference to the accompanying drawings. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Laminated film]
The laminated film of the present invention is formed by laminating an optical functional layer and a barrier layer on at least one surface of the optical functional layer, and has a refractive index larger than the refractive index of the optical functional layer on the side surface of the optical functional layer. Has a membrane.

  FIG. 1 is a cross-sectional view showing a configuration of a laminated film. FIG. 1A shows a laminated film 7 in which a barrier layer 6 composed of a support 1, an organic layer 2, and an inorganic layer 3 is provided on both surfaces with an optical functional layer 4 interposed therebetween. FIG. 1B shows a laminated film 8 in which a barrier layer 6 composed of a support 1, an organic layer 2, and an inorganic layer 3 is formed on one surface of the optical functional layer 4.

(Optical function layer)
The optical function layer means a layer such as a wavelength conversion layer, a high refractive index layer, a medium refractive index layer, a low refractive index layer, an antiglare layer, an antiglare antireflection layer, an intermediate layer, or a hard coat layer. In the present embodiment, the optical functional layer is particularly preferably used as a wavelength conversion layer including at least one of quantum dots and quantum rods that are excited by incident excitation light to emit fluorescence.

  When the optical functional layer is used as a wavelength conversion layer, the optical functional layer is formed including a quantum dot or quantum rod, a curable compound, a thixotropic agent, a polymerization initiator, a silane coupling agent, and the like. The optical functional layer mixes these components to prepare an optical functional layer forming coating liquid (hereinafter also referred to as “coating liquid”), and applies the coating liquid to a barrier support (barrier layer) described later, Formed by irradiation.

<Quantum dots and quantum rods>
The quantum dots emit fluorescence by being excited at least by incident excitation light.

  The quantum dots included in the optical functional layer of the present embodiment include at least one kind of quantum dot, and can also include two or more kinds of quantum dots having different emission characteristics. Known quantum dots include quantum dots (A) having an emission center wavelength in the wavelength band of 600 nm to 680 nm, quantum dots (B) having an emission center wavelength in the wavelength band of 500 nm to 600 nm, and 400 nm to 500 nm. There is a quantum dot (C) having a light emission center wavelength in the wavelength band, and the quantum dot (A) is excited by excitation light to emit red light, the quantum dot (B) emits green light, and the quantum dot (C). Emits blue light. For example, when blue light is incident as excitation light on an optical functional layer including quantum dots (A) and quantum dots (B), red light emitted from the quantum dots (A) and light emitted from the quantum dots (B) White light can be realized by green light and blue light transmitted through the optical functional layer. Alternatively, the red light emitted from the quantum dot (A), quantum by making the ultraviolet light incident as the excitation light on the laminated film having the optical functional layer containing the quantum dots (A), (B), and (C) White light can be embodied by green light emitted by the dots (B) and blue light emitted by the quantum dots (C).

  Regarding quantum dots, for example, JP 2012-169271 A paragraphs 0060 to 0066 can be referred to, but are not limited to those described here. As the quantum dots, commercially available products can be used without any limitation. The emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.

  The quantum dots may be added in the form of particles in the coating liquid, or may be added in the form of a dispersion dispersed in a solvent. The addition in the state of a dispersion is preferable from the viewpoint of suppressing the aggregation of the quantum dot particles. The solvent used here is not particularly limited. However, it is preferable that the coating solution does not contain a substantially volatile organic solvent. Therefore, when the quantum dots are added to the coating liquid in the state of dispersion in a solvent, the solvent of the coating liquid is dried before the coating liquid is applied on the barrier support to form the optical functional layer. It is preferable to contain. From the viewpoint of reducing the step of drying the solvent, it is also preferable to add the quantum dots to the coating liquid in the form of particles.

  Note that the volatile organic solvent means a curable compound in the coating solution having a boiling point of 160 ° C. or less and a compound that is not cured by an external stimulus and is liquid at 20 ° C. The boiling point of the volatile organic solvent is 160 ° C. or lower, more preferably 115 ° C. or lower, and most preferably 30 ° C. or higher and 100 ° C. or lower.

  When the coating solution does not contain a substantially volatile organic solvent, the ratio of the volatile organic solvent in the coating solution is preferably 10,000 ppm or less, and more preferably 1000 ppm or less.

  A quantum dot can be added about 0.1-10 mass parts with respect to 100 mass parts of whole quantity of a coating liquid, for example.

  Moreover, it can replace with a quantum dot and can use a quantum rod. Quantum rods are elongated particles and have properties similar to quantum dots. About the addition amount of a quantum rod, the addition method to a coating liquid, etc., it can carry out by the same amount and the same method as a quantum dot. A combination of quantum dots and quantum rods can also be used.

<Curable compound>
As the curable compound used in the present embodiment, those having a polymerizable group can be widely employed. Although the kind of polymeric group is not specifically limited, Preferably, it is a (meth) acrylate group, a vinyl group, or an epoxy group, More preferably, it is a (meth) acrylate group, More preferably, it is an acrylate group. Moreover, as for the polymerizable monomer which has 2 or more polymeric groups, each polymeric group may be the same and may differ.

-(Meth) acrylate-
From the viewpoint of transparency and adhesion of the cured film after curing, (meth) acrylate compounds such as monofunctional or polyfunctional (meth) acrylate monomers, polymers thereof, prepolymers, and the like are preferable. In addition, in this invention and this specification, description with "(meth) acrylate" shall be used by the meaning of at least one of an acrylate and a methacrylate, or either. The same applies to “(meth) acryloyl” and the like.

--2 Functional ones--
Examples of the polymerizable monomer having two polymerizable groups include a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups. Bifunctional polymerizable unsaturated monomers are suitable for reducing the viscosity of the composition. In the present embodiment, (meth) acrylate compounds that are excellent in reactivity and have no problems such as residual catalyst are preferable.

  In particular, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, This includes hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, etc. It is suitably used in the invention.

  The amount of the bifunctional (meth) acrylate monomer used is 5 parts by mass or more from the viewpoint of adjusting the viscosity of the coating liquid to a preferable range with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. Is preferable, and it is more preferable to set it as 10-80 mass parts.

--Three or more functional--
Examples of the polymerizable monomer having three or more polymerizable groups include polyfunctional polymerizable unsaturated monomers having three or more ethylenically unsaturated bond-containing groups. These polyfunctional polymerizable unsaturated monomers are excellent in terms of imparting mechanical strength. In the present embodiment, (meth) acrylate compounds that are excellent in reactivity and have no problems such as residual catalyst are preferable.

  Specifically, ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, EO-modified phosphate triacrylate, tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaeryth Tall hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are suitable.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferably used in the present invention.

  The amount of the polyfunctional (meth) acrylate monomer used is 5 parts by mass or more from the viewpoint of the coating strength of the optical functional layer after curing with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. It is preferable that it is 95 mass parts or less from a viewpoint of gelatinization suppression of a coating liquid.

--Monofunctional--
Monofunctional (meth) acrylate monomers include acrylic acid and methacrylic acid, derivatives thereof, and more specifically, monomers having one polymerizable unsaturated bond ((meth) acryloyl group) of (meth) acrylic acid in the molecule Can be mentioned. Specific examples thereof include the following compounds, but the present embodiment is not limited thereto.

Methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( Alkyl (meth) acrylates having an alkyl group such as meth) acrylate having 1 to 30 carbon atoms; aralkyl (meth) acrylates having an aralkyl group such as benzyl (meth) acrylate having 7 to 20 carbon atoms; butoxyethyl (meta) ) An alkoxyalkyl (meth) acrylate having 2 to 30 carbon atoms of an alkoxyalkyl group such as acrylate; the total carbon number of a (monoalkyl or dialkyl) aminoalkyl group such as N, N-dimethylaminoethyl (meth) acrylate 1-20 Aminoalkyl (meth) acrylates; (meth) acrylates of diethylene glycol ethyl ether, (meth) acrylates of triethylene glycol butyl ether, (meth) acrylates of tetraethylene glycol monomethyl ether, (meth) acrylates of hexaethylene glycol monomethyl ether, octa Monomethyl ether (meth) acrylate of ethylene glycol, monomethyl ether (meth) acrylate of nonaethylene glycol, monomethyl ether (meth) acrylate of dipropylene glycol, monomethyl ether (meth) acrylate of heptapropylene glycol, monoethyl ether of tetraethylene glycol Alkylene chain such as (meth) acrylate has 1 to 10 carbon atoms and terminal alkyl (Meth) acrylate of polyalkylene glycol alkyl ether having 1 to 10 carbon atoms; alkylene chain such as (meth) acrylate of hexaethylene glycol phenyl ether having 1 to 30 carbon atoms and terminal aryl ether having 6 carbon atoms (Meth) acrylate of -20 polyalkylene glycol aryl ethers; alicyclic structures such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and methylene oxide-added cyclodecatriene (meth) acrylate (Meth) acrylate having 4 to 30 carbon atoms in total; fluorinated alkyl (meth) acrylate having 4 to 30 carbon atoms in total such as heptadecafluorodecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono ( (Meth) acrylate, (meth) acrylate having a hydroxyl group such as glycerol mono- or di (meth) acrylate; (meth) acrylate having a glycidyl group such as glycidyl (meth) acrylate; tetraethylene glycol mono (meth) acrylate, hexaethylene Polyethylene glycol mono (meth) having 1 to 30 carbon atoms in the alkylene chain such as glycol mono (meth) acrylate and octapropylene glycol mono (meth) acrylate Acrylate; (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, acryloyl morpholine (meth) acrylamide and the like.

  The amount of the monofunctional (meth) acrylate monomer used is 10 parts by mass or more from the viewpoint of adjusting the viscosity of the coating liquid to a preferable range with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. Is preferable, and it is more preferable to set it as 10-80 mass parts.

