WO2016076219A1 - Film optique et procédé de fabrication d'un film optique - Google Patents

Film optique et procédé de fabrication d'un film optique Download PDF

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Publication number
WO2016076219A1
WO2016076219A1 PCT/JP2015/081301 JP2015081301W WO2016076219A1 WO 2016076219 A1 WO2016076219 A1 WO 2016076219A1 JP 2015081301 W JP2015081301 W JP 2015081301W WO 2016076219 A1 WO2016076219 A1 WO 2016076219A1
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layer
gas barrier
optical film
barrier layer
polymer
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PCT/JP2015/081301
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English (en)
Japanese (ja)
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晃矢子 和地
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コニカミノルタ株式会社
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials

Definitions

  • the present invention relates to an optical film and a method for producing the same. More specifically, semiconductor nanoparticles can be prevented from degrading due to the intrusion of oxygen, water, etc. over a long period of time, with excellent failure resistance (dark spot resistance) and end film peeling resistance (adhesion) during punching, and luminous efficiency
  • the present invention relates to a high optical film and a method for producing the same.
  • semiconductor nanoparticles have gained commercial interest due to their size-tunable electronic properties.
  • Semiconductor nanoparticles can be used in a wide variety of applications, such as biolabeling, solar power generation, catalysis, bioimaging, light emitting diode (Light Emitting Diode, abbreviated as “LED”), general spatial illumination, and electroluminescent display. It is expected to be used in the field.
  • LED Light Emitting Diode
  • a liquid crystal display device (Liquid Crystal Display, abbreviated as “LCD”) is emitted by irradiating semiconductor nanoparticles dispersed in a transparent matrix resin material with LED light.
  • LCD Liquid Crystal Display
  • a technique for increasing the amount of incident light on the LCD and improving the brightness of the LCD has been proposed.
  • deterioration preventing means for example, by heating the semiconductor nanoparticles coated with silazane on the surface, thermally decomposing the silazane, and forming a silica film on the surface of the semiconductor nanoparticles to coat,
  • a surface treatment method for improving the weather resistance of semiconductor nanoparticles is disclosed (for example, see Patent Document 1).
  • the surface treatment method disclosed here coats each particle, the yield of the semiconductor nanoparticles after coating is low, the luminous efficiency after coating decreases, and the matrix due to the surface coating with silica. There was a problem that the dispersion stability in the resin was lowered.
  • an optical material layer including the semiconductor nanoparticles provided on the substrate is covered with an adhesive material, and another method is performed through the adhesive material.
  • a method is disclosed in which a sealed structure is formed by adhering substrates to sandwich an optical material layer between two substrates (see, for example, Patent Document 2).
  • the adhesive material is also required to have a barrier against oxygen and moisture entering from the external environment, a material having a specific structure is inevitably required, resulting in an increase in manufacturing cost.
  • cures an optical material layer, and the process which hardens an adhesive material the manufacturing cost accompanying the increase in the number of processes will also rise.
  • a phosphor in which a matrix resin layer in which semiconductor nanoparticles are dispersed is provided on a substrate, and a water-impermeable material layer formed of a silicone resin, a cycloolefin resin, a fluoride-based resin, or the like is laminated thereon.
  • a film is disclosed (for example, see Patent Document 3). According to Patent Document 3, even when a chalcogenite-based phosphor material is used as a semiconductor nanoparticle, the non-water-permeable material layer prevents the semiconductor nanoparticle from coming into contact with oxygen or water, thereby improving durability. It is supposed to be possible.
  • the non-water-permeable material layer formed of silicone resin, cycloolefin resin, fluoride-based resin, etc. has a low barrier property against oxygen and moisture, and maintains the performance of semiconductor nanoparticles.
  • the barrier layer needs to have a layer thickness of 5 ⁇ m or more, and in reality, a layer thickness of 20 ⁇ m or more. Therefore, there is a problem that the optical characteristics deteriorate as the layer thickness increases. I had it.
  • microbeads in which semiconductor nanoparticles are embedded in a host matrix material
  • a host matrix material polyacrylate, polystyrene, polyester and the like are described.
  • a method of further coating the surface of these microbeads with a coating material such as a dielectric, a metal oxide, or a silica-based material is disclosed.
  • a coating material such as a dielectric, a metal oxide, or a silica-based material.
  • the adhesion between the microbeads and the coating material is insufficient.
  • the optical film when punched into a predetermined size, delamination occurs at the end, When oxygen or moisture permeates from the surrounding environment where the separation occurs, the semiconductor nanoparticles are deteriorated, resulting in a decrease in luminous efficiency.
  • JP 2001-181620 A Special table 2013-508895 gazette Japanese Patent No. 4579065 International Publication No. 2013/041864
  • the present invention has been made in view of the above-mentioned problems and situations, and the solution is to suppress deterioration of semiconductor nanoparticles due to infiltration of oxygen, water, etc. over a long period of time, and failure resistance (dark spot resistance, hereinafter, It is also referred to as DS resistance) and an optical film having excellent peeling resistance (adhesiveness) and high luminous efficiency, and a manufacturing method thereof.
  • an optical film at least a base material A, a first gas barrier layer A having a metal oxide, semiconductor nanoparticles, and ultraviolet curing A structure in which a semiconductor nanoparticle layer containing a mold resin, a first gas barrier layer B and a base material B are laminated in this order, and further containing a polymer compound having a cyclic structure group, It is possible to suppress degradation of semiconductor nanoparticles due to the intrusion of oxygen, water, etc. over a long period of time, and to obtain an optical film having excellent failure resistance and film peeling resistance (adhesion) at the end, and high luminous efficiency. I found it.
  • At least the substrate A, the first gas barrier layer A having a metal oxide, the semiconductor nanoparticles containing the semiconductor nanoparticles and the ultraviolet curable resin, the first gas barrier layer B and the substrate B are arranged in this order.
