WO2015087792A1 - Film optique, et procédé pour produire un film optique - Google Patents

Film optique, et procédé pour produire un film optique Download PDF

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Publication number
WO2015087792A1
WO2015087792A1 PCT/JP2014/082200 JP2014082200W WO2015087792A1 WO 2015087792 A1 WO2015087792 A1 WO 2015087792A1 JP 2014082200 W JP2014082200 W JP 2014082200W WO 2015087792 A1 WO2015087792 A1 WO 2015087792A1
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Prior art keywords
metal
gas barrier
layer
barrier layer
oxide gas
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PCT/JP2014/082200
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English (en)
Japanese (ja)
Inventor
河村　朋紀
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コニカミノルタ株式会社
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Priority to CN201480066497.5A priority Critical patent/CN105793745B/zh
Priority to JP2015552415A priority patent/JP6414075B2/ja
Publication of WO2015087792A1 publication Critical patent/WO2015087792A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to an optical film comprising semiconductor nanoparticles in a transparent layer.
  • the present invention includes a backlight unit (BLU) for a display device such as a liquid crystal display (LCD), a television, a computer, a mobile phone, a smart phone, a personal digital assistant (PDA), a game machine, an electronic reading device, and a digital camera.
  • BLU backlight unit
  • the present invention relates to an optical film including semiconductor nanoparticles having high efficiency and pure color.
  • the present invention relates to an optical film that can suppress deterioration of semiconductor nanoparticles due to intrusion of oxygen, water, or the like over a long period of time and is excellent in transparency.
  • semiconductor nanoparticles have gained commercial interest due to their size-tunable electronic properties.
  • Semiconductor nanoparticles are used in a wide variety of fields, for example, biolabeling, solar power generation, catalysis, bioimaging, light emitting diodes (LEDs), general spatial lighting, and electroluminescent displays. Is expected.
  • liquid crystal display For example, in an optical device using semiconductor nanoparticles, light incident on a liquid crystal display (LCD) is emitted by irradiating the semiconductor nanoparticles dispersed in a transparent matrix resin material with light.
  • LCD liquid crystal display
  • semiconductor nanoparticles deteriorate when they come into contact with oxygen or water, and various means for preventing the semiconductor nanoparticles from coming into contact with oxygen or water are employed.
  • various means for preventing the semiconductor nanoparticles from coming into contact with oxygen or water are employed.
  • covers covers is mentioned.
  • the surface treatment method coats each particle, the yield of the semiconductor nanoparticles after coating is low, the luminous efficiency after coating decreases, and the dispersion stability to the matrix resin due to the surface coating with silica. (For example, refer to Patent Document 1).
  • the semiconductor nanoparticle layer provided on one substrate is covered with an adhesive material, and another substrate is bonded via the adhesive material
  • a method for sealing an optical material layer between two substrates has been proposed (see, for example, Patent Document 3).
  • the adhesive material is also required to have an oxygen barrier property. Becomes higher.
  • the present invention has been made in view of the above-described problems and circumstances, and its solution is to suppress deterioration of semiconductor nanoparticles due to intrusion of oxygen, water, etc. over a long period of time, and an optical film excellent in transparency and a method for producing the same Is to provide.
  • a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin are formed on a substrate.
  • An optical film comprising a metal derived from a metal alkoxide or a metal chelate compound at an interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer, or the semiconductor nanoparticle layer and the metal oxide.
  • An optical film comprising a metal oxide gas barrier layer on a substrate, and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin,
  • the interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer contains a metal alkoxide or a metal derived from a metal chelate compound, or between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • an intermediate layer containing a metal derived from a metal alkoxide or a metal chelate compound.
  • the metal derived from the metal alkoxide or metal chelate compound is at least one metal selected from aluminum (Al) and titanium (Ti).
  • middle layer contains the modified body of perhydropolysilazane,
  • the content of the metal derived from the metal alkoxide or metal chelate compound in the interface or the intermediate layer is 0.2 to 10 at% with respect to the total atomic weight in the interface or the intermediate layer. 8.
  • a method for producing an optical film comprising a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, Forming the metal oxide gas barrier layer; Forming the semiconductor nanoparticle layer; Forming an intermediate layer by a coating method using a coating liquid containing a metal alkoxide or a metal chelate compound between the metal oxide gas barrier layer and the semiconductor nanoparticle layer;
  • a method for producing an optical film comprising:
  • a method for producing an optical film comprising a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, Forming the metal oxide gas barrier layer by a coating method using a coating solution containing a metal alkoxide or a metal chelate compound and perhydropolysilazane; And a step of forming the semiconductor nanoparticle layer.
  • a method for producing an optical film comprising a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, Forming the metal oxide gas barrier layer;
  • ADVANTAGE OF THE INVENTION According to this invention, degradation of the semiconductor nanoparticle by penetration
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the metal oxide gas barrier layer obtained by chemical vapor deposition such as plasma CVD, physical vapor deposition represented by sputtering, etc., or a method in which perhydropolysilazane is applied and modified by vacuum ultraviolet light is relatively thin. However, it is presumed that oxygen and water can be effectively prevented from coming into contact with semiconductor nanoparticles, and sufficient durability can be secured.
  • the barrier layer has low adhesiveness with the semiconductor nanoparticle layer in which the semiconductor nanoparticles are dispersed in the ultraviolet curable resin, and it is difficult to suppress deterioration of the semiconductor nanoparticles over a long period of time.
  • the metal alkoxide or metal chelate compound-derived metal is included in the interface between the semiconductor nanoparticle layer and the barrier layer, or the metal alkoxide or metal chelate compound-derived metal is interposed between the semiconductor nanoparticle layer and the barrier layer.
  • Schematic configuration diagram showing an example of an apparatus for forming a metal oxide gas barrier layer by vapor deposition Diagram for explaining the interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer Schematic sectional view showing an example of an embodiment of the optical film of the present invention
  • Schematic sectional view showing an example of an embodiment of the optical film of the present invention Schematic sectional view showing an example of an embodiment of the optical film of the present invention
  • the optical film of the present invention is an optical film comprising a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin on a substrate, the semiconductor nanoparticle layer and the semiconductor nanoparticle layer A metal alkoxide or metal chelate compound-derived metal is contained at the interface with the metal oxide gas barrier layer, or a metal alkoxide or metal chelate compound is interposed between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • An intermediate layer containing a metal derived therefrom is provided. This feature is a technical feature common to or corresponding to each of claims 1 to 13.
  • the metal derived from the metal alkoxide or metal chelate compound is aluminum (Al), titanium (Ti), zinc (Zn), zirconium (Zr), silicon (Si), magnesium (Mg), germanium (Ge). Boron (B), lithium (Li), iron (Fe), gallium (Ga), tin (Sn), tantalum (Ta), and vanadium (V) are preferred.
  • the metal alkoxide or metal chelate compound containing these elements is relatively stable as a single substance in the solution, and can improve the adhesion between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • the metal derived from the metal alkoxide or metal chelate compound is preferably aluminum (Al).