-Epoxy compounds, etc.-
Examples of the polymerizable monomer used in the present embodiment include compounds having a cyclic group such as a cyclic ether group capable of ring-opening polymerization such as an epoxy group and an oxetanyl group. More preferable examples of such a compound include compounds having an epoxy group-containing compound (epoxy compound). By using a compound having an epoxy group or an oxetanyl group in combination with a (meth) acrylate compound, the adhesion with the barrier layer tends to be improved.

  Examples of the compound having an epoxy group include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Other examples of the compound having an epoxy group that can be preferably used include, for example, an aliphatic cyclic epoxy compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Glycidyl ethers, polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; higher fatty acid Examples thereof include glycidyl esters.

  Among these components, aliphatic cyclic epoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as compounds having an epoxy group or an oxetanyl group include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, Cyclomer A200, Celoxide 2021P, Celoxide 8000 (above, Daicel Chemical Industries, Ltd.) ), 4-vinylcyclohexene dioxide manufactured by Sigma-Aldrich, Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM -2408, KRM-2490, KRM-2720, KRM-2750 (manufactured by Asahi Denka Kogyo Co., Ltd.). These can be used alone or in combination of two or more.

  The compounds having these epoxy groups and oxetanyl groups are not particularly limited in their production methods. For example, Maruzen KK Publishing Co., Ltd., Fourth Edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. by Alfred Hasfner, The Chemistry OF Heterocyclic compounds, Vol. 30, Bonds, Small Ring Heterocycles part3, Oxiranes, John & Wiley and Sons, An Inc. No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

  As the curable compound used in the present embodiment, a vinyl ether compound may be used.

  A well-known thing can be selected suitably for a vinyl ether compound, For example, the thing of paragraph number 0057 of Unexamined-Japanese-Patent No. 2009-73078 can be employ | adopted preferably.

  These vinyl ether compounds are described in, for example, Stephen. C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, synthesis by reaction of polyhydric alcohol or polyhydric phenol and acetylene, or reaction of polyhydric alcohol or polyhydric phenol and halogenated alkyl vinyl ether. These can be used alone or in combination of two or more.

  For the coating liquid of this embodiment, a silsesquioxane compound having a reactive group described in JP-A-2009-73078 can also be used from the viewpoint of lowering viscosity and increasing hardness.

<Thixotropic agent>
The thixotropic agent is an inorganic compound or an organic compound.

-Inorganic matter-
One preferred embodiment of the thixotropic agent is an inorganic thixotropic agent. For example, an acicular compound, a chain compound, a flat compound, or a layered compound can be preferably used. Of these, a layered compound is preferable.

  There are no particular restrictions on the layered compound, but talc, mica, feldspar, kaolinite (kaolin clay), pyrophyllite (waxite clay), sericite (sericite), bentonite, smectite vermiculites (montmorillonite, beidellite, Nontronite, saponite, etc.), organic bentonite, organic smectite and the like.

  These can be used alone or in combination of two or more. Examples of commercially available layered compounds include, for example, crown clay, Burgess clay # 60, Burgess clay KF, Opti White (manufactured by Shiroishi Kogyo Co., Ltd.), Kaolin JP-100, NN Kaolin clay, ST kaolin. Clay, Hardsil (above, manufactured by Tsuchiya Kaolin Industry Co., Ltd.), ASP-072, Satinton Plus, Translink 37, Hydras Delami NCD (above, manufactured by Angelhard Co., Ltd.), SY Kaolin, OS clay, HA clay MC hard clay (above, manufactured by Maruo Calcium Co., Ltd.), Lucentite SWN, Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN (above manufactured by Coop Chemical Co.), Smecton (produced by Kunimine Industries), Wenger, Wenger FW, S , Sven 74, Organite, Organite T (above, Hojun Co., Ltd.), Hotaka, Olven, 250M, Benton 34, Benton 38 (above, Wilber Ellis), Laponite, Laponite RD, Laponite RDS (Nippon Silica Industry Co., Ltd.). These compounds may be dispersed in a solvent.

In the thixotropic agent added to the coating solution, among the layered inorganic compounds, a silicate compound represented by xM (I) ₂ O.ySiO ₂ (M (II) O, M (III having an oxidation number of 2 or 3) ) ₂ O _{3. Some} of them correspond to ₂ O _3. x and y represent positive numbers), and more preferable compounds are swellable layered clay minerals such as hectorite, bentonite, smectite, and vermiculite.

  Particularly preferably, a layered (clay) compound modified with an organic cation (a cation compound obtained by exchanging an interlayer cation such as sodium of a silicate compound with an organic cation compound) can be suitably used. For example, sodium silicate / magnesium (hectorite) ) In which the sodium ion is exchanged with the following ammonium ion.

  Examples of ammonium ions include monoalkyltrimethylammonium ions having 6 to 18 carbon atoms, dialkyldimethylammonium ions, trialkylmethylammonium ions, and dipolyoxyethylene coconut oil alkyls having 4 to 18 oxyethylene chains. Examples include methylammonium ion, bis (2-hydroxyethyl) coconut oil alkylmethylammonium ion, and polyoxypropylenemethyldiethylammonium ion having an oxopropylene chain of 4 to 25. These ammonium ions can be used alone or in combination of two or more.

  As a method for producing a silicate mineral modified with an organic cation obtained by exchanging sodium ions of sodium silicate / magnesium with ammonium ions, the sodium silicate / magnesium is dispersed in water and sufficiently stirred, and then allowed to stand for 16 hours or more. Adjust the dispersion. While stirring the dispersion, 30% to 200% by mass of a desired ammonium salt is added to sodium magnesium silicate. After the addition, cation exchange occurs, and hectorite containing an ammonium salt between layers becomes insoluble in water and precipitates. Therefore, the precipitate is collected by filtration and dried. During the preparation, heating may be performed in order to accelerate dispersion.

  Examples of commercially available alkylammonium-modified silicate minerals include Lucentite SAN, Lucentite SAN-316, Lucentite STN, Lucentite SEN, and Lucentite SPN (manufactured by Coop Chemical Co., Ltd.) alone or in combination of two or more. Can be used in combination.

  In this embodiment, silica, alumina, silicon nitride, titanium dioxide, calcium carbonate, zinc oxide, or the like can be used as an inorganic thixotropic agent. If necessary, these compounds can be subjected to a treatment for adjusting hydrophilicity or hydrophobicity on the surface.

-Organic matter-
As the thixotropic agent, an organic thixotropic agent can be used.

  Examples of organic thixotropic agents include polyolefin oxide and modified urea.

  The above-mentioned oxidized polyolefin may be prepared in-house or a commercially available product may be used. Examples of commercially available products include Disparon 4200-20 (trade name, manufactured by Enomoto Kasei Co., Ltd.), Flownon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

  The aforementioned modified urea is a reaction product of an isocyanate monomer or an adduct thereof and an organic amine. The above-mentioned modified urea may be prepared in-house or a commercially available product may be used. As a commercial item, BYK410 (made by Big Chemie) etc. are mention | raise | lifted, for example.

-Content-
The content of the thixotropic agent is preferably 0.15 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the curable compound in the coating solution, and 0.2 It is especially preferable that it is -8 mass parts. In particular, in the case of an inorganic thixotropic agent, brittleness tends to be improved when it is 20 parts by mass or less with respect to 100 parts by mass of the curable compound.

<Polymerization initiator>
The coating solution may contain a known polymerization initiator as a polymerization initiator. JP, 2013-043382, A paragraph 0037 can be referred to for a polymerization initiator, for example. The polymerization initiator is preferably 0.1 mol% or more of the total amount of the curable compound contained in the coating solution, and more preferably 0.5 to 2 mol%. Moreover, it is preferable to contain 0.1 mass%-10 mass% as mass% in all the curable compositions except a volatile organic solvent, More preferably, it is 0.2 mass%-8 mass%.

<Silane coupling agent>
An optical functional layer formed from a coating solution containing a silane coupling agent can exhibit excellent light resistance because the silane coupling agent has strong adhesion to an adjacent layer. This is mainly due to the fact that the silane coupling agent contained in the optical functional layer forms a covalent bond with the surface of the adjacent layer and the constituent components of the optical functional layer by a hydrolysis reaction or a condensation reaction. In addition, when the silane coupling agent has a reactive functional group such as a radical polymerizable group, a monomer component constituting the optical functional layer and a crosslinked structure can also be formed, which improves the adhesion between the optical functional layer and the adjacent layer. Can contribute.

  As the silane coupling agent, a known silane coupling agent can be used without any limitation. As a preferable silane coupling agent from the viewpoint of adhesion, a silane coupling agent represented by the following general formula (1) described in JP2013-43382A can be exemplified.

(In General Formula (1), R _{1 to} R ₆ are each independently a substituted or unsubstituted alkyl group or an aryl group, provided that at least one of R _{1 to} R ₆ is a radical polymerizable group. This is a substituent containing a carbon-carbon double bond.)
R _{1 to} R ₆ are each independently a substituted or unsubstituted alkyl group or aryl group. R _{1 to} R ₆ are preferably an unsubstituted alkyl group or an unsubstituted aryl group, except for a case where the R _{1 to} R ₆ are a substituent containing a radically polymerizable carbon-carbon double bond. As an alkyl group, a C1-C6 alkyl group is preferable and a methyl group is more preferable. As the aryl group, a phenyl group is preferable. R _{1 to} R ₆ are particularly preferably a methyl group.