  • the polymer layer A is provided, and the semiconductor nanoparticles and the ultraviolet curable resin are included.
  • the polymer layer B is included between the semiconductor nanoparticle layer containing the first gas barrier layer B and the polymer layer A and the polymer layer B contain at least the polymer compound having the cyclic structure group.
  • Content of the polymer compound having the cyclic structure group in the polymer layer A and the polymer layer B is in a range of 4.0 to 30% by mass with respect to the total mass of the ultraviolet curable resin. 4.
  • Content of the polymer compound having the cyclic structure group in the polymer layer A and the polymer layer B is in the range of 5.0 to 20% by mass with respect to the total mass of the ultraviolet curable resin. 4.
  • the content of the polymer compound having a cyclic structure group in the semiconductor nanoparticle layer is in the range of 4.0 to 30% by mass with respect to the total mass of the ultraviolet curable resin.
  • the content of the polymer compound having a cyclic structure group in the semiconductor nanoparticle layer is in the range of 5.0 to 20% by mass with respect to the total mass of the ultraviolet curable resin.
  • Item 10 The optical film as described in Item 9, wherein the polymer compound having a benzene ring has a weight average molecular weight in the range of 10,000 to 300,000.
  • Item 11 The optical film according to Item 9 or 10, wherein the polymer compound having a benzene ring is polystyrene.
  • the second gas barrier layer A containing perhydropolysilazane is included between the semiconductor nanoparticle layer containing the semiconductor nanoparticles and the ultraviolet curable resin and the first gas barrier layer B.
  • the optical film according to any one of Items 1 to 11.
  • At least the substrate A, the first gas barrier layer A having a metal oxide, the semiconductor nanoparticles containing the semiconductor nanoparticles and the ultraviolet curable resin, the first gas barrier layer B and the substrate B are arranged in this order.
  • a second unit in which a first gas barrier layer B having an oxide and a polymer layer B containing at least a polymer compound having a cyclic structure group are stacked, a semiconductor nanoparticle layer surface of the first unit, and a second unit Item 14.
  • a coating liquid containing perhydropolysilazane is used between the first gas barrier layer A and the polymer layer A containing the polymer compound having at least a cyclic structure group, and the second gas is irradiated by vacuum ultraviolet light.
  • a coating liquid containing perhydropolysilazane is formed between the step of forming the gas barrier layer A, the first gas barrier layer B, and the polymer layer B containing the polymer compound having at least the cyclic structure group.
  • the semiconductor nanoparticle layer surface of the first unit and the first gas barrier layer B surface of the second unit are bonded and then irradiated with ultraviolet rays. 14.
  • the semiconductor nanoparticle layer is formed by forming a coating film with a coating liquid containing semiconductor nanoparticles, an ultraviolet curable resin monomer, and a polymer compound having a cyclic structure group, and then irradiating the coating film with ultraviolet rays.
  • Item 18 A method for producing an optical film according to Item 16,
  • deterioration of semiconductor nanoparticles due to infiltration of oxygen, water, or the like can be suppressed over a long period of time, failure resistance (DS resistance), and end film peeling resistance (adhesion) during stamping are excellent, and luminous efficiency Can provide an optical film and a method for producing the same.
  • the substrate A the first gas barrier layer A having a metal oxide, the semiconductor nanoparticles containing the semiconductor nanoparticles and the ultraviolet curable resin, the first gas barrier. It has a layer B and a base material B in this order, and further contains a polymer compound having a cyclic structure group.
  • the polymer compound having a cyclic structure group according to the present invention provides a polymer layer between the first gas barrier layer having a metal oxide and the semiconductor nanoparticle layer containing the semiconductor nanoparticles and the ultraviolet curable resin, You may make it exist in the layer, or you may make it coexist in the semiconductor nanoparticle layer containing a semiconductor nanoparticle and an ultraviolet curable resin.
  • the presence of such a polymer compound having a cyclic structure group in the polymer layer or semiconductor nanoparticle layer improves the end film peeling resistance (adhesion) and the associated failure resistance (DS resistance) during punching. can do.
  • the light emission efficiency can be further improved by adopting such a configuration.
  • the reason why the end film peeling resistance at the time of the punching process, that is, the adhesiveness and the failure resistance associated therewith is improved by the configuration specified in the present invention is estimated as follows.
  • the flexibility of the semiconductor nanoparticle layer and the adjacent layer is improved, and stress is applied to the optical film.
  • the flexibility and stress relaxation in the interlayer or in the layer by the polymer compound having a cyclic structure group is made, for example, when the produced optical film is punched into a predetermined size, the stress in the vertical direction can be relaxed, Peeling between layers can be prevented, and as a result, damage to semiconductor nanoparticles caused by oxygen and moisture entering from the cross-sectional side can be prevented, and fault tolerance (DS resistance) can be improved.
  • the reason why the luminous efficiency is improved is that a polymer compound having a cyclic structure group, for example, polystyrene, is added to the semiconductor nanoparticle layer or the adjacent polymer layer, thereby coexisting matrix resin such as epoxy acrylate. It is presumed that the photon efficiency has been improved by increasing the degree of diffusion of light emitted from the semiconductor nanoparticle layer due to a difference in refractive index within the layer or between layers with the resin.
  • a polymer compound having a cyclic structure group for example, polystyrene
  • the optical film of the present invention includes at least a substrate A, a first gas barrier layer A having a metal oxide, a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, a first gas barrier layer B, and It has a base material B in this order, and further contains a polymer compound having a cyclic structure group.
  • This feature is a technical feature common to or corresponding to each of claims 1 to 18.
  • the first gas barrier layer A having the metal oxide, the semiconductor nanoparticles, and the ultraviolet curable resin are used.
  • the polymer layer A and the polymer layer B contain at least the polymer compound having the cyclic structure group, and the polymer layer A and the polymer layer B contain an ultraviolet curable resin.
  • the configuration is preferable in that the adhesion between each gas barrier layer and the semiconductor nanoparticle layer can be further improved, and the failure resistance (DS resistance) can also be improved. .