  • the ultraviolet curable resin preferably has an epoxy group. Since the ultraviolet curable resin having an epoxy group has a strong interaction with the metal alkoxide or the metal chelate compound, the adhesion between the semiconductor nanoparticle layer and the metal oxide gas barrier layer can be improved more effectively.
  • the intermediate layer preferably contains a modified product of perhydropolysilazane. In the present invention, it is preferable that the metal derived from the metal alkoxide or the metal chelate compound is contained in the intermediate layer.
  • the metal derived from a metal alkoxide or a metal chelate compound can exist more reliably between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • the metal alkoxide or the metal derived from the metal chelate compound is preferably contained in the metal oxide gas barrier layer.
  • the layer thickness of the whole optical film can be reduced.
  • the metal alkoxide or metal chelate compound-derived metal content in the interface or the intermediate layer is 0.2 to 10 at% relative to the total atomic weight in the interface or the intermediate layer. preferable. Thereby, the adhesiveness of a semiconductor nanoparticle layer and a metal oxide gas barrier layer can be improved more effectively.
  • ⁇ 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.
  • the optical film of the present invention comprises a metal oxide gas barrier layer and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin on a substrate, the semiconductor nanoparticle layer and the metal oxide gas barrier layer. Or a metal containing a metal derived from a metal alkoxide or a metal chelate compound or an intermediate containing a metal derived from a metal alkoxide or a metal chelate compound between the semiconductor nanoparticle layer and the metal oxide gas barrier layer. With layers. Each layer and its material constituting the optical film of the present invention will be described below.
  • the base material that can be used in the optical film of the present invention is not particularly limited, such as glass and plastic, but those having translucency are used.
  • Examples of the material that is preferably used as the light-transmitting substrate include glass, quartz, and a resin film. Particularly preferred is a resin film capable of giving flexibility to the optical film.
  • the thickness of the base material is not particularly limited and may be any thickness. However, the film has a flexibility of 6 ⁇ m or more from the viewpoint of obtaining good handling properties that are less likely to cause wrinkles and creases as a film. From the point of ensuring, 300 micrometers or less are preferable. Furthermore, 12 ⁇ m or more and 150 ⁇ m or less are more preferable from the viewpoint of heat resistance and material cost.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
  • the semiconductor nanoparticle layer is configured to contain semiconductor nanoparticles and an ultraviolet curable resin. Two or more semiconductor nanoparticle layers may be provided. In this case, it is preferable that semiconductor nanoparticles having different emission wavelengths are contained in each of the two or more semiconductor nanoparticle layers.
  • a semiconductor nanoparticle layer forming coating solution containing semiconductor nanoparticles and an ultraviolet curable resin is applied on a substrate, then dried, and subjected to active energy ray irradiation treatment with ultraviolet rays or the like. Can be formed.
  • any appropriate method can be adopted as a method for applying the coating solution for forming a semiconductor nanoparticle layer.
  • Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, gravure printing method, reverse coating method, die coating method. Law.
  • the coating amount is suitably 0.1 to 40 ⁇ m, preferably 0.5 to 30 ⁇ m, as the wet layer thickness.
  • the dry layer thickness is an average layer thickness of 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m.
  • the semiconductor nanoparticle layer forming coating solution for forming the semiconductor nanoparticle layer may contain a solvent.
  • the organic solvent contained in the coating solution include hydrocarbons (for example, toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). ), Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, other organic solvents, or a mixture thereof.
  • a solvent it is preferable that it does not react with a semiconductor nanoparticle, For example, toluene etc. are mentioned.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • the irradiation conditions vary depending on individual lamps, the dose of ultraviolet radiation is typically 50 ⁇ 5000mJ / cm 2, preferably 50 ⁇ 1500mJ / cm 2.
  • the semiconductor nanoparticle layer constituting the optical film of the present invention contains semiconductor nanoparticles. That is, the semiconductor nanoparticles are contained in the coating solution for forming the semiconductor nanoparticle layer.
  • the semiconductor nanoparticle according to the present invention refers to a particle having a predetermined size that is composed of a crystal of a semiconductor material and has a quantum confinement effect, and is a fine particle having a particle diameter of about several nanometers to several tens of nanometers. The quantum dot effect shown is obtained.
  • the particle diameter of the semiconductor nanoparticles according to the present invention is preferably in the range of 1 to 20 nm, more preferably in the range of 1 to 10 nm.
  • the energy level E of such semiconductor nanoparticles is generally expressed by the following formula (1) when the Planck constant is “h”, the effective mass of electrons is “m”, and the radius of the semiconductor nanoparticles is “R”. ).
  • the band gap of the semiconductor nanoparticles increases in proportion to “R ⁇ 2 ”, and a so-called quantum dot effect is obtained.
  • the band gap value of the semiconductor nanoparticles can be controlled by controlling and defining the particle diameter of the semiconductor nanoparticles. That is, by controlling and defining the particle diameter of the fine particles, it is possible to provide diversity that is not found in ordinary atoms. Therefore, it can be excited by light, or converted into light having a desired wavelength and emitted.
  • such a light-emitting semiconductor nanoparticle material is defined as a semiconductor nanoparticle.
  • the average particle size of the semiconductor nanoparticles is about several nm to several tens of nm, but is set to an average particle size corresponding to the target emission color.
  • the average particle diameter of the semiconductor nanoparticles is preferably set within a range of 3.0 to 20 nm.
  • the average particle size of the semiconductor nanoparticles is set.
  • the diameter is preferably set in the range of 1.5 to 10 nm.
  • the average particle diameter of the semiconductor nanoparticles is preferably set in the range of 1.0 to 3.0 nm. .
  • a known method can be used. For example, a method of observing semiconductor nanoparticles using a transmission electron microscope (TEM) and obtaining the number average particle size of the particle size distribution therefrom, or a method of obtaining an average particle size using an atomic force microscope (AFM)
  • the particle size can be measured using a particle size measuring apparatus using a dynamic light scattering method, for example, “ZETASIZER Nano Series Nano-ZS” manufactured by Malvern.
  • an atomic force microscope A method of obtaining an average particle size using AFM is preferred.
  • the aspect ratio (major axis diameter / minor axis diameter) value is preferably in the range of 1.0 to 2.0, more preferably 1.1 to 2.0. The range is 1.7.
  • the aspect ratio (major axis diameter / minor axis diameter) of the semiconductor nanoparticles according to the present invention can also be determined by measuring the major axis diameter and the minor axis diameter using, for example, an atomic force microscope (AFM). it can.
  • the number of individuals to be measured is preferably 300 or more.
  • the addition amount of the semiconductor nanoparticles is preferably in the range of 0.01 to 50% by mass, and in the range of 0.5 to 30% by mass, when the total constituent substances of the semiconductor nanoparticle layer are 100% by mass. More preferably, it is most preferably in the range of 2.0 to 25% by mass. If the addition amount is 0.01% by mass or more, sufficient luminance efficiency can be obtained, and if it is 50% by mass or less, an appropriate inter-particle distance of the semiconductor nanoparticles can be maintained, and the quantum size effect can be sufficiently obtained. It can be demonstrated.
  • Constituent material of semiconductor nanoparticles for example, a simple substance of Group 14 element of periodic table such as carbon, silicon, germanium, tin, etc., Group 15 of periodic table such as phosphorus (black phosphorus), etc.