At least one of R ₁ to R _6, the carbon radical polymerizable - having a substituent containing a carbon double bond, two of R ₁ to R ₆ is a radical polymerizable carbon - carbon double bonds A substituent is preferred. Further, among R _{1 to} R ₃ , the number of those having a substituent containing a radical polymerizable carbon-carbon double bond is 1, and among R _{4 to} R ₆ , the radical polymerizable carbon-carbon It is particularly preferred that the number of those having a substituent containing a double bond is 1.

  The substituents in which the silane coupling agent represented by the general formula (1) includes two or more radically polymerizable carbon-carbon double bonds may be the same or different. The same is preferable.

  The substituent containing a radically polymerizable carbon-carbon double bond is preferably represented by -XY. Here, X is a single bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group, and preferably a single bond, a methylene group, an ethylene group, a propylene group, or a phenylene group. Y is a radically polymerizable carbon-carbon double bond group, and is preferably an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a propenyl group, a vinyloxy group, or a vinylsulfonyl group. ) An acryloyloxy group is more preferred.

R _{1 to} R ₆ may have a substituent other than a substituent containing a radical polymerizable carbon-carbon double bond. Examples of the substituent include alkyl groups (for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group). Etc.), aryl groups (eg phenyl group, naphthyl group etc.), halogen atoms (eg fluorine, chlorine, bromine, iodine), acyl groups (eg acetyl group, benzoyl group, formyl group, pivaloyl group etc.), acyloxy Groups (for example, acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl groups (for example, phenyloxycarbonyl group, etc.), sulfonyl groups ( For example, methanesulfonyl group, benzene Honiru group), and the like.

  From the viewpoint of further improving the adhesion with the adjacent layer, the silane coupling agent is preferably contained in the coating liquid in the range of 1 to 30% by mass, more preferably 3 to 30% by mass. More preferably, it is 5 to 25% by mass.

  In the present embodiment, the aforementioned volatile organic solvent can be used in the coating solution. In a preferred embodiment, the coating solution does not contain a substantially volatile organic solvent. As another aspect, a volatile organic solvent can be contained in the coating solution, and for example, it can be contained in an amount of 10% by mass or more and 50% by mass or less, and is contained in an amount of 10% by mass or more and 40% by mass. It is also possible. JP, 2013-105160, A paragraphs 0038-0041 can be referred to for the specific example of the solvent which can be used.

(Barrier layer)
In the laminated film of this embodiment, a barrier layer is laminated on at least one surface of the optical functional layer. The barrier layer may be any known barrier film. Although FIG. 1 shows the barrier layer 6 formed including at least the support 1, the organic layer 2, and the inorganic layer 3, the present invention is not limited to this. The barrier layer 6 may be formed on both surfaces of the optical functional layer 4 as shown in FIG. 1A, or may be formed on either one as shown in FIG. When the barrier layer 6 is formed on both surfaces of the optical functional layer 4, it is preferable that the support 1 of at least one of the barrier layers 6 is a flexible support.

The barrier layer only needs to include at least an inorganic layer, and may include at least one inorganic layer and at least one organic layer on a flexible support. Laminating a plurality of layers in this manner is preferable from the viewpoint of improving light resistance because the barrier property can be further enhanced. On the other hand, as the number of layers to be stacked increases, the light transmittance of the wavelength conversion member tends to decrease. Therefore, it is desirable to increase the number of layers within a range in which good light transmittance can be maintained. Specifically, the barrier layer preferably has a total light transmittance in the visible light region of 80% or more and an oxygen permeability of 1.00 cm ³ / (m ² · day · atm) or less. preferable. The total light transmittance is an average value of light transmittance over the visible light region.

The oxygen permeability of the barrier layer is more preferably 0.1 cm ³ / (m ² · day · atm) or less, particularly preferably 0.01 cm ³ / (m ² · day · atm) or less, and particularly preferably. Is 0.001 cm ³ / (m ² · day · atm) or less. Here, the oxygen permeability is a value measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%. It is. Further, the visible light region means a wavelength band of 380 to 780 nm, and the total light transmittance means an average value of light transmittance excluding contributions of light absorption and reflection of the optical functional layer.

  The total light transmittance in the visible light region is more preferably 90% or more. The lower the oxygen transmittance, the better. The higher the total light transmittance in the visible light region, the better.

-Flexible support-
The barrier layer may have a flexible support for improving strength, easiness of film formation, and the like.

  In FIG. 1, the barrier layer 6 is formed in the order of the inorganic layer 3, the organic layer 2, and the support 1. The barrier layer is not limited to this, and may be formed in the order of the inorganic layer and the support. In addition, a support may be disposed between the organic layer and the inorganic layer, between the two organic layers, or between the two inorganic layers. Furthermore, two or three or more supports may be included in the laminated film.

  The flexible support is preferably a transparent support that is transparent to visible light. Here, “transparent to visible light” means that the linear transmittance in the visible light region is 80% or more, preferably 85% or more. The light transmittance used as a measure of transparency is measured by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device, and diffusing transmission from the total light transmittance. It can be calculated by subtracting the rate. JP, 2007-290369, A paragraphs 0046-0052 and JP, 2005-096108, A paragraphs 0040-0055 can be referred to for a support. The thickness of the support is in the range of 10 to 500 μm, particularly in the range of 15 to 300 μm, particularly in the range of 15 to 120 μm, more particularly in the range of 15 to 100 μm, from the viewpoints of gas barrier properties, impact resistance, etc. Furthermore, it is preferable that it is 25-110 micrometers, and also 25-60 micrometers. A commercially available product may be used as the flexible support, for example, Cosmo Shine A4100 manufactured by Toyobo Co., Ltd., which is a polyethylene terephthalate (PET) film with an easy adhesion layer.

  The support can be used for either or both of the barrier layers. When the barrier layer is included on both sides of the support, it may be the same or different.

-Inorganic layer-
The barrier layer may include an inorganic layer. An inorganic layer is a layer which has an inorganic material as a main component, Preferably it is a layer formed only from an inorganic material.

The inorganic layer is preferably a layer having a gas barrier function of blocking oxygen. Specifically, the oxygen permeability of the inorganic layer is preferably 1.00 cm ³ / (m ² · day · atm) or less. The oxygen permeability coefficient of the inorganic layer can be obtained by attaching a wavelength conversion layer to the detection part of an oxygen meter made by Orbis Fair Laboratories via silicon grease and converting the oxygen permeability coefficient from the equilibrium oxygen concentration value. It is also preferable that the inorganic layer has a function of blocking water vapor.

  Two or more inorganic layers may be contained in the barrier layer.

  The inorganic material constituting the inorganic layer is not particularly limited, and for example, various inorganic compounds such as metals or inorganic oxides, nitrides, oxynitrides, and the like can be used. As an element constituting the inorganic material, silicon, aluminum, magnesium, titanium, tin, indium and cerium are preferable, and one or two or more of these may be included. Specific examples of the inorganic compound include silicon oxide, silicon oxynitride, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, silicon nitride, aluminum nitride, and titanium nitride. As the inorganic layer, a metal film such as an aluminum film, a silver film, a tin film, a chromium film, a nickel film, or a titanium film may be provided.

  Among the above materials, the inorganic layer having the barrier property is particularly preferably an inorganic layer containing at least one compound selected from silicon nitride, silicon oxynitride, silicon oxide, and aluminum oxide. Since the inorganic layer made of these materials has good adhesion to the organic layer, even when the inorganic layer has pinholes, the organic layer can effectively fill the pinholes and suppress breakage. In addition, it is possible to form an extremely excellent inorganic layer film even in a case where an inorganic layer is further laminated, and to further increase the barrier property.

  A method for forming the inorganic layer is not particularly limited, and various film forming methods that can evaporate or scatter the film forming material and deposit it on the deposition surface can be used.

  Examples of the method for forming the inorganic layer include a vacuum evaporation method in which an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced. Oxidation reaction vapor deposition method for oxidizing and vapor-depositing; Sputtering method for vapor deposition by introducing and sputtering argon gas and oxygen gas using an inorganic material as a target raw material; When a vapor deposition film of silicon oxide or silicon nitride is formed by using a physical vapor deposition method (physical vapor deposition method) such as an ion plating method, which is heated by a plasma beam and deposited, an organic silicon compound is used as a raw material. Plasma Chemical Vapor Deposition (Chemical Vapor Deposition) ), And the like. Vapor deposition may be performed on the surface of a support, a substrate film, a wavelength conversion layer, an organic layer, etc. as a substrate.

  The silicon oxide film is preferably formed by using a low temperature plasma chemical vapor deposition method using an organosilicon compound as a raw material. Specific examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propyl. Examples thereof include silane, phenylsilane, vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among the organosilicon compounds, tetramethoxysilane (TMOS) and hexamethyldisiloxane (HMDSO) are preferably used. This is because these are excellent in handleability and vapor deposition film characteristics.

  The thickness of the inorganic layer may be 1 nm to 500 nm, preferably 5 nm to 300 nm, and particularly preferably 10 nm to 150 nm. When the film thickness of the adjacent inorganic layer is within the above-described range, it is possible to suppress the reflection in the inorganic layer while providing good barrier properties, and to provide a laminated film with higher light transmittance. Because it can.

  In the laminated film, it is preferable that at least one inorganic layer adjacent to the optical functional layer is included. It is also preferable that the inorganic layer is in direct contact with both surfaces of the optical functional layer.

-Organic layer-
The organic layer is a layer mainly composed of an organic material, and preferably refers to a layer in which the organic material occupies 50% by mass or more, more preferably 80% by mass or more, and particularly 90% by mass or more.