  • each gas barrier layer includes a semiconductor nanoparticle layer containing a semiconductor nanoparticle and an ultraviolet curable resin containing a polymer compound having a cyclic structure group according to the present invention. And the semiconductor nanoparticle layer are further improved, and failure resistance (DS resistance) can be improved.
  • the polymer layer A and the polymer layer B when the polymer layer A and the polymer layer B are configured to contain an ultraviolet curable resin together with a polymer compound having a cyclic structure group, the polymer layer A and the polymer layer B have the cyclic structure group.
  • the content of the polymer compound is in the range of 4.0 to 30% by mass, and more preferably in the range of 5.0 to 20% by mass, with respect to the total mass of the ultraviolet curable resin.
  • the viewpoint that the stress relaxation effect is the optimum condition, and the film peeling resistance (adhesion) at the edge during punching processing and durability in high temperature and high humidity environments are improved, thereby further improving the luminous efficiency. To preferred.
  • the content of the polymer compound having a cyclic structure group in the semiconductor nanoparticle layer is in the range of 4.0 to 30% by mass with respect to the total mass of the ultraviolet curable resin. Furthermore, within the range of 5.0 to 20% by mass, the stress relaxation effect is the optimum condition, and the film peel-off resistance (adhesion) at the end during punching and durability in a high-temperature and high-humidity environment. This is preferable from the viewpoint of improving the light emission efficiency and further improving the light emission efficiency.
  • the polymer compound having a cyclic structure group is a polymer compound having a benzene ring, and the polymer compound having a benzene ring has a weight average molecular weight of 10,000 to 300,000. It is preferable that the polymer compound having a benzene ring is in the range, in particular, polystyrene, from the viewpoint that the above-described effect intended by the present invention can be further expressed.
  • the gas barrier layer A having a metal oxide, and a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin
  • the method for producing an optical film of the present invention includes at least a substrate A, a first gas barrier layer A having a metal oxide, a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, and a first gas barrier.
  • the layer B and the base material B are formed and manufactured in this order, and further include a polymer compound having a cyclic structure group.
  • the first gas barrier layer A having a metal oxide formed on the substrate A by chemical vapor deposition or physical vapor deposition, at least a cyclic structure is used.
  • perhydropolysilazane is contained between the first gas barrier layer A and the polymer layer A containing the polymer compound having at least the cyclic structure group.
  • the first gas barrier layer A having at least a metal oxide formed on the substrate A by chemical vapor deposition or physical vapor deposition, At least chemical vapor deposition or physics on the first unit in which semiconductor nanoparticles containing a semiconductor nanoparticle, an ultraviolet curable resin and a polymer compound having a cyclic structure group are laminated in this order, and the substrate B After producing the 2nd unit which laminated
  • a semiconductor nanoparticle layer is prepared by preparing a coating solution containing semiconductor nanoparticles, an unpolymerized ultraviolet curable resin monomer, and a polymer compound having a polymerized cyclic structure group. It is preferable from the viewpoint that a stable semiconductor nanoparticle layer can be formed after forming a coating film by using ultraviolet irradiation to the coating film.
  • the optical film of the present invention includes at least a substrate A, a first gas barrier layer A having a metal oxide, a semiconductor nanoparticle layer containing semiconductor nanoparticles and an ultraviolet curable resin, a first gas barrier layer B, and It has a base material B in this order, and further contains a polymer compound having a cyclic structure group.
  • Embodiment 1 at least the substrate A, the first gas barrier layer A having a metal oxide, the semiconductor nanoparticles containing the semiconductor nanoparticles and the ultraviolet curable resin, the first gas barrier layer B and the base material B in this order, and the polymer layer A is provided between the first gas barrier layer A having a metal oxide and the semiconductor nanoparticle layer containing the semiconductor nanoparticles and the ultraviolet curable resin. And having a polymer layer B between the semiconductor nanoparticle layer containing the semiconductor nanoparticles and the ultraviolet curable resin and the first gas barrier layer B, both of the polymer layer A and the polymer layer B are in the present invention. A constitution containing a polymer compound having such a cyclic structural group is preferred.
  • the polymer layer A and the polymer layer B containing the polymer compound having a cyclic structure group according to the present invention further contain an ultraviolet curable resin.
  • the semiconductor nanoparticle layer containing B and the base material B in this order and containing the semiconductor nanoparticles and the ultraviolet curable resin contains a polymer compound having a cyclic structure group according to the present invention.
  • FIG. 1 shows a typical configuration of an optical film (1) having a conventional semiconductor nanoparticle layer. From the bottom, a base A (2A) and a first gas barrier layer A (3A) having a metal oxide are shown.
  • the semiconductor nanoparticle layer (4) constituted by dispersing and holding the semiconductor nanoparticles (5) in the ultraviolet curable resin (6) as the resin matrix, the first gas barrier layer B (3B), and finally The base material B (2B) is laminated.
  • FIGS. 2A, 2B, 3A, and 3B show typical configurations of the optical film of the present invention.
  • FIGS. 2A and 2B are schematic cross-sectional views showing an example of the configuration of Embodiment 1 of the optical film of the present invention.
  • Semiconductor nanoparticle layer (4), polymer layer B (7B), first gas barrier layer B (3B), and substrate which are configured by dispersing and holding semiconductor nanoparticles (5) in mold resin (6) B (2B) is laminated in this order.
  • each of the polymer layer A (7A) and the polymer layer B (7B) includes a polymer compound having a cyclic structure group according to the present invention, and further includes an ultraviolet curable resin. It may be a configuration.
  • a first method is the first having at least a metal oxide formed on the substrate A (2A) by chemical vapor deposition or physical vapor deposition.