  • Elemental element simple substance, periodic table group 16 element such as selenium, tellurium, etc., compound consisting of a plurality of periodic table group 14 elements such as silicon carbide (SiC), tin (IV) (SnO 2 ), tin sulfide ( II, IV) (Sn (II) Sn (IV) S 3 ), tin sulfide (IV) (SnS 2 ), tin sulfide (II) (SnS), tin selenide (II) (SnSe), tin telluride ( II) (SnTe), lead sulfide (II) (PbS), lead selenide (II) (PbSe), lead telluride (II) (PbTe) periodic table group 14 elements and periodic table group 16 elements , Boron nitride (BN), boron phosphide (BP), boron arsenide ( BAs), aluminum nitride (AlN
  • periodic table group 2 element and period Front It is preferably a compound of Group 6 elements, among them, Si, Ge, GaN, GaP , InN, InP, Ga 2 O 3, Ga 2 S 3, In 2 O 3, In 2 S 3, ZnO, ZnS, CdO, CdS Is more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and because a pure spectrum can be stably obtained in the visible light region, light emitting devices Is advantageous for the formation of Of these materials, CdSe, ZnSe, and CdS are preferable in terms of light emission stability. From the viewpoints of luminous efficiency, high refractive index, safety and economy, ZnO and ZnS semiconductor nanoparticles are preferred. Moreover, said material may be used by 1 type and may be used in combination of 2 or more type.
  • the semiconductor nanoparticles described above can be doped with trace amounts of various elements as impurities as necessary. By adding such a doping substance, the emission characteristics can be greatly improved.
  • the band gap (eV) of the semiconductor nanoparticles can be measured using a Tauc plot.
  • the Tauc plot which is one of the optical scientific measurement methods of the band gap (eV), will be described.
  • the maximum wavelength of the emission spectrum can be simply used as an index of the band gap.
  • the surface of the semiconductor nanoparticles is preferably coated with an inorganic coating layer or a coating composed of an organic ligand. That is, the surface of the semiconductor nanoparticle has a core-shell structure having a core region composed of a semiconductor nanoparticle material and a shell region composed of an inorganic coating layer or an organic ligand. preferable.
  • This core / shell structure is preferably formed of at least two kinds of compounds, and may form a gradient structure (gradient structure) with two or more kinds of compounds.
  • gradient structure gradient structure
  • aggregation of the semiconductor nanoparticles in the coating liquid can be effectively prevented, the dispersibility of the semiconductor nanoparticles can be improved, the luminance efficiency is improved, and the optical film of the present invention is used.
  • Generation of color misregistration can be suppressed when the light emitting device is continuously driven. Further, the light emission characteristics can be stably obtained due to the presence of the coating layer.
  • a surface modifier as described later can be reliably supported in the vicinity of the surface of the semiconductor nanoparticles.
  • the thickness of the coating (shell part) is not particularly limited, but is preferably in the range of 0.1 to 10 nm, and more preferably in the range of 0.1 to 5 nm.
  • the emission color can be controlled by the average particle diameter of the semiconductor nanoparticles, and if the thickness of the coating is within the above range, the thickness of the coating can be reduced from the thickness corresponding to several atoms.
  • the thickness is less than one particle, the semiconductor nanoparticles can be filled with high density, and a sufficient amount of light emission can be obtained.
  • the presence of the coating can suppress non-luminous electron energy transfer due to defects existing on the particle surfaces of the core particles and electron traps on the dangling bonds, thereby suppressing a decrease in quantum efficiency.
  • the surface of the semiconductor nanoparticles is attached to the surface of the semiconductor nanoparticles, so that the shape of the formed semiconductor nanoparticles becomes high in sphericity, and the particle size distribution of the semiconductor nanoparticles Can be kept narrow, and therefore can be made particularly excellent.
  • the surface modifier that can be applied in the present invention may be those directly attached to the surface of the semiconductor nanoparticles, or those attached via the shell (the surface modifier is directly attached to the shell, the semiconductor It may be one that is not in contact with the core part of the nanoparticles.
  • the surface modifier examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, and the like.
  • Trialkylphosphines polyoxyethylene alkylphenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; tri (n-hexyl) amine, tri (n-octyl) amine, tri ( tertiary amines such as n-decyl) amine; tripropylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphineoxy Organic phosphorus compounds such as tridecylphosphine oxide; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; organic nitrogen compounds such as nitrogen-containing aromatic compounds such as pyridine, lutidine, collidine and quinolines; hexylamine; Aminoalkanes such as octylamine, decylamine, dodecyl
  • semiconductor nanoparticles are prepared by the method described later, as surface modifiers, semiconductor nanoparticles are used in a high-temperature liquid phase. It is preferable that the substance be coordinated to the fine particles of the above and stabilized, specifically, trialkylphosphines, organic phosphorus compounds, aminoalkanes, tertiary amines, organic nitrogen compounds, dialkyl sulfides, Dialkyl sulfoxides, organic sulfur compounds, higher fatty acids and alcohols are preferred.
  • the dispersibility of the semiconductor nanoparticles in the coating solution can be made particularly excellent.
  • the shape of the semiconductor nanoparticles formed during the production of the semiconductor nanoparticles can be made higher in sphericity, and the particle size distribution of the semiconductor nanoparticles can be made sharper.
  • the size (average particle diameter) of the semiconductor nanoparticles is preferably in the range of 1 to 20 nm.
  • the size of a semiconductor nanoparticle is composed of a core region composed of a semiconductor nanoparticle material, a shell region composed of an inert inorganic coating layer or an organic ligand, and a surface modifier. Represents the total size. If the surface modifier or shell is not included, the size does not include it.
  • an aqueous raw material is used, for example, alkanes such as n-heptane, n-octane, isooctane, or benzene, toluene.
  • Inverted micelles which exist as reverse micelles in non-polar organic solvents such as aromatic hydrocarbons such as xylene, and crystal growth in this reverse micelle phase, inject a thermally decomposable raw material into a high-temperature liquid-phase organic medium
  • examples thereof include a hot soap method for crystal growth and a solution reaction method involving crystal growth at a relatively low temperature using an acid-base reaction as a driving force, as in the hot soap method. Any method can be used from these production methods, and among these, the liquid phase production method is preferred.
  • the organic surface modifier present on the surface when the semiconductor nanoparticles are synthesized is referred to as an initial surface modifier.
  • the initial surface modifier in the hot soap method include trialkylphosphines, trialkylphosphine oxides, alkylamines, dialkyl sulfoxides, alkanephosphonic acid and the like. These initial surface modifiers are preferably exchanged for the above-mentioned surface modifiers by an exchange reaction.
  • the initial surface modifier such as trioctylphosphine oxide obtained by the hot soap method described above is exchanged with the above-described surface modifier by an exchange reaction performed in a liquid phase containing the surface modifier. It is possible.