  JP, 2007-290369, A paragraphs 0020-0042 and JP, 2005-096108, A paragraphs 0074-0105 can be referred to as an organic layer. The organic layer preferably contains a cardo polymer. Thereby, the adhesiveness between the organic layer and the adjacent layer, particularly the adhesiveness with the inorganic layer is improved, and a further excellent gas barrier property can be realized. For details of the cardo polymer, reference can be made to paragraphs 0085 to 0095 of the above-mentioned JP-A-2005-096108. The thickness of the organic layer is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.5 to 10 μm. When the organic layer is formed by a wet coating method, the film thickness of the organic layer is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 1 μm to 5 μm. Moreover, when formed by the dry coating method, it is preferable that it exists in the range of 0.05 micrometer-5 micrometers, especially in the range of 0.05 micrometer-1 micrometer. This is because when the film thickness of the organic layer formed by the wet coating method or the dry coating method is within the above-described range, the adhesion with the inorganic layer can be further improved.

  As for other details of the inorganic layer and the organic layer, reference can be made to the descriptions in JP-A-2007-290369, JP-A-2005-096108, and US2012 / 0113672A1.

[Method for forming barrier layer and optical functional layer]
Next, a method for forming the barrier layer and the optical functional layer in the production of the laminated film will be described. FIG. 2 is a schematic view of an example of manufacturing equipment used for forming the organic layer, and FIG. 3 is a schematic view of an example of manufacturing equipment used for forming the inorganic layer. FIG. 4 is a schematic view of an example of manufacturing equipment used for manufacturing the optical functional layer. 2 to 4 is an example, and each layer can be formed by the method described above.

  In forming the organic layer, as shown in FIG. 2, first, the support 1 is continuously conveyed from the delivery machine 12 to the coating unit 10. In the coating unit 10, an organic layer forming coating solution is applied to the surface of the support 1 that is continuously conveyed to form an organic layer.

  In the coating unit 10, for example, a die coater 14 and a backup roller 16 disposed to face the die coater 14 are installed. The surface of the support 1 opposite to the surface on which the organic layer is formed is wound around the backup roller 16, and the coating liquid for forming the organic layer is applied to the surface of the support 1 that is continuously conveyed from the discharge port of the die coater 14. An organic layer is formed.

  The support 1 coated with the organic layer forming coating solution is conveyed to the drying unit 20. The drying unit 20 includes a drying device 22 and a heating device 24, and dries the organic layer forming coating solution coated on the support 1. The drying device 22 evaporates the solvent contained in the organic layer. The heating device 24 may be used for heating to remove the solvent or to cure the film as necessary.

  The support 1 dried by the drying unit 20 is conveyed to the ultraviolet irradiation unit 30. The ultraviolet irradiation unit 30 includes an ultraviolet irradiation device 32 and irradiates the organic layer forming coating solution with ultraviolet rays by an ultraviolet lamp. The organic layer is formed by crosslinking monomers and the like in the coating solution for forming an organic layer with ultraviolet rays.

  The support 1 on which the organic layer is formed by the ultraviolet irradiation unit 30 has a protective film attached to the organic layer (not shown), and the support 1 is rolled up and collected by the winder 34. In addition, in FIG. 2, although the protective film was affixed on the support body 1 and demonstrated with the apparatus wound up with the winder 34, the protective film is not affixed and the next process (formation of an inorganic layer etc.) is performed as it is. You may go.

  The inorganic layer can be formed by a roll-to-roll vacuum film forming apparatus as shown in FIG. An inorganic film manufacturing apparatus 50 shown in FIG. 3 is an apparatus that forms an inorganic layer on an organic layer.

  The support 1 on which the organic layer 2 is formed and wound by the winder is loaded on the rotating shaft 60 of the support supply chamber 54 as a support roll 52.

  The support supply chamber 54 rotates the rotary shaft 60 counterclockwise in the figure by a driving source (not shown), feeds the support 1 from the support roll 52, and guides a predetermined path by the guide roller 62. 1 is sent to the inorganic film forming chamber 56. While the support 1 is being sent to the inorganic film forming chamber 56, the protective film attached after the organic layer is formed is peeled off. The support supply chamber 54 is a vacuum chamber, and is evacuated to a predetermined pressure (degree of vacuum) by the evacuation means 55. In the inorganic film manufacturing apparatus 50, this prevents the pressure in the support supply chamber 54 from adversely affecting the formation of the inorganic film in the inorganic film forming chamber 56 described later.

  The inorganic film forming chamber 56 includes a drum 66, film forming means 68a, 68b, 68c and 68d, and a vacuum exhaust means 74. In the case where an inorganic film is formed by sputtering, plasma CVD, or the like, a high frequency power source or the like is also installed in the inorganic film forming chamber 56.

  The support transported from the support supply chamber 54 is wound around a predetermined area on the peripheral surface of the drum 66 and is transported through a predetermined transport path while being supported / guided by the drum 66, and film forming means 68a to 68d. Thus, an inorganic layer is formed on the organic layer 2 of the support 1.

  The film forming means 68a to 68d are for forming the inorganic layer 3 on the organic layer 2 of the support 1 by a vacuum film forming method, and are composed of various members according to the vacuum film forming method to be performed. Is done. For example, if the inorganic layer is formed by the CVD method, the film forming means 68a to 68d are configured to include a reaction gas introduction means. Further, if the inorganic layer is formed by sputtering, the film forming means 68a to 68d are configured to include a target holding means, a high frequency electrode, a sputtering gas supply means, and the like.

  The support 1 on which the inorganic layer is formed is then sent to the support take-up chamber 58. The support take-up chamber 58 rotates the rotary shaft 70 in the clockwise direction in the drawing by a driving source (not shown), and takes up the support by the support roll 72. A touch roll 76 is provided on the transport path of the support 1 after the inorganic layer is formed, and a protective film (not shown) is bonded to the touch roll 76. The support take-up chamber 58 is a vacuum chamber, similar to the support supply chamber 54, and is evacuated to a predetermined pressure (degree of vacuum) by the vacuum exhaust means 78, thereby adversely affecting the formation of the inorganic layer. To prevent giving.

  The barrier support 110 in which the organic layer 2 and the inorganic layer 3 are formed on the support 1 as the barrier layer is next formed into an optical functional layer and a barrier layer is formed on the formed optical functional layer. . FIG. 4 is an example of a manufacturing facility 100 for forming an optical functional layer.

  The barrier support 110 (the protective film is peeled off when the protective film is bonded) is continuously conveyed from the unillustrated feeder to the application unit 120. For example, the barrier support 110 is sent out from the feeder at a conveyance speed of 1 to 50 m / min. However, it is not limited to this conveyance speed. When delivered, for example, a tension of 20 to 150 N / m, preferably 30 to 100 N / m, is applied to the barrier support 110.

  In the application part 120, a coating liquid is apply | coated to the surface of the barrier support body 110 conveyed continuously, and a coating film is formed. In the application unit 120, for example, a die coater 124 and a backup roller 126 disposed to face the die coater 124 are installed. The surface of the barrier support 110 opposite to the surface on which the optical functional layer is formed is wound around the backup roller 126, and the coating liquid is applied from the discharge port of the die coater 124 to the surface of the barrier support 110 that is continuously conveyed. A coating film is formed. Here, the coating film refers to a coating solution applied on the barrier support 110 before polymerization.

  In FIG. 4, the die coater 124 to which the extrusion coating method is applied is shown as the coating apparatus. However, the coating device is not limited to this, and various coating methods such as a curtain coating method, an extrusion coating method, a rod coating method, or a roll coating method can be used. A coating apparatus to which the method is applied can be used.

  The barrier support 110 that has passed through the coating unit 120 and has a coating film formed thereon is continuously conveyed to the laminating unit 130. In the laminating unit 130, the barrier support 150 is laminated on the coating film, and the coating film is sandwiched between the barrier support 110 and the barrier support 150. The barrier support 110 and the barrier support 150 may have the same composition and the same configuration, or may be different.

  A backup roller 162 is disposed at a position facing the laminating roller 132. The barrier support 110 on which the coating film is formed is wound around the backup roller 162 on the surface opposite to the coating film forming surface and is continuously conveyed to the laminating position P. Lamination position P means the position where the contact between the barrier support 150 and the coating starts. The barrier support 110 is preferably wound around the backup roller 162 before reaching the laminating position P. This is because even if wrinkles are generated in the barrier support 110, the wrinkles are corrected and removed by the backup roller 162 until they reach the laminate position P. Therefore, it is preferable that the distance L1 between the position (contact position) where the barrier support 110 is wound around the backup roller 162 and the laminate position P is longer, for example, 30 mm or more, and the upper limit value is usually backup. It is determined by the diameter of the roller 162 and the pass line.

  In this embodiment, the barrier support 150 is laminated by the backup roller 162 and the laminating roller 132 used in the polymerization processing unit 160. That is, the backup roller 162 used in the polymerization processing unit 160 is also used as a roller used in the laminating unit 130. However, the present invention is not limited to the above form, and a laminating roller may be installed in the laminating unit 130 in addition to the backup roller 162 so that the backup roller 162 is not used.

  By using the backup roller 162 used in the polymerization processing unit 160 in the laminating unit 130, the number of rollers can be reduced. The backup roller 162 can also be used as a heat roller for the barrier support 110.

  The barrier support 150 delivered from a delivery machine (not shown) is wound around the laminating roller 132 and continuously conveyed between the laminating roller 132 and the backup roller 162. The barrier support 150 is laminated on the coating film formed on the barrier support 110 at the laminating position P. Thereby, the coating film is sandwiched between the barrier support 110 and the barrier support 150. Lamination refers to laminating the barrier support 150 on the coating film.