  • Gas barrier layer A (3A) polymer layer A (7A) containing a polymer compound having a cyclic structure group, and semiconductor nanoparticle layer (4) containing semiconductor nanoparticles (5) and ultraviolet curable resin (6)
  • a first gas barrier layer B having a metal oxide at least by chemical vapor deposition or physical vapor deposition on the base unit B (2B) and the base unit B (2B).
  • a first gas barrier layer A (3A) and a polymer layer A (7A) containing a polymer compound having a cyclic structure group In the meantime, a coating liquid containing perhydropolysilazane was used, and the second gas barrier layer A (8A), the first gas barrier layer B (3B), and a ring structure group were formed by irradiation with vacuum ultraviolet light.
  • a configuration is shown in which a coating liquid containing perhydropolysilazane is used and a second gas barrier layer B (8B) is irradiated with vacuum ultraviolet light between the polymer layer B (7B) containing a molecular compound.
  • the optical film (1) having the configuration shown in FIG. 2B is also prepared with the first unit (U1) and the second unit (U2), and then the semiconductor nanoparticle layer of the first unit (U1).
  • the surface and the polymer layer B (7B) surface of the second unit (U2) are bonded and pressure-bonded, ultraviolet rays are irradiated from one surface or both surfaces, and the ultraviolet curable type contained in each layer It is manufactured by curing the resin.
  • 3A and 3B are schematic cross-sectional views showing an example of the configuration of Embodiment 2 of the optical film of the present invention.
  • the base material A (2A), the first gas barrier layer A (3A) having a metal oxide, an ultraviolet curable resin, and a polymer compound having a cyclic structure group The semiconductor nanoparticle layer (4), the first gas barrier layer B (3B), and the base material B (2B) constituted by dispersing and holding the semiconductor nanoparticles (5) in the hybrid resin layer (9) comprising Are stacked in this order.
  • a first method is one in which at least a metal oxide formed on a base material A (2A) by chemical vapor deposition or physical vapor deposition is used.
  • Semiconductor nanoparticles comprising a semiconductor resin (5) dispersed and held in a gas barrier layer A (3A), a hybrid resin layer (9) comprising a polymer compound having an ultraviolet curable resin and a cyclic structure group
  • the surface of the semiconductor nanoparticle layer (4) of the first unit (U1) and the polymer layer B (7B) of the second unit (U2) After bonding and pressure bonding to the surface One side or the ultraviolet from both sides are irradiated, it is produced by curing the ultraviolet curable resin contained in each layer.
  • the semiconductor nanoparticle layer (4) constituting the first unit (U1) is formed by coating with a coating liquid containing semiconductor nanoparticles, a UV curable resin monomer, and a polymer compound having a cyclic structure group
  • a method of curing the ultraviolet curable resin monomer of the semiconductor nanoparticle layer (4) by irradiating with ultraviolet rays after being bonded to the second unit (U2) is preferable.
  • FIG. 3B is different from FIG. 3A in that the first gas barrier layer A (3A) having a metal oxide, an ultraviolet curable resin, a polymer compound having a cyclic structure group, and semiconductor nanoparticles (5) are dispersed and held.
  • a second gas barrier layer A (8A) containing perhydropolysilazane between the semiconductor nanoparticle layer (4) and the semiconductor nanoparticle layer (4) and the first gas The structure which has 2nd gas barrier layer B (8B) containing perhydropolysilazane between barrier layer B (7B) is shown.
  • the optical film of the present invention is characterized by containing a polymer compound having a cyclic structure group.
  • the polymer layer (7A and 7B) or FIG. As shown to 3A and FIG. 3B, it is preferable that the semiconductor nanoparticle layer (4) containing the semiconductor nanoparticles (5) and the ultraviolet curable resin (6) contains a polymer compound having a cyclic structure group. It is.
  • the polymer compound having a cyclic structural group as used in the present invention is a polymer compound having an alicyclic hydrocarbon group, an aromatic group, or a heterocyclic group as at least a cyclic structural group in the structure.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.).
  • a cycloalkyl group for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.
  • aromatic group examples include a phenyl group, a naphthyl group, and an anthracenyl group.
  • heterocyclic group examples include furan ring, pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine ring, thiazoline.
  • the polymer compound (polymer) having a cyclic structure group according to the present invention can be used without particular limitation as long as it has a cyclic structure group in the polymer, and various polymers can be exemplified.
  • polymers described in JP-T-2002-509279 examples include polymers described in JP-T-2002-509279. Specific examples include, as a basic structure, polyethylene naphthalate (PEN) and isomers thereof (for example, 2,6-, 1,4-, 1,5-, 2,7- and 2,3-PEN), Polyalkylene terephthalate (for example, polyethylene terephthalate (PET), polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate), polyimide (for example, polyacrylimide), polyetherimide, atactic polystyrene, polycarbonate, Polymethacrylate (eg, polyisobutyl methacrylate, polypropyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate (PMMA)), polyacrylate (eg, polybutyl acrylate, polymethyl acrylate, etc.), Rulose derivatives (for example, ethyl cellulose,
  • the polymer compound (polymer) having a cyclic structure group according to the present invention has a structure having an olefin hydrocarbon group (ethylene hydrocarbon group) as a polymerizable group in the main chain and a cyclic structure group in the side chain.
  • a polymer compound having a structure having a benzene ring as a cyclic structure in the side chain is preferred, and polystyrene is particularly preferred.
  • the polymer compound (polymer) having a cyclic structure group according to the present invention is a polymer having a structure having an acryloyl group as a polymerizable group in the main chain and a group having a cyclic structure group in the side chain, and an ultraviolet ray.
  • An acrylate compound that undergoes a polymerization reaction upon irradiation is preferred.
  • polystyrene an acryloyl group as a polymerizable group in the main chain shown below, and a cyclic structure group in a side chain.
  • An acrylate compound comprising a monomer containing a group can be mentioned.
  • the monomer examples include a photo-curable monomer (trade name: NK ester) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Examples of monofunctional acrylate monomers include ethoxylated o-phenylphenol acrylate (product name: A-LEN-10), phenoxypolyethylene glycol acrylate (product name: AMP-20GY), and the like.