  • the semiconductor nanoparticle layer constituting the optical film of the present invention contains an ultraviolet curable resin. That is, the ultraviolet curable resin is contained in the coating solution for forming the semiconductor nanoparticle layer.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferably used. It is done. Among them, an ultraviolet curable acrylate resin having an epoxy group in the composition is preferable because of its strong interaction with a metal alkoxide or a metal chelate compound described later. Thus, the semiconductor nanoparticle layer and the metal oxide can be interacted or reacted with a metal alkoxide or a metal chelate compound present at the interface or intermediate layer of the metal oxide gas barrier layer of the semiconductor nanoparticle layer, although it is not certain. It is estimated that the adhesion and durability with the gas barrier layer are improved.
  • UV curable urethane acrylate resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate) in the product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Only acrylates are indicated as such), and can be easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. Further, for example, a mixture of 100 parts Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Corporation) is preferably used.
  • UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, generally as disclosed in JP-A-59-151112. Those described in the publication can be used.
  • ultraviolet curable epoxy acrylate resin examples include those produced by reacting epoxy acrylate with an oligomer, a reactive diluent and a photopolymerization initiator added thereto. Those described in Japanese Patent No. 105738 can be used.
  • UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.
  • photopolymerization initiators for these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.
  • the photopolymerization initiator can also be used as a photosensitizer.
  • a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • the photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.
  • the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. Further, as monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate And pentaerythritol tetraacrylic ester.
  • monomers having two or more unsaturated double bonds ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate
  • Adekaoptomer KR / BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by ADEKA Corporation); Koei Hard A-101-KK A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20 , AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100 , P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, KRM703 , KRM7130
  • Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol.
  • a pentaacrylate etc. can be mentioned.
  • the metal oxide gas barrier layer contains a metal oxide and is a layer that suppresses oxygen and water from entering the semiconductor nanoparticle layer.
  • a physical vapor deposition method in which a metal or its oxide is evaporated to form a film on a substrate, or a raw material containing a desired thin film component
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • a gas for example, an organosilicon compound typified by tetraethoxysilane (TEOS), etc.
  • TEOS tetraethoxysilane
  • a semiconductor for example, a sputtering method in which metal Si is evaporated and deposited on a substrate in the presence of oxygen using a laser or the like can be used.
  • the chemical vapor deposition method (CVD method) or the physical vapor deposition method (PVD method) is preferable, and more preferably, the plasma chemical vapor deposition method (plasma CVD method) in which plasma discharge is performed.
  • plasma CVD method plasma chemical vapor deposition method
  • a discharge plasma chemical vapor deposition method also referred to as “roller CVD method” having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound is used. Is the method.
  • a coating liquid for forming a metal oxide gas barrier layer containing polysilazane is applied and dried to form a coating film, and then vacuum ultraviolet light is applied to the formed coating film. It can also be formed by irradiating and performing a modification treatment.
  • the layer thickness of the metal oxide gas barrier layer is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 50 to 1000 nm.
  • the thickness of the metal oxide gas barrier layer is within the above range, the gas barrier property against oxygen and water vapor is excellent, and the deterioration of the gas barrier property due to bending is not observed.
  • the metal oxide gas barrier layer is preferably formed on the substrate surface by a roll-to-roll method from the viewpoint of productivity.
  • a forming apparatus that can be used when producing a gas barrier layer by a plasma CVD method is not particularly limited, and includes a film forming roller to which at least a pair of magnetic fields are applied, a plasma power source, and a pair of It is preferable that the apparatus has a configuration capable of discharging between film forming rollers to which a magnetic field is applied.
  • a CVD apparatus S1 as shown in FIG. 1 can be used, and the CVD apparatus S1 can be manufactured by a roll-to-roll method using a plasma CVD method.
  • the CVD apparatus S1 mainly includes a roll-shaped feeding roller 11A in which a base material 2 is laminated, transport rollers 22 and 23 for transporting the base material 2, and a pair of film formations.
  • Rollers 31 and 32, a film forming gas supply pipe 41, a plasma generating power source 51, and a winding roller 11B are provided.
  • magnetic field generators 61 and 62 are provided, which are fixed so as not to rotate even when the film forming roller rotates.
  • the components such as the film forming rollers 31 and 32 are arranged in the vacuum chamber 16 as shown in FIG. Further, a vacuum pump 17 which is a vacuum exhaust means is connected to the vacuum chamber 16 via an exhaust port 18, and the pressure in the vacuum chamber 16 is appropriately adjusted by the vacuum pump 17 and the film forming gas supply pipe 41. It is possible.
  • the vacuum pump 17 can evacuate the inside of the vacuum chamber 16 to a vacuum state or a low pressure state according to vacuum.
  • the base material 2 is routed around each of the pair of film forming rollers 31 and 32. Then, a voltage is applied between the pair of film forming rollers 31 and 32 to generate plasma, thereby forming a plasma discharge space. Next, the metal oxide gas barrier layer is formed on one surface of the substrate 2 that is continuously conveyed while supplying the film forming gas for forming the metal oxide gas barrier layer from the film forming gas supply pipe 41 to the discharge space. After forming, it is wound up into a roll by the winding roller 11B.
  • a raw material gas, a reaction gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
  • the source gas in the film forming gas used for forming the metal oxide gas barrier layer can be appropriately selected and used according to the material of the gas barrier layer to be formed.
  • a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used, but the metal oxide gas barrier layer according to the present invention contains at least carbon atoms.
  • a source gas capable of forming a metal oxide layer is preferred.
  • organosilicon compound applicable to the present invention examples include hexamethyldisiloxane (abbreviation: HMSO), hexamethyldisilane (abbreviation: HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, Methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (abbreviation: TMOS), tetraethoxysilane (abbreviation: TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like.
  • HMSO hexamethyldisiloxane
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer.
  • organosilicon compounds can be used alone or in combination of two or more.
  • the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene.
  • an appropriate source gas is selected according to the type of the metal oxide gas barrier layer.
  • a reactive gas may be used in addition to the raw material gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example.
  • These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction for forming a nitride are used. It can be used in combination with gas.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.
  • the pressure (vacuum degree) in the vacuum chamber 16 can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
  • the optical film of the present invention may have a plurality of metal oxide gas barrier layers, at least one of which is a chemical vapor deposition method (CVD method) or a physical vapor deposition method (PVD method) as described above. ).
  • CVD method chemical vapor deposition method
  • PVD method physical vapor deposition method
  • a coating liquid for forming a metal oxide gas barrier layer containing polysilazane is used as a method for forming a metal oxide gas barrier layer on a substrate by a coating method.
  • a metal oxide which is a polysilazane modified layer having gas barrier properties by subjecting a layer (polysilazane-containing layer) formed by applying and drying on a substrate to a modification of polysilazane irradiated with vacuum ultraviolet light A method of converting to a gas barrier layer is used.
  • the polysilazane-containing layer formed by coating and drying is coated with a protective layer, laminated, and subjected to a modification treatment such as irradiating vacuum ultraviolet light from the coating surface side of the protective layer. It can also be formed by modifying the layer into a gas barrier layer.
  • the metal oxide gas barrier layer can be formed by a wet coating method in which a coating liquid for forming a metal oxide gas barrier layer containing polysilazane is applied to form a coating film.