  The distance between the laminating roller 132 and the backup roller 162 is preferably equal to or greater than the total thickness of the barrier support 110, the optical functional layer obtained by polymerizing and curing the coating film, and the barrier support 150. The distance between the laminating roller 132 and the backup roller 162 is preferably equal to or shorter than the total thickness of the barrier support 110, the coating film, and the barrier support 150 plus 5 mm. By making the distance between the laminating roller 132 and the backup roller 162 equal to or less than the total thickness plus 5 mm, it is possible to prevent bubbles from entering between the barrier support 150 and the coating film. Here, the distance between the laminating roller 132 and the backup roller 162 is the shortest distance between the outer circumferential surface of the laminating roller 132 and the outer circumferential surface of the backup roller 162.

  By attaching a temperature controller to the main body of the backup roller 162, the temperature of the backup roller 162 can be adjusted.

  In the step of laminating the barrier support 150 on the coating film, it is preferable to nip between the linear pressures of 5 to 300 N / cm and bond the barrier support 150 onto the coating film. It is more preferable to nip between 200 N / cm, and it is particularly preferable to nip between linear pressures of 30 to 100 N / cm. Moreover, there is no restriction | limiting in the bonding method, The bonding method which does not use a nip roll may be used.

  Further, in order to suppress thermal deformation after the coating film is sandwiched between the barrier support 110 and the barrier support 150, the difference between the temperature of the backup roller 162 of the polymerization processing unit 160 and the temperature of the barrier support 110, and the backup The difference between the temperature of the roller 162 and the temperature of the barrier support 150 is preferably 30 ° C. or less, more preferably 15 ° C. or less, and most preferably the same.

  In order to reduce the difference from the temperature of the backup roller 162, when the heating chamber 134 is provided, it is preferable to heat the barrier support 110 and the barrier support 150 in the heating chamber 134. For example, hot air is supplied to the heating chamber 134 by a hot air generator (not shown), and the barrier support 110 and the barrier support 150 can be heated.

  The barrier support 110 may be heated by the backup roller 162 by being wound around the temperature-adjusted backup roller 162.

  On the other hand, the barrier support 150 can be heated by the laminating roller 132 by using the laminating roller 132 as a heat roller. However, the heating chamber 134 and the heat roller are not essential, and can be provided as necessary.

  Note that FIG. 4 illustrates the case where the optical functional layer (coating film) is sandwiched between the barrier support 110 and the barrier support 150 and the barrier layer is provided on both surfaces. When only the surface is a barrier layer, the barrier support 150 can be another film or support.

  After forming a coating film on the barrier support 110 and laminating the barrier support 150, the coating film is polymerized and cured by light irradiation to obtain an optical functional layer. Curing conditions can be appropriately set according to the type of curable compound to be used and the composition of the coating solution. Moreover, when a solvent is contained in the coating solution, a drying treatment for removing the solvent may be performed before the polymerization treatment. Polymerization treatment of the coating film is performed in a state where the coating film is sandwiched between two barrier supports.

  In the apparatus illustrated in FIG. 4, the barrier support 110 is conveyed to the polymerization processing unit 160 in a state where a coating film is formed and the barrier support 150 is laminated. The polymerization processing unit 160 includes a backup roller 162 and a light irradiation device 164 at a position facing the backup roller 162. Between the backup roller 162 and the light irradiation device 164, the barrier support 110 and the barrier support 150 sandwiching the coating film are continuously conveyed.

What is necessary is just to determine the light irradiated by the light irradiation apparatus 164 according to the kind of curable compound contained in a coating liquid, and an ultraviolet-ray is mentioned as an example. As a light source that generates ultraviolet rays, for example, 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, an LED, a laser, or the like can be used. What is necessary is just to set the light irradiation amount to the range which can advance polymerization hardening of a coating film, for example, can irradiate the coating film with the ultraviolet-ray of the irradiation amount of 10-10000 mJ / cm < ² > as an example. Light irradiation amount to the coating may be a 10 to 10000 mJ / cm ² as an example, it is preferable to 10~1000mJ / cm ^2, and more preferably set to 50 to 800 mJ / cm ^2.

  In the polymerization processing section 160, the barrier support 110 and the barrier support 150 sandwich the coating film, the barrier support 110 is wound around the backup roller 162, and light is irradiated from the light irradiation device 164 while continuously transporting. The optical functional layer can be formed by curing the coating film.

  In the present embodiment, the barrier support 110 side is wound around the backup roller 162 and continuously conveyed, but the barrier support 150 may be wound around the backup roller 162 and continuously conveyed.

  Wrapping around the backup roller 162 means a state in which one of the barrier support 110 and the barrier support 150 is in contact with the surface of the backup roller 162 at a certain wrap angle. Therefore, the barrier support 110 and the barrier support 150 move in synchronization with the rotation of the backup roller 162 during continuous conveyance. The winding around the backup roller 162 may be performed at least while light is irradiated.

  The temperature of the backup roller 162 is determined in consideration of heat generation during light irradiation, curing efficiency of the coating film, and occurrence of wrinkle deformation on the backup roller 162 of the barrier support 110 and the barrier support 150. be able to. For example, the backup roller 162 is preferably set to a temperature range of 10 to 95 ° C, and more preferably 15 to 85 ° C. Here, the temperature related to the roller refers to the surface temperature of the roller.

  The distance between the laminate position P and the light irradiation device 164 can be set to 30 mm or more, for example.

  By sandwiching between the barrier support 110 and the barrier support 150 and curing the coating film by light irradiation to form an optical functional layer, a laminated film 170 including a barrier layer on both sides is manufactured. The laminated film 170 is peeled off from the backup roller 162 by the peeling roller 180. The laminated film 170 is continuously conveyed to a winder (not shown) and wound into a roll.

  In addition, in FIG. 4, although demonstrated by the method of performing a polymerization process by light irradiation, when the sclerosing | hardenable compound contained in a coating liquid is what superposes | polymerizes by heating, a polymerization process is performed by heating, such as blowing of warm air. It can be carried out. Moreover, the bonding method of the barrier support body 110 and the barrier support body 150 can use the bonding method by which the clearance gap was provided between the bonding method by a nip roller other than what was mentioned above.

(Film having a refractive index larger than that of the optical functional layer)
The laminated film of the present embodiment further includes a film 5 having a refractive index larger than the refractive index of the optical functional layer on the side surface of the optical functional layer (FIG. 1). Hereinafter, the film 5 having a refractive index larger than the refractive index of the optical functional layer and a method for forming the film will be described.

The film 5 having a refractive index larger than that of the optical function layer is preferably an inorganic film. By forming it with an inorganic film, the film 5 can be provided with a gas barrier property. As the gas barrier property, the oxygen permeability is preferably 1.00 cm ³ / (m ² · day · atm) or less, more preferably 0.1 cm ³ / (m ² · m, as in the barrier layer described above. day · atm) or less, more preferably 0.1 cm ³ / (m ² · day · atm) or less, and particularly preferably 0.001 cm ³ / (m ² · day · atm) or less.

  The material constituting the inorganic film having a refractive index larger than that of the optical functional layer is one or more selected from silicon, aluminum, indium, tin, zinc, titanium, chromium, nickel, copper, silver and gold. It is preferable to include at least one of metal oxide, nitride, and oxynitride.

  The film 5 having a refractive index larger than the refractive index of the optical functional layer is preferably a laminated film in which the laminated structure of the first metal layer and the metal oxide layer is repeated one or more times. The material for forming the first metal layer is preferably one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper, and silver. The material for forming the metal oxide layer is preferably an oxide of one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper and silver.

  Furthermore, it is preferable to have the second metal layer on the laminated film, that is, on the metal oxide layer. The material forming the second metal layer is preferably one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper, and silver. The metals constituting the first metal layer, the metal oxide layer, and the second metal layer may be the same metal or different from each other, but the same metal is preferably used.

  As a method of forming the film 5 having a refractive index larger than that of the optical functional layer, it can be formed by sputtering, vacuum deposition, ion plating, or plasma CVD. By forming by these methods, a plurality of films can be overlapped and the film 5 can be provided on the side surface of the optical functional layer, so that the film can be efficiently formed on the side surface of the optical functional layer. Specifically, as described above, after the laminated film 170 formed by laminating the barrier layer on the optical functional layer is formed, the laminated film 170 is cut into a predetermined size, and a plurality of sheets are overlapped. Moreover, a protective film is laminated | stacked on the upper surface of the laminated | multilayer film laminated several sheets. And the film | membrane 5 can be efficiently formed in the side surface of an optical functional layer by putting in the apparatus which forms the laminated | stacked laminated film in the said method, and forming into a film. As an apparatus for forming the film 5, for example, a sputtering apparatus shown in FIG. 5 can be used.

  The thickness of the film 5 is preferably 5 to 500 nm, more preferably 10 to 200 nm, still more preferably 15 to 100 nm, and preferably 20 to 50 nm. By setting the thickness of the film 5 within the above range, water vapor and oxygen can be prevented from entering the laminated film, and the function can be maintained for a long time.

  Further, when the film 5 is a laminated film composed of the first metal layer and the metal oxide layer, the thickness of the first metal layer is preferably 5 nm or more and 50 nm or less, and the thickness of the metal oxide layer is 0.1 nm or more. It is preferable that it is 5 nm or less. Furthermore, when it has a 2nd metal layer, it is preferable that the thickness of a 2nd metal layer is 10 to 200 nm.

  The refractive index of the film 5 is preferably 1.5 or more. Further, the refractive index of the optical functional layer 4 needs to be equal to that of the protective resin (ligand) of the quantum dots contained in the optical functional layer 4, and is preferably in the range of 1.3 to 1.6. The difference between the refractive index of the optical functional layer 4 and the refractive index of the film 5 is preferably 0.2 or more, more preferably 0.4 or more. By making the difference between the refractive index of the optical functional layer 4 and the refractive index of the film 5 within this range, light can be reflected from the side surface of the laminated film, so that the optical path length inside the laminated film can be extended, Brightness can be improved. The upper limit of the refractive index of the film 5 is not particularly limited, but is preferably 3.0 or less in view of the material constituting the film 5. Similarly, the upper limit of the difference between the refractive index of the optical function layer 4 and the refractive index of the film 5 is not particularly limited, but is preferably 1.5 or less.