  • Examples of the bifunctional acrylate monomer include propoxylated ethoxylated bisphenol A diacrylate (product name: A-B1206PE), ethoxylated bisphenol A diacrylate (product names: ABE-300, A-BPE-10, A-BPE-20, A-BPE-30), propoxylated bisphenol A diacrylate (product name: A-BPP-3), tricyclodecane dimethanol diacrylate (product name: A-DCP), and the like.
  • phenoxyethylene glycol methacrylate (product name: PHE-1G) is used as the monofunctional methacrylate
  • ethoxylated bisphenol A dimethacrylate (product names: BPE-80N, BPE-100, BPE-200, BPE) is used as the bifunctional acrylate monomer.
  • tricyclodecane dimethanol dimethacrylate product name: DCP
  • an ultraviolet absorbing polymer manufactured by Shin-Nakamura Chemical Co., Ltd. can be mentioned.
  • the polymer compound having a cyclic structure group according to the present invention preferably has a weight average molecular weight in the range of 50,000 to 300,000, more preferably in the range of 10,000 to 50,000.
  • gel permeation chromatography as a method for measuring the weight average molecular weight of the polymer compound, gel permeation chromatography can be used.
  • Base material As a base material (2A and 2B described in FIGS. 2A, 2B and 3A, and 3B) disposed on both surfaces of the optical film of the present invention, there is no particular limitation, such as glass and plastic. What you have is 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 light transmittance as used in the field of this invention means that the light transmittance in wavelength 550nm is 50% or more, Preferably it is 60% or more, More preferably, it is 70% or more.
  • the thickness of the substrate is not particularly limited.
  • polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose triacetate.
  • TAC cellulose acetate butyrate, cellulose acetate propionate
  • CAP cellulose esters
  • polyvinylidene chloride polyvinyl alcohol, polyethylene vinyl alcohol, Syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyether Sulfone (abbreviation: PES), polyphenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel ( And cycloolefin (abbreviation: COP) resin such as trade name of Mitsui Chemicals.
  • PES polyether Sulfone
  • various functional layers such as a clear hard coat layer, an adhesion layer, or a smooth layer may be provided on the surface of the substrate as necessary.
  • the semiconductor nanoparticle layer (Embodiment 2) is preferably configured to contain a polymer compound having a cyclic structure group according to the present invention.
  • the semiconductor nanoparticle layer according to the present invention is configured to contain semiconductor nanoparticles and an ultraviolet curable resin.
  • the semiconductor nanoparticle layer may have a laminated structure in which two or more layers are 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.
  • the semiconductor nanoparticle layer according to 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 which is composed of a crystal of a semiconductor material and has a quantum confinement effect, and the particle diameter thereof is in the range of several nanometers to several tens of nanometers. That means that the following quantum dot effect can be 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”. expressed.
  • 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 “semiconductor nanoparticle”.
  • the average particle size of the semiconductor nanoparticles is in the range of several nanometers to several tens of nanometers, but is preferably 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. Note that 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. Can be expressed.
  • 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 semiconductor nanoparticle layer forming coating solution contains semiconductor nanoparticles. It is preferable that a surface modifier is attached in the vicinity of the surface. Thereby, the dispersion stability of the semiconductor nanoparticles in the coating solution for forming the semiconductor nanoparticle layer can be made particularly excellent.
  • 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 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.
  • combination of the semiconductor nanoparticle in a liquid phase manufacturing method is called initial stage 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 together with the semiconductor nanoparticles.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable.
  • 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.
  • the semiconductor nanoparticle layer and the metal oxide gas barrier layer can interact with or react with a metal alkoxide or a metal chelate compound present at the metal oxide gas barrier layer side interface of the semiconductor nanoparticle layer, although it is not certain. It is estimated that the adhesion and durability 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 resin examples include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyol. No. 151112 can be used.
  • ultraviolet curable epoxy acrylate resin examples include an epoxy acrylate oligomer, a reactive diluent and a photopolymerization initiator added to the oligomer, and a reaction product. Those described in JP-A No. 1-105738 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.
  • 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 (above, 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 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM70 3, KRM 7039, KRM 7130, K
  • 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.
  • 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 in the range of 0.1 to 15 parts by mass, preferably 1 to 10 parts per 100 parts by mass of the ultraviolet curable resin composition. Within the range of parts by mass.
  • the content of the polymer compound having a cyclic structure group in the semiconductor nanoparticle layer is within a range of 4.0 to 30% by mass with respect to the total mass of the ultraviolet curable resin constituting the semiconductor nanoparticle layer. It is preferable that it is within a range of 5.0 to 20% by mass.
  • a semiconductor nanoparticle layer-forming coating solution is prepared by containing semiconductor nanoparticles and an ultraviolet curable resin, and as a second embodiment, a polymer compound having a cyclic structure group.
  • the semiconductor nanoparticle layer forming coating solution can be applied on a substrate and then dried.
  • the active energy ray irradiation treatment of the formed semiconductor nanoparticle layer with ultraviolet rays or the like is a method of irradiating and curing immediately after forming the semiconductor nanoparticle layer, or by laminating all the constituent layers to form an optical film. After production, a method of performing active energy ray irradiation treatment with ultraviolet rays or the like in a lump may be used.
  • any appropriate method can be adopted as a method of applying the coating solution for forming the 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 in the range of 0.1 to 40 ⁇ m as a wet film thickness, and preferably in the range of 0.5 to 30 ⁇ m.
  • the dry film thickness is in the range of 0.1 to 30 ⁇ m, preferably in the range of 0.5 to 20 ⁇ m, in terms of average film thickness.
  • 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 (eg, toluene, xylene, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), ketones (eg, acetone). , Methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, and 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 ray is within the range of usually 50 ⁇ 5000mJ / cm 2, preferably in the range of 50 ⁇ 1500mJ / cm 2.