  • the “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, SiO 2 having a bond such as Si—N, Si—H, N—H, etc., Si 3 N 4 and both intermediate solid solutions SiO x. a ceramic precursor inorganic polymer composed of N y or the like.
  • the wet coating method for coating the metal oxide gas barrier layer-forming coating solution containing the polysilazane it can be appropriately selected from conventionally known methods. Specific examples of coating methods include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, and gravure printing. It is done.
  • the layer thickness of the polysilazane-containing layer formed on the substrate is appropriately set according to the purpose, but the layer thickness after drying is preferably in the range of 1 nm to 100 ⁇ m, more preferably 10 nm to It is in the range of 10 ⁇ m, and most preferably in the range of 10 nm to 1 ⁇ m.
  • the metal oxide gas barrier layer is coated with a coating liquid for forming a metal oxide gas barrier layer containing polysilazane as described above, dried, and irradiated with vacuum ultraviolet light for modification treatment.
  • the metal oxide gas barrier layer is preferably laminated on the semiconductor nanoparticle layer. According to this aspect, a base material for supporting the metal oxide gas barrier layer becomes unnecessary, the thickness as an optical film can be reduced, and at the same time, the configuration is advantageous in terms of flexibility and material cost. it can.
  • the metal derived from the metal alkoxide or the metal chelate compound is present at the interface or the intermediate layer, so that the semiconductor nanoparticle layer and the metal oxide gas barrier layer react and interact with each other to improve adhesion. be able to.
  • the metal alkoxide or metal chelate compound is contained in the interface or intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer, but after laminating other various layers, The metal alkoxide or metal chelate compound is considered to be bonded or interacting with the constituent components of the semiconductor nanoparticle layer or the metal oxide gas barrier layer.
  • the added metal alkoxide or metal chelate compound exists not as a form of metal alkoxide or metal chelate compound but as a metal derived from the metal alkoxide or metal chelate compound.
  • the metal derived from the metal alkoxide or metal chelate compound according to the present invention is an unreacted metal alkoxide or metal chelate at the interface or intermediate layer containing the metal, or an organic substance of a ligand deviated from the coordination of the metal chelate. It can be judged from the existence of a part. Although the cause is not clear, it is presumed that the presence of these compounds affects the interaction at the interface and the effects of the present invention are expressed. The presence of these can be easily detected by an analysis method such as infrared spectroscopy, solid-state NMR, and X-ray photoelectron spectroscopy alone or in combination.
  • metal alkoxide or metal chelate examples include, for example, beryllium acetylacetonate, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, boric acid Tri-tert-butyl, magnesium ethoxide, magnesium ethoxyethoxide, magnesium methoxyethoxide, magnesium acetylacetonate, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n -Butoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, aluminum acetylacetonate, acetoalkoxyaluminum diisopropylate Aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, aluminum diethyl
  • the metal element contained in the metal alkoxide or metal chelate compound according to the present invention is aluminum (Al), titanium (Ti), zinc (Zn), zirconium (Zr), silicon (Si), magnesium (Mg), germanium ( It is preferably at least one metal selected from Ge), boron (B), lithium (Li), iron (Fe), gallium (Ga), tin (Sn), tantalum (Ta) and vanadium (V). . More preferably, it is at least one metal selected from aluminum (Al) and titanium (Ti).
  • the metal alkoxide or metal chelate compound containing these metal elements is relatively stable as a single substance in the solution, and can improve the adhesion between the semiconductor nanoparticle layer and the metal oxide gas barrier layer. it can.
  • the metal element contained in a metal alkoxide or a metal chelate compound is aluminum (Al) in the point that there is little coloring and transparency is high.
  • the metal alkoxide or metal chelate compound containing aluminum include, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec.
  • aluminum tri-sec-butoxide, aluminum ethyl acetoacetate diisopropylate, aluminum diisopropylate monosec-butyrate, aluminum ethyl acetoacetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate and the like are preferable.
  • the interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer in the optical film of the present invention is a surface where the semiconductor nanoparticle layer and the metal oxide gas barrier layer are in contact with each other, and is a constituent component of the metal oxide gas barrier layer. Is defined as the inside of a region of 20 nm before and after in the thickness direction centering on the position where the minimum is.
  • the interface will be described with reference to FIG. In FIG. 2, the horizontal axis represents the distance in the thickness direction (nm) when the surface of the metal oxide gas barrier layer on the substrate side is 0, and the vertical axis represents the atomic composition ratio (%) of the constituent components of each layer. It is a graph which shows.
  • line A indicates the ratio of the constituent components of the metal oxide gas barrier layer
  • line B indicates the ratio of the metal derived from the metal alkoxide or metal chelate compound. Ratios are omitted.
  • a region D which is a combination of regions of 20 nm in the thickness direction around the position C where the ratio of the constituent components of the metal oxide gas barrier layer is the minimum (0% in FIG. 2), is the interface.
  • the intermediate layer contains a metal derived from a metal alkoxide or a metal chelate compound. Is.
  • the amount is such that the metal atomic composition ratio (at%) with respect to the total atomic weight in the interface or intermediate layer is in the range of 0.2 to 10 at%.
  • the metal atomic composition ratio (at%) with respect to the total atomic weight in the interface or intermediate layer is in the range of 0.2 to 10 at%.
  • the method for measuring the content of the metal derived from the metal alkoxide or metal chelate compound at the interface or intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer can be measured by the following method. That is, the metal content can be obtained by measuring the composition in the depth (thickness) direction from the surface of the metal oxide gas barrier layer by XPS analysis under the following measurement conditions. It is preferable that the measurement is performed on 10 points randomly selected in the surface direction of the optical film, and whether or not the average value is within the above numerical range is determined.
  • ⁇ Device QUANTERASXM (manufactured by ULVAC-PHI)
  • X-ray source Monochromatic Al-K ⁇ Measurement area: Si2p, C1s, N1s, O1s ⁇
  • Sputtering ion Ar (2 keV)
  • Depth profile repeat measurement after sputtering for 1 minute
  • Data processing MultiPak (manufactured by ULVAC-PHI Co., Ltd.) Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Examples of a method for containing a metal derived from a metal alkoxide or a metal chelate compound at the interface or intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer include the following methods.
  • the semiconductor nanoparticle layer or the metal oxide gas A method of laminating a barrier layer, a layer forming coating solution for forming a semiconductor nanoparticle layer or a metal oxide gas barrier layer, and a raw material thereof, a metal alkoxide or a metal chelate compound is added, and the metal alkoxide or By including a metal derived from a metal chelate compound in the semiconductor nanoparticle layer or the metal oxide gas barrier layer, a method of containing the metal at the interface can be exemplified. As another method, a method of adding it in the following intermediate layer is also a preferred embodiment.
  • the optical film of the present invention may further include an intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • the intermediate layer contains a metal derived from the metal alkoxide or metal chelate compound according to the present invention and an organic or inorganic compound for holding the metal.
  • the metal derived from the metal alkoxide or the metal chelate compound is retained, and the semiconductor nanoparticle layer and the metal oxide gas barrier layer due to the inclusion of the metal
  • the compound having such properties a compound obtained by applying an organic or inorganic perhydropolysilazane compound solution, drying it, and reacting it can be mentioned.