The refractive index can be adjusted by adjusting the amount of oxygen introduced when a film is formed by vacuum film formation. For example, the refractive index can be increased to 1.6 to 1.7 by reducing the amount of oxygen introduced and increasing the ratio of SiO in the film with respect to the refractive index of SiO ₂ of 1.5.

[Method for depositing film having refractive index higher than that of optical functional layer]
FIG. 5 is an example of an apparatus for forming a film 5 having a refractive index higher than that of the optical functional layer on the side surface of the optical functional layer. FIG. 5 is a diagram illustrating a film formation by a sputtering method.

  As shown in FIG. 5, the sputtering apparatus 200 is generally configured by a vacuum vessel 210 provided therein with a holder 211 that holds a laminated film and a plasma electrode (cathode electrode) 212 that generates plasma.

  In order to form a film on the side surface of the laminated film 170 formed in FIG. 4 by a sputtering method, the laminated film 170 wound by a winder is cut into a predetermined shape and size. The predetermined shape and size are sizes that can enter the sputtering apparatus, and can be determined depending on the use of the laminated film.

  Moreover, it is preferable that a laminated film forms a film | membrane on a side surface by overlapping a some laminated film. By forming a film by superimposing a plurality of laminated films, the entire processing time can be shortened when processed into a laminated film having a plurality of films. In consideration of productivity, it is preferable that the number of the laminated films to be laminated when forming the film 5 on the side surface of the optical functional layer is larger. The maximum number of sheets depends on the thickness of the film, the coating width of the film, the size of the vacuum chamber and the film, the fixing jig, and the gripping force. Considering general processes including handling, when the film thickness is 150 μm, about 100 to 3000 sheets are preferable. In addition, the protective film 216 is laminated | stacked on the upper surface of a laminated film in order to protect from film formation.

  The holder 211 and the plasma electrode 212 are spaced apart so as to face each other, and the target T is mounted on the plasma electrode 212. The plasma electrode 212 is connected to an RF (Radio Frequency) power source 213.

A gas introduction pipe 214 for introducing a gas G necessary for film formation into the vacuum container 210 and a gas discharge pipe 215 for exhausting the gas V in the vacuum container 210 are attached to the vacuum container 210. As the gas G, Ar, Ar / O ₂ mixed gas, or Ar / N ₂ mixed gas can be used. The target T is selected from silicon, aluminum, indium, tin, zinc, titanium, chromium, nickel, copper, silver and gold. By using at least one of oxygen or nitrogen as a reaction gas, oxide, nitridation A film can be formed as an oxide or oxynitride.

  In the case of forming a laminated film on the side surface of the laminated film 170, a first film made of at least one metal selected from aluminum, titanium, chromium, nickel, tin, copper, and silver is formed on the side surface of the cut laminated film 170 by a sputtering method. 1 metal layer is formed. Next, oxygen is introduced as a reaction gas, and a metal oxide layer is formed on the first metal layer by a sputtering method. By changing whether or not oxygen is introduced, the first metal layer and the metal oxide layer are repeatedly formed. In the case of having the second metal layer, after forming the metal oxide layer, the gas G (reactive gas) is Ar and the second metal layer is formed. By laminating the metal oxide layer on the first metal layer, pinholes and cracks in the first metal layer can be filled, and light can be prevented from leaking from the end face of the film. Moreover, a mirror surface can be obtained with the second metal layer by forming the second metal layer on the metal oxide layer. Therefore, since the light leaking from the end face of the laminated film can be reused with high reflectivity on the mirror surface of the second metal layer, when used as a wavelength conversion member, a wavelength conversion member with high luminance can be used.

[Wavelength conversion member]
The laminated film of this embodiment can be used as a wavelength conversion member by including either one of quantum dots or quantum rods, and can be used by being incorporated in a liquid crystal display device or the like.

  The laminated film including at least one of quantum dots and quantum rods (hereinafter also referred to as “quantum dots”) used as a wavelength conversion member has a wavelength including quantum dots that are excited by incident excitation light and emit fluorescence. It has a conversion layer.

  The wavelength conversion layer in the wavelength conversion member usually contains quantum dots or the like in an organic matrix. The organic matrix is usually a polymer obtained by polymerizing a curable compound by light irradiation or the like.

  The film thickness of the wavelength conversion layer is preferably in the range of 1 to 500 μm, more preferably in the range of 10 to 250 μm, and particularly preferably in the range of 30 to 150 μm. When the wavelength conversion layer is formed from a plurality of layers, the thickness of one layer is preferably in the range of 1 to 300 μm, more preferably in the range of 10 to 250 μm.

[Backlight unit]
The backlight unit according to one embodiment of the present invention includes at least the laminated film of the present invention and a light source. The laminated film is preferably included as a constituent member of the backlight unit of the liquid crystal display device.

  FIG. 6 is an explanatory diagram of an example of a backlight unit 300 including a laminated film according to one embodiment of the present invention. In FIG. 6, the backlight unit 300 includes a light source 300A and a light guide plate 300B for use as a surface light source. In the example shown in FIG. 6A, the laminated film as the wavelength conversion member is disposed on the path of light emitted from the light guide plate. On the other hand, in the example shown in FIG. 6B, the laminated film as the wavelength conversion member is disposed between the light guide plate and the light source.

  In the example shown in FIG. 6A, the light emitted from the light guide plate 300B enters the wavelength conversion member 300C. In the example shown in FIG. 6A, the light 310 emitted from the light source 300A arranged at the edge portion of the light guide plate 300B is blue light, and the liquid crystal is applied from the surface on the liquid crystal cell (not shown) side of the light guide plate 300B. It is emitted toward the cell. The wavelength conversion member 300C disposed on the path of the light (blue light 310) emitted from the light guide plate 300B has the quantum dots (A) that are excited by the blue light 310 and emit the red light 330, and the blue light 310. It includes at least quantum dots (B) that are excited to emit green light 320 (the quantum dots (B) are indicated by reference numeral 321 in the figure). In this way, the backlight unit 300 emits green light 320 and red light 330 excited and emitted, and blue light 310 transmitted through the quantum dot wavelength conversion member 300C. By emitting RGB bright line light in this way, white light can be realized.

  In the present embodiment, a film having a refractive index larger than the refractive index of the optical functional layer is provided on the side surface in the left-right direction of the wavelength conversion member 300C in FIG. The effect of the present invention will be described with a quantum dot (B) 321. The light emitted from the light guide plate 300 </ b> B emits green light 320 by the quantum dots (B) 321. However, among the green light excited by the quantum dots (B) 321, the light emitted obliquely is reflected at the interface of the wavelength conversion member 300C and reaches the end face. Conventionally, since no film is formed on the end face, the light reaching the end face may leak from the end face of the wavelength conversion member 300C. However, in this embodiment, the end face has a film and is reflected. Therefore, the luminance can be improved.

  The example shown in FIG. 6B is the same as the embodiment shown in FIG. 6A except that the arrangement of the light conversion member and the light guide plate is different. In the example shown in FIG. 6B, the excited green light 320 and red light 330, and the blue light 310 transmitted through the wavelength conversion member 300C are emitted from the wavelength conversion member 300C and incident on the light guide plate. Realized.

<Light emission wavelength of backlight unit>
From the viewpoint of realizing high luminance and high color reproducibility, it is preferable to use a backlight unit that has been converted to a multi-wavelength light source. As a preferred embodiment, blue light having an emission center wavelength in a wavelength band of 430 to 480 nm, a peak of emission intensity having a half width of 100 nm or less, and an emission center wavelength in a wavelength band of 500 to 600 nm. Green light having an emission intensity peak with a half width of 100 nm or less, and red light having an emission center wavelength in a wavelength band of 600 to 680 nm and having an emission intensity peak with a half width of 100 nm or less. A backlight unit that emits light can be given.

  From the viewpoint of further improving luminance and color reproducibility, the wavelength band of the blue light emitted from the backlight unit is preferably 450 to 480 nm, and more preferably 460 to 470 nm.

  From the same viewpoint, the wavelength band of the green light emitted from the backlight unit is preferably 520 to 550 nm, and more preferably 530 to 540 nm.

  From the same viewpoint, the wavelength band of red light emitted from the backlight unit is preferably 610 to 680 nm, and more preferably 620 to 640 nm.

  From the same viewpoint, the half-value widths of the emission intensity of blue light, green light, and red light emitted from the backlight unit are all preferably 80 nm or less, more preferably 50 nm or less, and 45 nm or less. It is more preferable that it is 40 nm or less. Among these, it is particularly preferable that the half-value width of each emission intensity of blue light is 30 nm or less.

  The backlight unit includes a light source together with at least the wavelength conversion member. In one embodiment, a light source that emits blue light having an emission center wavelength in a wavelength band of 430 nm to 480 nm, for example, a blue light emitting diode that emits blue light can be used. When using a light source that emits blue light, the quantum dot-containing laminate includes at least quantum dots (A) that are excited by excitation light and emit red light, and quantum dots (B) that emit green light. It is preferable. Thereby, white light can be embodied by blue light emitted from the light source and transmitted through the quantum dot-containing laminate, and red light and green light emitted from the wavelength conversion member.