  • an ultraviolet curable type is provided between the first gas barrier layer (3A and 3B) and the semiconductor nanoparticle layer and the polymer layer (4).
  • a configuration in which polymer layers (7A and 7B) containing a resin are provided and a polymer compound having a cyclic structure group is contained in the polymer layer is one of preferred embodiments.
  • UV curable resin As the ultraviolet curable resin applicable to the polymer layer according to the present invention, the same ultraviolet curable resin as described in the semiconductor nanoparticle layer can be used, and examples thereof include an ultraviolet curable urethane acrylate resin and an ultraviolet curable resin.
  • a curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable epoxy resin, or the like is preferably used.
  • the content of the polymer compound having a cyclic structure group in the polymer layer is in the range of 4.0 to 30% by mass with respect to the total mass of the ultraviolet curable resin constituting the polymer layer. More preferably, it is in the range of 5.0 to 20% by mass.
  • Method of forming polymer layer As a method for forming the polymer layer, a method similar to the method for forming the semiconductor nanoparticle layer can be used, and a coating solution for forming a polymer layer containing an ultraviolet curable resin and a polymer compound having a cyclic structure group is prepared. After application, it can be formed by drying.
  • the coating amount is suitably in the range of 0.1 to 40 ⁇ m as a wet film thickness, and preferably in the range of 0.5 to 30 ⁇ m.
  • the dry film thickness is in the range of an average film thickness of 0.1 to 30 ⁇ m, preferably in the range of 0.5 to 20 ⁇ m.
  • the formed polymer layer is cured by irradiation with active energy rays such as ultraviolet rays.
  • This ultraviolet irradiation treatment is a method of irradiating and curing immediately after forming the polymer layer, or a method in which all the constituent layers are laminated to produce an optical film and then subjected to the ultraviolet irradiation treatment collectively. It may be.
  • ⁇ Metal oxide gas barrier layer ⁇ In the optical film of the present invention, as shown in FIG. 2A, between the substrate (2A and 2B) and the polymer layer (7A and 7B), or as shown in FIG. 3A, the substrate (2A and 2B) A first gas barrier layer (7A and 7B) having a metal oxide is provided between the semiconductor nanoparticle layer (4).
  • the first gas barrier layer (7A and 7B) having a metal oxide is configured to contain a metal oxide, and is intended to prevent oxygen and water from entering the semiconductor nanoparticle layer (4). It is a layer to do.
  • a physical vapor deposition method in which a metal or an oxide thereof is evaporated and vapor-deposited to form a film on a substrate, or a target thin film component is used.
  • a chemical vapor deposition method in which a raw material gas (for example, an organosilicon compound typified by tetraethoxysilane (TEOS), etc.) is supplied and a film is deposited by a chemical reaction in the substrate surface or in the gas phase.
  • TEOS tetraethoxysilane
  • a sputtering method in which metal Si is evaporated and deposited on a substrate in the presence of oxygen using a semiconductor 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 a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound as shown in FIG. 4 described later. It is a method using.
  • the layer thickness of the first 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 first 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 (occurrence of cracks and the like) can be prevented.
  • the first gas barrier layer is preferably formed on the substrate surface using a roll-to-roll plasma CVD method.
  • a forming apparatus that can be used for forming the first gas barrier layer by plasma CVD 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. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers to which the magnetic field is applied.
  • a plasma CVD apparatus S1 as shown in FIG. 4 can be used, and by applying the plasma CVD apparatus (S1), a gas barrier layer is formed by a roll-to-roll method using a plasma CVD method. It becomes possible to form.
  • the plasma CVD apparatus (S1) mainly includes a roll-shaped feeding roller (11A) in which the base material (2) is laminated, and a transport roller for transporting the base material (2). (22 and 23), a pair of film forming rollers (31 and 32), a film forming gas supply pipe (41), a plasma generating power source (51), and a winding roller (11B).
  • a magnetic field generator (61 and 62) fixed so as not to rotate even when the film forming roller rotates is provided inside the film forming roller (31) and the film forming roller (32), respectively. .
  • the respective constituent parts such as the film forming rollers (31 and 32) are arranged in a vacuum chamber (16) as shown in FIG. Further, a vacuum pump (17) as a vacuum exhaust means is connected to the vacuum chamber (16) via an exhaust port (18), and the vacuum pump (17) and the film forming gas supply pipe (41) are connected.
  • the pressure in the vacuum chamber (16) can be adjusted as appropriate.
  • the vacuum pump (17) can evacuate the inside of the vacuum chamber (16) to a vacuum state or a low pressure state corresponding to vacuum.
  • a base material is provided on each of the pair of film forming rollers (31 and 32) as shown in FIG. (2) is routed and disposed, and a voltage is applied between the pair of film forming rollers (31 and 32) to generate plasma, thereby forming a plasma discharge space.
  • the first gas barrier layer-forming film forming gas is supplied from the film forming gas supply pipe (41) to the discharge space, while the first surface of the substrate (2) being continuously conveyed is supplied to the first surface. After forming a gas barrier layer, it is wound up in a roll shape by a winding roller (11B).
  • the surface temperature of the film forming rollers (31 and 32) at the time of forming the first gas barrier layer is controlled within a certain range.
  • the specific temperature range of the surface temperature of each film forming roller varies depending on the constituent material of the base material (2) to be applied, but is generally within the temperature range of 0 to 150 ° C., more preferably 15 It is in a temperature range of ⁇ 80 ° C., more preferably in a temperature range of 20 ° C. to 60 ° C.
  • the surface of the film forming roller is coated with titanium, stainless steel, chrome plating, cemented carbide, or the like.