  • the same compounds as those used for forming the metal oxide gas barrier layer can be preferably used.
  • the amount of metal alkoxide or metal chelate compound added to the perhydropolysilazane in the intermediate layer forming coating solution for forming the intermediate layer is preferably 1 to 30% in terms of mass ratio.
  • the thickness of the intermediate layer is preferably 1 to 1200 nm.
  • the intermediate layer contains the metal derived from the metal alkoxide or metal chelate compound, it can function as an adhesive layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • the ultraviolet ray curable resin contained in the semiconductor nanoparticle layer is irradiated with ultraviolet rays after the intermediate layer is formed, the intermediate layer configured as described above has a high transmittance of light having a wavelength in the ultraviolet region. The amount of energy required for ultraviolet curing of the semiconductor nanoparticle layer can be reduced.
  • the intermediate layer absorbs less light in the ultraviolet to blue wavelength region by the backlight light source, the transmittance of the light source light can be maintained high, and as a result, the luminous efficiency of the semiconductor nanoparticles in the semiconductor nanoparticle layer can be increased. It becomes possible to ensure high.
  • the intermediate layer can reduce the thickness of the layer required for bonding compared to the case of using a general bonding material, the color of the bonding material itself can be reduced without reducing the light transmittance. Coloring of the optical film due to taste can be suppressed.
  • the metal alkoxide or metal chelate compound-derived metal is contained at a position where the metal derived from the metal alkoxide or metal chelate compound is an interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer. Or as long as it exists in an intermediate
  • FIG. 3 is a schematic cross-sectional view showing a configuration example of the optical film of the present invention.
  • Each configuration of the optical film shown in FIGS. 3A to 3F is an example, and the present invention is not limited to these.
  • An optical film 100 shown in FIG. 3A includes a first metal oxide gas barrier layer 102 formed on a substrate 101 by a vapor deposition method, and a first intermediate layer 103 containing a metal derived from a metal alkoxide or a metal chelate compound.
  • an oxide gas barrier layer 107 that is, in the optical film 100 shown in FIG. 3A, the metal derived from the metal alkoxide or the metal chelate compound is contained in the first intermediate layer 103 and the second intermediate layer 106.
  • An optical film 200 shown in FIG. 3B includes a first metal oxide gas barrier layer 202 formed by vapor deposition on a base material 201, and a first intermediate layer 203 containing a metal derived from a metal alkoxide or a metal chelate compound.
  • An oxide gas barrier layer 207 and a substrate 208 are provided. That is, in the optical film 200 shown in FIG. 3B, the first intermediate layer 203 and the second intermediate layer 206 contain a metal derived from a metal alkoxide or a metal chelate compound.
  • An optical film 300 shown in FIG. 3C includes a first metal oxide gas barrier layer 302 formed by a coating method on a base material 301, and a first intermediate layer 303 containing a metal derived from a metal alkoxide or a metal chelate compound.
  • An optical film 400 shown in FIG. 3D includes a first metal oxide gas barrier layer 402 formed on a base material 401 by a coating method and containing a metal derived from a metal alkoxide or a metal chelate compound, semiconductor nanoparticles 404, and ultraviolet rays.
  • a semiconductor nanoparticle layer 405 containing a curable resin and a second metal oxide gas barrier layer 407 formed by a coating method and containing a metal derived from a metal alkoxide or a metal chelate compound are provided. That is, in the optical film 400 shown in FIG. 3D, the metal derived from the metal alkoxide or the metal chelate compound is contained in the first metal oxide gas barrier layer 402 and the second metal oxide gas barrier layer 407.
  • the optical film 500 shown in FIG. 3E includes a first metal oxide gas barrier layer 502 formed by a coating method on a substrate 501, an intermediate layer 503 containing a metal alkoxide or a metal derived from a metal chelate compound, A semiconductor nanoparticle layer 505 containing semiconductor nanoparticles 504 and an ultraviolet curable resin, and a second metal oxide gas barrier layer 507 containing a metal derived from a metal alkoxide or metal chelate compound formed by a coating method. Configured. That is, in the optical film 500 shown in FIG. 3E, the metal derived from the metal alkoxide or the metal chelate compound is contained in the intermediate layer 503 and the second metal oxide gas barrier layer 507.
  • An optical film 600 shown in FIG. 3F includes a first metal oxide gas barrier layer 602 formed on a substrate 601 by a coating method, semiconductor nanoparticles 604, an ultraviolet curable resin, a metal alkoxide, or a metal derived from a metal chelate compound. And a second metal oxide gas barrier layer 607 formed by a coating method. That is, in the optical film 600 shown in FIG. 3F, the metal derived from the metal alkoxide or the metal chelate compound is contained in the semiconductor nanoparticle layer 605.
  • the metal derived from the metal alkoxide or metal chelate compound may be contained in any layer as long as it can be present at the interface or intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer, When contained in the intermediate layer, the amount of metal alkoxide or metal chelate compound added can be reduced, which is preferable for reducing the production cost. Moreover, when it makes it contain in an intermediate
  • the metal oxide gas barrier layer generally has poor adhesion to the matrix resin (epoxy resin, acrylic resin, etc.) of the semiconductor nanoparticle layer, and the metal oxide gas barrier layer has a high temperature in a state where the metal oxide gas barrier layer is formed on the semiconductor nanoparticle layer.
  • the metal oxide gas barrier layer has a high temperature in a state where the metal oxide gas barrier layer is formed on the semiconductor nanoparticle layer.
  • peeling or floating occurs, and oxygen or water vapor permeates through the gap, thereby lowering the luminous efficiency of the semiconductor nanoparticles.
  • a metal alkoxide or a metal chelate compound is present at the interface or intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer. It is speculated that it can be bonded or interacted with the composition and the composition of the metal oxide gas barrier layer, and the adhesion between them can be improved.
  • ⁇ Preparation of Sample 1 (1) Preparation of Substrate As a substrate, a polyethylene terephthalate film having a thickness of 125 ⁇ m which is a thermoplastic resin support and easily bonded on both surfaces (abbreviated as Toyobo Co., Ltd., Cosmo Shine A4300, PET) The substrate was stored for 96 hours in an environment of a temperature of 25 ° C. and a relative humidity of 55% to adjust the humidity.
  • OPSTAR registered trademark
  • Z7501 manufactured by JSR Corporation
  • the first metal oxide gas barrier layer is formed on the substrate under the following film formation conditions (plasma CVD conditions). Was formed to a thickness of 300 nm.
  • Source gas Hexamethyldisiloxane (HMDSO) Supply amount: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
  • Reaction gas Oxygen gas (O 2 ) Supply amount: 500 sccm (0 ° C., 1 atm standard)
  • Degree of vacuum in the vacuum chamber 1.5 Pa
  • Applied power from the power source for plasma generation 0.9 kW
  • Frequency of power source for plasma generation 70 kHz
  • Transport speed of resin base unit 1.0 m / min
  • first intermediate layer Aluminum s-butoxide having the structure shown below was added to 10 g of 10% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials). 0.5 g of Wako Chemical Co., Ltd. (hereinafter referred to as C1) was added to prepare a first intermediate layer forming coating solution.