  Alternatively, in another aspect, a light source that emits ultraviolet light having an emission center wavelength in a wavelength band of 300 nm to 430 nm, for example, an ultraviolet light emitting diode can be used. In this case, it is preferable that the wavelength conversion layer includes quantum dots (A) and (B) and quantum dots (C) that are excited by excitation light and emit blue light. Thereby, white light can be embodied by red light, green light, and blue light emitted from the quantum dot-containing laminate.

  In another aspect, two types of light sources selected from the group consisting of a blue laser that emits blue light, a green laser that emits green light, and a red laser that emits red light are used. By having quantum dots that emit fluorescence having different emission wavelengths in the quantum dot-containing laminate, two types of light emitted from the light source and light emitted from the quantum dots of the quantum dot-containing laminate, White light can also be embodied.

<Scattering particles>
The wavelength conversion member can have a light scattering function in order to efficiently extract the fluorescence of the quantum dots to the outside. The light scattering function may be provided inside the wavelength conversion layer, or a layer having a light scattering function may be separately provided as the light scattering layer.

  As one aspect, it is also preferable to add scattering particles inside the wavelength conversion layer.

  As another aspect, it is also preferable to provide a light scattering layer on the surface of the wavelength conversion layer. Scattering in the light scattering layer may depend on scattering particles or surface irregularities.

<Configuration of backlight unit>
The configuration of the backlight unit may be an edge light system using a light guide plate, a reflection plate, or the like as a constituent member. Although FIG. 6 illustrates an example of an edge light type backlight unit, the backlight unit according to one embodiment of the present invention may be a direct type. Any known light guide plate can be used without any limitation.

  The backlight unit can also include a reflecting member at the rear of the light source. There is no restriction | limiting in particular as such a reflecting member, A well-known thing can be used, and it is described in patent 3416302, patent 3363565, patent 4091978, patent 3448626, etc., The content of these gazettes is this Incorporated into the invention.

  It is also preferable that the backlight unit has a blue wavelength selection filter that selectively transmits light having a wavelength shorter than 460 nm of blue light.

  It is also preferable that the backlight unit has a red wavelength selection filter that selectively transmits light having a wavelength longer than 630 nm out of red light.

  There is no restriction | limiting in particular as such a blue wavelength selection filter or a red wavelength selection filter, A well-known thing can be used. Such a filter is described in Japanese Patent Application Laid-Open No. 2008-52067, etc., and the content of this publication is incorporated in the present invention.

  In addition, the backlight unit preferably includes a known diffusion plate, diffusion sheet, prism sheet (for example, BEF series manufactured by Sumitomo 3M Limited), and a light guide. Other members are also described in Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated in the present invention.

[Liquid Crystal Display]
A liquid crystal display device according to one embodiment of the present invention includes at least the backlight unit of the present invention and a liquid crystal cell.

<Configuration of liquid crystal display device>
The driving mode of the liquid crystal cell is not particularly limited, and twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB) Various modes such as can be used. The liquid crystal cell is preferably VA mode, OCB mode, IPS mode, or TN mode, but is not limited thereto. As an example of the configuration of the VA mode liquid crystal display device, the configuration shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2008-262161 is given as an example. However, the specific configuration of the liquid crystal display device is not particularly limited, and a known configuration can be adopted.

  In one embodiment of the liquid crystal display device, a liquid crystal cell having a liquid crystal layer sandwiched between substrates provided with electrodes on at least one of the opposite sides is provided, and the liquid crystal cell is arranged between two polarizing plates. The liquid crystal display device includes a liquid crystal cell in which liquid crystal is sealed between upper and lower substrates, and displays an image by changing the alignment state of the liquid crystal by applying a voltage. Furthermore, it has an accompanying functional layer such as a polarizing plate protective film, an optical compensation member that performs optical compensation, and an adhesive layer as necessary. In addition to (or instead of) color filter substrates, thin layer transistor substrates, lens films, diffusion sheets, hard coat layers, antireflection layers, low reflection layers, antiglare layers, etc., forward scattering layers, primer layers, antistatic layers Further, a surface layer such as an undercoat layer may be disposed.

  FIG. 7 illustrates an example of a liquid crystal display device according to one embodiment of the present invention. A liquid crystal display device 351 illustrated in FIG. 7 includes a backlight-side polarizing plate 364 on the backlight-side surface of the liquid crystal cell 371. The backlight side polarizing plate 364 may or may not include the polarizing plate protective film 361 on the surface on the backlight side of the backlight side polarizer 362, but it is preferable to include it.

  The backlight side polarizing plate 364 preferably has a configuration in which a backlight side polarizer 362 is sandwiched between two polarizing plate protective films 361 and 363.

  In this specification, the polarizing plate protective film on the side closer to the liquid crystal cell with respect to the polarizer is referred to as the inner side polarizing plate protective film, and the polarizing plate protective film on the side farther from the liquid crystal cell with respect to the polarizer is referred to as the outer side polarizing plate. It is called a protective film. In the example shown in FIG. 7, the polarizing plate protective film 363 is an inner side polarizing plate protective film, and the polarizing plate protective film 361 is an outer side polarizing plate protective film.

  The backlight side polarizing plate may have a retardation film as an inner side polarizing plate protective film on the liquid crystal cell side. As such a retardation film, a known cellulose acylate film or the like can be used.

  The liquid crystal display device 351 has a display-side polarizing plate 394 on the surface of the liquid crystal cell 371 opposite to the surface on the backlight side. The display side polarizing plate 394 has a configuration in which a display side polarizer 392 is sandwiched between two polarizing plate protective films 391 and 393. The polarizing plate protective film 393 is an inner side polarizing plate protective film, and the polarizing plate protective film 391 is an outer side polarizing plate protective film.

  The backlight unit 300 included in the liquid crystal display device 351 is as described above.

  There is no particular limitation on the liquid crystal cell, the polarizing plate, the polarizing plate protective film, and the like constituting the liquid crystal display device according to one embodiment of the present invention, and those prepared by known methods and commercially available products can be used without any limitation. it can. It is of course possible to provide a known intermediate layer such as an adhesive layer between the layers.

(Color filter)
Various known methods can be used as the RGB pixel forming method of the color filter substrate. For example, a desired black matrix and R, G, and B pixel patterns can be formed on a glass substrate by using a photomask and a photoresist, and colored inks for R, G, and B pixels can be used. Using a black matrix having a predetermined width and an area (a concave portion surrounded by convex portions) divided by a black matrix wider than the width of the black matrix every n pieces, using an inkjet printer It is also possible to produce a color filter composed of R, G, and B patterns by discharging the ink composition until the density reaches a predetermined density. After image coloring, each pixel and the black matrix may be completely cured by baking or the like.

  Preferred characteristics of the color filter are described in Japanese Patent Application Laid-Open No. 2008-083611 and the like, and the content of this publication is incorporated in the present invention.

  As the color filter pigment, known pigments can be used without any limitation. Currently, pigments are generally used. However, color filters using dyes may be used as long as they are pigments that can control spectroscopy and ensure process stability and reliability.

(Black matrix)
In the liquid crystal display device, it is preferable that a black matrix is disposed between the pixels. Examples of the material for forming the black stripe include a material using a sputtered film of a metal such as chromium, and a light-shielding photosensitive composition in which a photosensitive resin and a black colorant are combined. Specific examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like. Among these, carbon black is preferable.

(Thin layer transistor)
The liquid crystal display device can further include a TFT substrate having a thin layer transistor (hereinafter also referred to as TFT). The thin film transistor preferably includes an oxide semiconductor layer having a carrier concentration of less than 1 × 10 ¹⁴ / cm ³ . A preferred embodiment of the thin layer transistor is described in Japanese Patent Application Laid-Open No. 2011-141522, and the content of this publication is incorporated in the present invention.

  Since the liquid crystal display device according to one embodiment of the present invention described above includes a backlight unit including a quantum dot-containing stacked body that can exhibit high light transmittance, high luminance and high color reproducibility can be realized. Is.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to this example, and materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. it can.

[Creation of laminated film]
<Support>
A polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300, thickness 50 μm, width 1000 mm, length 100 m) was used.

<Formation of organic layer>
An organic layer was formed on the support. First, the organic layer forming coating solution was adjusted. As the organic layer forming coating solution, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator (Lamberti Co., ESACUREKTO46) are prepared, and the weight ratio of TMPTA: photopolymerization initiator is 95. : Weighed to 5 and dissolved them in methyl ethyl ketone to give a solid content concentration of 15%.

This organic layer forming coating solution was applied to a PET film as a support by roll-to-roll using a die coater. The coated PET film was passed through a drying zone at 50 ° C. for 3 minutes, and then irradiated with ultraviolet rays (integrated irradiation amount: about 600 mJ / cm ² ), and cured by UV curing. A polyethylene film (PE film, manufactured by Sanei Kaken Co., Ltd., trade name: PAC2-30-T) as a protective film was attached to a pass roll immediately after UV curing, conveyed, and wound. The organic layer formed on the support had a thickness of 1 μm.

<Formation of inorganic layer>
Next, an inorganic layer (silicon nitride (SiN) layer) was formed on the surface of the organic layer using a roll-to-roll CVD apparatus. The support was sent out from the feeder, and the protective film was peeled off after passing through the final film surface touch roll before forming the inorganic layer, and an inorganic layer was formed on the exposed organic layer. In forming the inorganic layer, silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases. As a power source, a SiN layer was formed using a high frequency power source having a frequency of 13.56 MHz. The film formation pressure was 40 Pa, and the ultimate film thickness was 50 nm.

  In this way, an inorganic layer was formed on the organic layer, and a protective PE film was attached to the formed film surface touch roll part, and the inorganic film was transported without touching the pass roll, and then wound.