  • coolant or a heat carrier is mentioned. And it is preferable to control so that the surface temperature of the film-forming roller (31 and 32) may become the said range by distribute
  • a well-known thing can be used as a mechanism which distribute
  • the conveying speed (line speed) of the substrate (2) can be appropriately adjusted according to the type of film forming gas, the pressure in the vacuum chamber, etc., but is within the range of 0.25 to 100 m / min. It is more preferable that it be within the range of 0.3 to 30 m / min. If a conveyance speed is 0.25 m / min or more, generation
  • a film forming gas or the like a raw material gas, a reactive gas, a carrier gas, a discharge gas, or the like can be used alone or in combination of two or more. .
  • the source gas in the film forming gas used for forming the first gas barrier layer can be appropriately selected and used depending on 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 first 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 first 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 ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. It is preferable that the ratio of the reaction gas is not excessively increased from the viewpoint that excellent gas barrier properties and bending resistance can be obtained as the first gas barrier layer to be formed.
  • the film forming gas contains the organosilicon compound and oxygen, it may be less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. preferable.
  • the pressure (degree of vacuum) 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 about 0.5 to 50 Pa.
  • the optical film of the present invention may include a plurality of gas barrier layers.
  • the second gas barrier A (8A and 8B) formed by a coating method may be used. ) Is preferable.
  • the optical film of the present invention As shown in FIG. 2B, between the first gas barrier layer (3A and 3B) and the polymer layer A (7A and 7B) containing a polymer compound having a cyclic structure group.
  • the second gas barrier layer A (8A and 8B) by vacuum ultraviolet light irradiation using a coating liquid containing perhydropolysilazane (hereinafter also simply referred to as polysilazane).
  • polysilazane is contained between the first gas barrier layer A (3A and 3B) and the semiconductor nanoparticle layer (4) containing a polymer compound having a cyclic structure group. It is also a preferred embodiment to form the second gas barrier layer A (8A and 8B) by vacuum ultraviolet light irradiation using a coating solution.
  • a coating liquid for forming a metal oxide gas barrier layer containing polysilazane as a precursor for forming a metal oxide is applied on the substrate and A metal oxide which is a polysilazane modified layer having gas barrier properties by applying vacuum ultraviolet light (excimer light) to a layer formed by drying (perhydropolysilazane-containing layer) to modify polysilazane.
  • a method of converting to a second gas barrier layer composed of (for example, SiO 2 ) is used.
  • the second gas barrier layer can be formed by a wet coating method in which a coating liquid for forming a gas barrier layer containing polysilazane is applied.
  • 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 applying the second gas barrier layer-forming coating solution containing the polysilazane 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 second gas barrier layer (8A and 8B) formed on the first gas barrier layer (3A and 3B) 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 in the range of 10 nm to 10 ⁇ m, and most preferably in the range of 10 nm to 1 ⁇ m.
  • the polysilazane to be applied is preferably a compound which is ceramicized at a relatively low temperature condition and modified to silica (SiO 2 ) so as to be applied so as not to impair the properties of the substrate to be used.
  • SiO 2 silica
  • a compound having a main skeleton composed of a unit represented by the following general formula (1) described in Japanese Patent Publication (A) No. 1 is preferable.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • perhydropolysilazane (abbreviation: PHPS) in which all of R 1 , R 2 , and R 3 are hydrogen atoms is particularly preferable from the viewpoint of denseness as the resulting polysilazane-containing layer (gas barrier layer). .
  • the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the first gas barrier layer (3A and 3B) as a base
  • the ceramic film made of polysilazane which is hard and brittle, can be toughened, and even when the film thickness (average film thickness) is increased, the occurrence of cracks is improved. . Therefore, perhydropolysilazane and organopolysilazane can be appropriately selected or mixed as necessary according to the intended use.
  • organic solvent used for the preparation of the coating liquid for forming a metal oxide gas barrier layer containing polysilazane it is preferable to avoid alcohol-based or water-containing solvents that easily react with polysilazane.
  • hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, and ethers such as aliphatic ethers and alicyclic ethers can be used.
  • hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to characteristics such as the solubility of the polysilazane used and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
  • the polysilazane concentration in the polysilazane-containing coating solution for forming a metal oxide gas barrier layer varies depending on the layer thickness of the target polysilazane-containing layer (8A and 8B) and the pot life of the coating solution, but is generally 0.2 to It is preferably within the range of 35% by mass.
  • an amine or a metal catalyst can be added to accelerate the reaction for converting polysilazane into a silicon oxide compound.
  • AQUAMICA NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. may be mentioned.
  • a catalyst having a function of promoting a reaction for converting at least a part of the polysilazane in the polysilazane-containing layer into a silicon oxide compound may be used.
  • the addition amount of these catalysts with respect to polysilazane is 0.1 ppm or more and 5.0% or less as a mass ratio with respect to the total mass of polysilazane as a solid content concentration ratio in the coating liquid for forming a metal oxide gas barrier layer containing polysilazane.
  • the organic solvent is mainly removed, Drying conditions (temperature, processing time) can be set, and the heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but given in consideration of thermal damage to the substrate that is the resin film used It is preferable to appropriately determine the temperature and the processing time.
  • the polysilazane modification treatment in the present invention refers to a treatment for converting a part or most of the polysilazane compound into silicon oxide or silicon oxynitride.
  • a conversion reaction using ultraviolet light capable of a conversion reaction at a lower temperature is preferably used from the viewpoint of adapting to a plastic substrate when producing the optical film of the present invention.
  • the polysilazane-containing layer from which moisture has been removed is modified by irradiation with ultraviolet light.
  • Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.
  • UV light irradiation O 2 and H 2 O, UV absorbers, polysilazane itself, etc. that contribute to ceramics are excited and activated. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective even if it is carried out at an arbitrary time after the formation of the coating film.
  • the ultraviolet light referred to in the present invention generally refers to ultraviolet light containing electromagnetic waves having a wavelength in the range of 10 to 200 nm called vacuum ultraviolet light.
  • the irradiation intensity and the irradiation time are appropriately set within a range in which the base material carrying the polysilazane-containing layer before the irradiation is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the substrate surface is within a range of 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm 2.