  • the prepared coating solution for forming the first intermediate layer was applied so that the layer thickness after drying was 90 nm and dried to form a first intermediate layer.
  • trioctylphosphine oxide TOPO
  • 12 g of 1-heptadecyl-octadecylamine HDA
  • the temperature of the chamber was heated to 220 ° C., and further increased to 250 ° C. over 120 minutes at a constant rate (0.25 ° C./min).
  • the obtained particles were CdSe / ZnS semiconductor nanoparticles having a core-shell structure in which the surface of the core portion of CdSe was covered with a ZnS shell. .
  • the CdSe / ZnS semiconductor nanoparticles were confirmed to have a core part particle size of 2.0 to 4.0 nm and a core part particle size distribution of 6 to 40%.
  • the optical characteristics it was confirmed that the emission peak wavelength was 410 to 700 nm and the emission half width was 35 to 90 nm. The luminous efficiency reached a maximum of 73.9%.
  • a UV curable resin adjusted to 95/5 was added to prepare a coating solution for forming a semiconductor nanoparticle layer in which the weight content of the semiconductor nanoparticles was 1%.
  • the prepared coating solution for forming a semiconductor nanoparticle layer is applied on the first intermediate layer so as to have a dry layer thickness of 100 ⁇ m, heated at 75 ° C. for 3 minutes, and then cured using a high-pressure mercury lamp; Curing was performed at 5 J / cm 2 . In this way, a semiconductor nanoparticle layer was formed.
  • Second intermediate layer In the same manner as the first intermediate layer, a second intermediate layer was formed on the surface of the semiconductor nanoparticle layer opposite to the surface where the first intermediate layer was formed.
  • Dibutyl ether is added to 10 g of 20% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-10, manufactured by AZ Electronic Materials Co., Ltd.) and diluted. Thus, a coating solution for forming a second metal oxide gas barrier layer was prepared.
  • the above-prepared coating solution for forming the second metal oxide gas barrier layer was applied with a wireless bar so that the (average) layer thickness after drying was 120 nm, and the atmosphere was at a temperature of 85 ° C. and a relative humidity of 55%. And dried for 1 minute, and further kept in an atmosphere of a temperature of 25 ° C. and a relative humidity of 10% (dew point temperature of ⁇ 8 ° C.) for 10 minutes to perform a dehumidification treatment to form a polysilazane-containing layer.
  • the polysilazane-containing layer formed above was subjected to ultraviolet irradiation treatment under the following conditions with the following ultraviolet device to modify the polysilazane-containing layer, and a second metal oxide gas barrier layer was formed on the second intermediate layer. .
  • the optical film of Sample 1 was produced as described above.
  • Preparation of Sample 5 (1) Preparation of Substrate As a substrate, a polyethylene terephthalate film having a thickness of 125 ⁇ m which is a thermoplastic resin support and easily bonded on both surfaces (abbreviated as Toyobo Co., Ltd., Cosmo Shine A4300, PET) The substrate was stored for 96 hours in an environment of a temperature of 25 ° C. and a relative humidity of 55% to adjust the humidity.
  • OPSTAR registered trademark
  • Z7501 manufactured by JSR Corporation
  • the prepared coating solution for forming the first metal oxide gas barrier layer was applied so that the layer thickness after drying was 180 nm and dried to form a polysilazane-containing layer.
  • the polysilazane-containing layer thus formed was subjected to ultraviolet irradiation treatment under the following conditions using the following ultraviolet device to modify the polysilazane-containing layer, thereby forming a first metal oxide gas barrier layer.
  • a semiconductor nanoparticle layer was formed on the first metal oxide gas barrier layer in the same manner as the formation of the semiconductor nanoparticle layer in the preparation of Sample 1.
  • Second Metal Oxide Gas Barrier Layer To 10 g of 10% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.), aluminum organic compound C2 was added. 0.1 g was added to prepare a coating solution for forming a second metal oxide gas barrier layer.
  • a second metal oxide gas barrier layer was formed on the semiconductor nanoparticle layer in the same manner as the first metal oxide gas barrier layer using the prepared coating liquid for forming the second metal oxide gas barrier layer. .
  • the optical film of Sample 5 was produced as described above.
  • first metal oxide gas barrier layer was formed on the first substrate in the same manner as the first metal oxide gas barrier layer of Sample 2.
  • Second Metal Oxide Gas Barrier Layer In the same manner as the first metal oxide gas barrier layer of Sample 2, a second metal oxide gas barrier layer was formed on the second substrate.
  • Formation of semiconductor nanoparticle layer A coating solution for forming a semiconductor nanoparticle layer prepared in the same manner as in Sample 2 was applied on the first intermediate layer so as to have a dry layer thickness of 100 ⁇ m, and at 75 ° C. for 3 minutes. Heated. The first base material and the second base material are pasted so that the second intermediate layer and the second metal oxide gas barrier layer face the semiconductor nanoparticle layer forming coating solution applied on the first intermediate layer. After combining, curing was performed using a high-pressure mercury lamp under curing conditions: 2.5 J / cm 2 . In this way, a semiconductor nanoparticle layer was formed.
  • the optical film of Sample 7 was produced as described above.
  • Coating solution for forming a first metal oxide gas barrier layer by adding dilute ether to 10 g of a 20% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-10, manufactured by AZ Electronic Materials Co., Ltd.) was prepared.
  • the prepared coating solution for forming the first metal oxide gas barrier layer was applied with a wireless bar so that the (average) layer thickness after drying was 120 nm, and the atmosphere was at a temperature of 85 ° C. and a relative humidity of 55%. And dried for 1 minute, and further kept in an atmosphere of a temperature of 25 ° C. and a relative humidity of 10% (dew point temperature of ⁇ 8 ° C.) for 10 minutes to perform a dehumidification treatment to form a polysilazane-containing layer.
  • the polysilazane-containing layer thus formed was subjected to ultraviolet irradiation treatment under the following conditions using the following ultraviolet device to modify the polysilazane-containing layer, thereby forming a first metal oxide gas barrier layer.
  • a UV curable resin solution adjusted to 95/5 was added to prepare a coating solution with a semiconductor nanoparticle mass content of 1%.
  • a hexane solution of aluminum organic compound C2 was added to the coating solution so that the total mass solid content was 0.5% to prepare a coating solution for forming a semiconductor nanoparticle layer.
  • the prepared coating solution for forming a semiconductor nanoparticle layer was applied on the first metal oxide gas barrier layer.
  • a second metal oxide gas barrier layer is formed on the semiconductor nanoparticle layer forming coating solution applied on the first metal oxide gas barrier layer in the same manner as the second metal oxide gas barrier layer of Sample 10. After the formation, curing was performed using a high-pressure mercury lamp at a curing condition of 2.5 J / cm 2 . In this way, a semiconductor nanoparticle layer was formed.
  • the atomic composition ratio of the metal derived from the metal alkoxide or the metal chelate compound with respect to the total atomic weight in the interface or intermediate layer is as follows: I asked for it. That is, the composition in the depth (thickness) direction from the surface of the first metal oxide gas barrier layer on the substrate side was measured by XPS analysis. The XPS analysis conditions are shown below.