<Formation of optical functional layer>
The protective PE film of the barrier support (barrier layer) composed of the support, the organic film and the inorganic film formed as described above was peeled off, and the coating solution was formed on the inorganic layer by applying the coating solution for forming the optical functional layer. . The coating solution for forming the optical functional layer was adjusted to have the following composition. The coating film of the optical functional layer was sandwiched between barrier supports formed by the same method as described above, and UV-cured to form a composite film by roll-to-roll.

(Composition of coating solution for forming optical functional layer)
-Toluene dispersion of quantum dots 1 (luminescence maximum: 520 nm) 10 parts by mass-Toluene dispersion of quantum dots 2 (luminescence maximum: 630 nm) 1 part by weight-Lauryl methacrylate 2.4 parts by weight-Trimethylolpropane triacrylate 0. 54 parts by mass / photopolymerization initiator 0.009 parts by mass (Irgacure 819 (manufactured by Ciba Specialty Chemicals))
As the quantum dots 1 and 2, nanocrystals having the following core-shell structure (InP / ZnS) were used.

Quantum dot 1: INP530-10 (manufactured by NN-labs)
Quantum dot 2: INP620-10 (manufactured by NN-labs)
The viscosity of the coating solution for forming an optical functional layer was 50 mPa · s.

<Sheet processing>
The formed composite film was punched out into an A4 size sheet using a Thomson blade having a blade edge angle of 17 °.

<End face treatment>
1000 sheets of composite films cut into a sheet were stacked, and an inorganic layer was formed on the side surface of the composite film laminate using a sputtering apparatus. Silicon was used as a target, argon was used as a discharge gas, and oxygen was used as a reaction gas. The film formation pressure was 0.1 Pa, and the ultimate film thickness was 50 nm (Example 1).

  Further, the amount of oxygen introduced into the reaction gas was reduced, and the side film was made of SiO (Example 2). Alumina was used as a target, and the thickness of the side film was changed to create a laminated film (Examples 3 to 6). A side film was formed using titanium as a target (Example 7).

  Moreover, the laminated film was formed in the side surface of the laminated film as follows. The same procedure as in Example 1 was performed until the formed composite film was set in the sputtering apparatus. Aluminum was used as the target, argon was used as the discharge gas, the film forming pressure was 0.5 Pa, and an aluminum layer having a thickness of 20 nm was formed as the first metal layer. Subsequently, oxygen was introduced as a reaction gas, and a 1 nm-thick aluminum oxide metal oxide layer was formed on the first metal layer. The formation of the aluminum layer and the aluminum oxide layer was repeated 5 times to form a laminated film having a total film thickness of 105 nm (Example 8). On the laminated film of Example 8, an aluminum layer having a thickness of 200 nm was formed as the second metal layer by the same method as the formation of the first metal layer of Example 8 (Example 9). The total film thickness was 305 nm.

  The results are shown in Table 1. In addition, evaluation of Table 1 was performed with the following method and reference | standard. In addition, as Comparative Example 1, a film that does not form a film on the side surface of the film of Example 1 was also evaluated.

<Refractive index and film thickness measurement>
Otsuka Electronics Co., Ltd. Measurement was performed using a spectroscopic ellipsometer FE-5000.

<Brightness measurement>
It was mounted on Kindle fire HDX 7in and the luminance was judged visually.

  A comparative example having no film on the side face was evaluated as D: reference, C: luminance slightly improved, B: luminance improved, and A: luminance significantly improved.

  The luminance half time was mounted on Kindle fire HDX 7in after a predetermined time in an environment of temperature 60 and humidity 90%, and the time when the luminance was reduced by half from the initial stage was confirmed.

<Bending>
Winding around a φ100 mm cylinder was repeated 100 times, and it was confirmed whether cracks occurred at the end of the laminated film. The confirmation of the crack was confirmed using an optical microscope at a magnification of 400 times and evaluated according to the following criteria.
AA: The surface is a mirror surface visually. A: No crack at the end is observed. B: A partial crack is observed. C: A crack is confirmed throughout.

  As shown in Table 1, compared with Comparative Example 1 in which no film is formed on the side surface of the optical functional layer, Examples 1 to 4 in which the film is formed have improved brightness, and the refractive index of the side film is increased. By doing so, the luminance could be improved. In addition, by increasing the thickness of the side film, it was possible to extend the luminance half-life. However, as the film thickness increases, cracks occur at the end in bending evaluation, so the film thickness is 20 nm to 50 nm. It is preferable that

  In Examples 1 to 4 in which the film was formed with a film thickness of 20 nm to 200 nm, the luminance half time was extended, and it was confirmed that the function could be maintained for a long time. Further, it was confirmed that the surface brightness was improved as compared with Comparative Example 1. A thicker film is preferable from the viewpoint of luminance half-life time and surface luminance. However, if the film is thick, film cracking occurs. Therefore, the thickness is preferably 20 nm or more and 100 nm or less.

  Further, from Example 8, it was confirmed that a favorable result was obtained by bending evaluation by forming the side film as a laminated film of the first metal layer and the metal oxide layer, and a high strength film could be formed. Furthermore, from Example 9, the luminance could be improved by forming the second metal layer.

  DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Organic layer, 3 ... Inorganic layer, 4 ... Optical functional layer, 5 ... Film, 6 ... Barrier layer, 7, 8 ... Laminated film, 10 ... Coating part, 12 ... Delivery machine, 14 ... Daiko 16 ... backup roller, 20 ... drying section, 22 ... drying apparatus, 24 ... heating apparatus, 30 ... ultraviolet irradiation section, 32 ... ultraviolet irradiation apparatus, 34 ... winder, 50 ... inorganic film manufacturing apparatus, 52, 72 DESCRIPTION OF SYMBOLS ... Support body roll 54 ... Support body supply chamber 55, 74, 78 ... Vacuum exhaust means 56 ... Inorganic film forming chamber 58 ... Support body take-up chamber 60, 70 ... Rotating shaft 62 ... Guide roll 66 DESCRIPTION OF SYMBOLS ... Drum, 68 ... Film-forming means, 76 ... Touch roll, 100 ... Manufacturing equipment, 110, 150 ... Barrier support, 120 ... Application | coating part, 124 ... Die coater, 126, 162 ... Backup roller, 130 ... Laminating part, 132 ... Laminate low DESCRIPTION OF SYMBOLS 134 ... Heating chamber 160 ... Polymerization process part 164 ... Light irradiation apparatus 170 ... Laminated film 180 ... Peeling roller 200 ... Sputtering apparatus 210 ... Vacuum vessel 211 ... Holder 212 ... Plasma electrode 213 ... RF Power source, 214 ... gas introduction pipe, 215 ... gas discharge pipe, 216 ... protective film, 300 ... backlight unit, 300A ... light source, 300B ... light guide plate, 300C ... wavelength conversion member, 310 ... blue light, 320 ... green light, 330: Red light, 351: Liquid crystal display device, 361, 363, 391, 393 ... Polarizing plate protective film, 362 ... Back light side polarizer, 364 ... Back light side polarizing plate, 371 ... Liquid crystal cell, 392 ... Display side polarized light Child, 394 ... Display-side polarizing plate

Claims (17)

A laminated film formed by laminating an optical functional layer and a barrier layer on at least one surface of the optical functional layer,
The laminated film which has a film | membrane which has a refractive index larger than the refractive index of the said optical functional layer on the side surface of the said optical functional layer.   The laminated film according to claim 1, wherein the optical functional layer includes at least one of quantum dots and quantum rods.   The laminated film according to claim 1 or 2, wherein the film is a film having gas barrier properties.   The laminated film according to any one of claims 1 to 3, wherein the film is an inorganic film.   The film comprises at least one of one or more metal oxides, nitrides, and oxynitrides selected from silicon, aluminum, indium, tin, zinc, titanium, chromium, nickel, copper, silver, and gold. Item 5. The laminated film according to Item 4.   The film is selected from a first metal layer made of one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper and silver, and from aluminum, titanium, chromium, nickel, tin, copper and silver. The laminated film according to claim 4, which is a laminated film obtained by repeating a laminated structure of at least one metal oxide layer composed of one or more metal oxides at least once.   The laminated film according to claim 6, further comprising a second metal layer made of one or more metals selected from aluminum, titanium, chromium, nickel, tin, copper, and silver on the laminated film.   The laminated film according to claim 6 or 7, wherein the thickness of the first metal layer is 5 nm or more and 50 nm or less, and the thickness of the metal oxide layer is 0.1 nm or more and 5 nm or less.   The laminated film according to any one of claims 1 to 8, wherein the film has a thickness of 5 to 500 nm.   The laminated film according to any one of claims 1 to 9, wherein the film has a thickness of 20 to 200 nm.   The laminated film according to claim 7, wherein the thickness of the second metal layer is 10 nm or more and 200 nm or less.   The laminated film according to any one of claims 1 to 11, wherein the refractive index of the optical functional layer is in the range of 1.3 to 1.6, and the refractive index of the film is 1.5 or more.   The laminated film according to any one of claims 1 to 12, wherein a difference between a refractive index of the optical functional layer and a refractive index of the film is 0.2 or more. The laminated film according to any one of claims 1 to 13,
A backlight unit including at least a light source. The backlight unit according to claim 14,
A liquid crystal display device comprising at least a liquid crystal cell. A plurality of laminated films formed by laminating both sides of the optical functional layer and the optical functional layer with a barrier layer,
The manufacturing method of the laminated | multilayer film which forms the film | membrane which has a refractive index larger than the refractive index of the said optical functional layer on the side surface of the said optical functional layer of the several laminated | multilayer film laminated | stacked.   The method for producing a laminated film according to claim 16, wherein the film is formed by a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method.

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