  • ⁇ Device QUANTERASXM (manufactured by ULVAC-PHI)
  • X-ray source Monochromatic Al-K ⁇ Measurement area: Si2p, C1s, N1s, O1s ⁇
  • Sputtering ion Ar (2 keV)
  • Depth profile repeat measurement after sputtering for 1 minute
  • Data processing MultiPak (manufactured by ULVAC-PHI Co., Ltd.)
  • Quantification The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Note that the atomic composition ratio of the interface is the interface obtained by adding a region of 20 nm in the thickness direction around the position where the ratio of the constituent components of the first metal oxide gas barrier layer is minimum in the layer. As sought.
  • a metal alkoxide or metal is used at the interface between the semiconductor nanoparticle layer and the metal oxide gas barrier layer, or at an intermediate layer between the semiconductor nanoparticle layer and the metal oxide gas barrier layer.
  • the optical films of Samples 1 to 3, 5 to 7, and 10 to 17 of the present invention containing a metal derived from a chelate compound are superior to the optical films of Comparative Samples 4, 8, and 9 in functionality. I understand that. Since the optical film of the present invention has excellent bending resistance, adhesion between the semiconductor nanoparticle layer and the metal oxide gas barrier layer can be achieved by containing a metal alkoxide or a metal derived from a metal chelate compound at the interface or intermediate layer.
  • the optical film of the present invention is excellent in luminous efficiency, it does not increase the layer thickness of the entire optical film simply by containing a metal alkoxide or a metal derived from a metal chelate compound in the interface or intermediate layer, so that it is high. It is considered to have transparency. Moreover, since the light emission efficiency of the optical film of the present invention is not significantly lowered before and after storage, it is considered that the durability can be maintained for a long time.
  • the optical films of Samples 1 to 3, 5 to 7, and 10 to 17 of the present invention are all excellent in functionality, the metal derived from the metal alkoxide or the metal chelate compound is separated from the semiconductor nanoparticle layer and the metal oxide. As long as it exists at the interface or intermediate layer with the physical gas barrier layer, it may be contained in any position of the metal oxide gas barrier layer, the intermediate layer and the semiconductor nanoparticle layer, You can see that you can. In addition, since the optical films of Samples 13 and 14 of the present invention are superior in functionality to the optical films of Samples 12 and 15, the amount of metal contained in the interface or intermediate layer is 0.2 to It can be seen that it is preferably within the range of 10 at%.
  • the ultraviolet curable resin contained in the semiconductor nanoparticle layer is preferably an epoxy resin. I understand.
  • the metal derived from the metal alkoxide or metal chelate compound contained in the interface or intermediate layer is aluminum. It turns out that it is preferable.
  • the present invention is suitable for providing an optical film excellent in transparency that can suppress deterioration of semiconductor nanoparticles due to intrusion of oxygen, water, or the like over a long period of time, and a method for producing the same.

Abstract

La présente invention vise à fournir un film optique qui peut éliminer la détérioration de nanoparticules à semi-conducteurs en raison d'une invasion d'oxygène, d'eau ou analogue pendant une longue période de temps, tout en ayant une excellente transparence. Le film optique est caractérisé en ce qu'il comprend, sur une base (101), des couches de barrière de gaz d'oxyde métallique (102, 107) et une couche de nanoparticules à semi-conducteurs (105) qui contient des nanoparticules à semi-conducteurs (104) et une résine durcissable aux rayons ultraviolets. Le film optique est également caractérisé en ce que : un métal dérivé d'un composé d'alcoxyde métallique ou de chélate métallique est contenu au niveau des interfaces entre la couche de nanoparticules à semi-conducteurs (105) et les couches de barrière de gaz d'oxyde métallique (102, 107) ; ou, sinon, des couches intermédiaires (103, 106), qui contiennent un métal dérivé d'un composé d'alcoxyde métallique ou de chélate métallique, sont disposées respectivement entre la couche de nanoparticules à semi-conducteurs (105) et les couches de barrière de gaz d'oxyde métallique (102, 107).
PCT/JP2014/082200 2013-12-09 2014-12-05 Film optique, et procédé pour produire un film optique WO2015087792A1 (fr)

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JP2017136737A (ja) * 2016-02-03 2017-08-10 凸版印刷株式会社 蛍光体用保護フィルム、及びそれを用いた波長変換シート
KR20190044124A (ko) * 2016-09-28 2019-04-29 사빅 글로벌 테크놀러지스 비.브이. 양자점 필름과 이의 사용
JP2019116525A (ja) * 2017-12-26 2019-07-18 東洋インキＳｃホールディングス株式会社 量子ドットを含有するインキ組成物、それを用いたインクジェットインキ、およびそれらの用途

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JP2012023123A (ja) * 2010-07-13 2012-02-02 Sumitomo Bakelite Co Ltd 複合粒子、組成物、波長変換層および光起電装置。
WO2012064562A1 (fr) * 2010-11-10 2012-05-18 Nanosys, Inc. Films constitués de points quantiques, dispositifs d'éclairage et procédés d'éclairage
JP2013161865A (ja) * 2012-02-02 2013-08-19 Konica Minolta Inc Ｌｅｄ装置、及びその製造方法
WO2014196319A1 (fr) * 2013-06-05 2014-12-11 コニカミノルタ株式会社 Matériau optique, film optique, et dispositif luminescent
WO2014208478A1 (fr) * 2013-06-25 2014-12-31 コニカミノルタ株式会社 Matériau électroluminescent, son procédé de production, film optique et dispositif électroluminescent

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JP2012023123A (ja) * 2010-07-13 2012-02-02 Sumitomo Bakelite Co Ltd 複合粒子、組成物、波長変換層および光起電装置。
WO2012064562A1 (fr) * 2010-11-10 2012-05-18 Nanosys, Inc. Films constitués de points quantiques, dispositifs d'éclairage et procédés d'éclairage
JP2013161865A (ja) * 2012-02-02 2013-08-19 Konica Minolta Inc Ｌｅｄ装置、及びその製造方法
WO2014196319A1 (fr) * 2013-06-05 2014-12-11 コニカミノルタ株式会社 Matériau optique, film optique, et dispositif luminescent
WO2014208478A1 (fr) * 2013-06-25 2014-12-31 コニカミノルタ株式会社 Matériau électroluminescent, son procédé de production, film optique et dispositif électroluminescent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017136737A (ja) * 2016-02-03 2017-08-10 凸版印刷株式会社 蛍光体用保護フィルム、及びそれを用いた波長変換シート
KR20190044124A (ko) * 2016-09-28 2019-04-29 사빅 글로벌 테크놀러지스 비.브이. 양자점 필름과 이의 사용
KR102073080B1 (ko) * 2016-09-28 2020-03-02 사빅 글로벌 테크놀러지스 비.브이. 양자점 필름과 이의 사용
JP2019116525A (ja) * 2017-12-26 2019-07-18 東洋インキＳｃホールディングス株式会社 量子ドットを含有するインキ組成物、それを用いたインクジェットインキ、およびそれらの用途

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