  • Irradiation can be performed within a range of 0.1 second to 10 minutes by setting the distance between the base material and the ultraviolet irradiation lamp to be irradiated so that it is within the range of cm 2 .
  • the temperature of the substrate during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the substrate are impaired in the case of a plastic film or the like, for example, the substrate is deformed or its strength is deteriorated. .
  • a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit as the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate applied.
  • limiting in particular as an ultraviolet irradiation atmosphere In many cases, what is necessary is just to implement in atmospheric pressure environment (in the air).
  • Examples of the ultraviolet ray generating means applied to such reforming treatment include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, UV light lasers, etc. It is not limited.
  • the ultraviolet rays from the generation source are reflected by the reflector before the modification.
  • a method of applying to the polysilazane-containing layer is also preferred.
  • UV irradiation can be adapted to either batch processing (offline processing) or continuous processing (online processing), and can be appropriately selected depending on the shape of the substrate used.
  • the substrate having a polysilazane-containing layer is a long film, it is converted into ceramics by continuously irradiating with ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do.
  • the time required for ultraviolet irradiation generally depends on the composition and concentration of the base material used and the polysilazane-containing layer (metal oxide gas barrier layer), but is generally in the range of 0.1 second to 10 minutes, preferably 0.8. Within 5 seconds to 3 minutes.
  • the oxygen concentration in the environment irradiated with vacuum ultraviolet light is preferably in the range of 300 to 10000 ppm (1%), more preferably in the range of 500 to 5000 ppm. It is. By adjusting to such an oxygen concentration range, generation of a metal oxide gas barrier layer in which oxygen is excessive can be suppressed, and deterioration of the barrier property of the gas barrier layer to be formed can be prevented.
  • VUV vacuum ultraviolet light
  • the second gas barrier layer is coated with the second gas barrier layer-forming coating solution containing polysilazane as described above, dried, and irradiated with vacuum ultraviolet light for modification treatment.
  • the second gas barrier layer can be advantageously laminated on the semiconductor nanoparticle layer (4) in terms of flexibility and material cost.
  • the optical film having the configuration of Embodiment 1 having the polymer layers (7A and 7B) shown in FIGS. 2A and 2B can be produced according to the following steps.
  • a first gas barrier layer A (3A) having a formed metal oxide is formed on the substrate A (2A) by chemical vapor deposition or physical vapor deposition.
  • a second gas barrier layer A (8A) is formed by vacuum ultraviolet irradiation using a coating solution containing perhydropolysilazane as necessary.
  • a polymer layer A (7A) containing at least a polymer compound having a cyclic structure group is applied and dried only on it, and is formed in a state where ultraviolet irradiation is not performed.
  • the semiconductor nanoparticle layer (4) containing the semiconductor nanoparticles (5) and the ultraviolet curable resin (6) is applied, and the first unit (U1) is manufactured by stacking without applying ultraviolet irradiation. .
  • a first gas barrier layer B (3B) and, if necessary, a second gas barrier layer B (8B) formed by irradiation with vacuum ultraviolet rays are provided on the substrate B (2B).
  • a polymer layer B (7B) containing at least a polymer compound having a cyclic structure group is laminated in a state where ultraviolet irradiation is not performed to produce a second unit (U2).
  • the semiconductor nanoparticle layer (4) surface of the first unit (U1) and the polymer layer B (7B) surface of the second unit (U2) are bonded and pressure-bonded, and then irradiated with ultraviolet rays.
  • An optical film is manufactured by performing a treatment and bonding the polymer layers (7A and 7B) containing the ultraviolet curable resin and the semiconductor nanoparticle layer by batch curing.
  • the polymer layer A (7A) and the polymer layer (7B) may include an ultraviolet curable resin together with a polymer compound having a cyclic structure group.
  • the optical film having the configuration of the embodiment 3 shown in FIGS. 3A and 3B can be manufactured according to the following steps.
  • a first gas barrier layer A (3A) having a metal oxide and, if necessary, a coating solution containing perhydropolysilazane, are irradiated with vacuum ultraviolet rays.
  • a second gas barrier layer A (8A) is formed.
  • a semiconductor nanoparticle layer (4) containing a semiconductor matrix (5) and a resin matrix (9) composed of a polymer compound having an ultraviolet curable resin and a cyclic structure group is applied to the semiconductor nanoparticle (5).
  • stacked in the state which does not perform is produced.
  • a first gas barrier layer B (3B) and, if necessary, a second gas barrier layer B (8B) formed by vacuum ultraviolet irradiation are laminated on the substrate B (2B).
  • a second unit (U2) is produced.
  • the semiconductor nanoparticle layer (4) surface of the first unit (U1), the first gas barrier layer B (3B) surface of the second unit (U2), or the second gas barrier layer B ( 8B) After bonding and pressure bonding to the surface, the semiconductor nanoparticle layer (4) is cured and bonded by performing ultraviolet irradiation treatment to produce an optical film.
  • the coating liquid used for forming the semiconductor nanoparticle layer (4) includes semiconductor nanoparticles, a monomer of an ultraviolet curable resin, and a polymer having a polymerized cyclic structure group.
  • a method of forming a compound of a monomer of an ultraviolet curable resin by forming a compound and performing ultraviolet irradiation after film formation is preferable.
  • 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 composition and metal in the semiconductor nanoparticle layer can be obtained by adding a polymer compound having a cyclic structure group to the semiconductor nanoparticle layer or a polymer layer adjacent thereto as in the present invention. It is presumed that the oxide gas barrier layer can be bonded or interacted with the composition and the adhesion between them can be improved.
  • the optical film containing the semiconductor nanoparticles of the present invention can be used in fields such as biolabeling, solar power generation, catalysis, bioimaging, light emitting diode (LED), general spatial illumination, and electroluminescent display, for example.
  • fields such as biolabeling, solar power generation, catalysis, bioimaging, light emitting diode (LED), general spatial illumination, and electroluminescent display, for example.
  • LED light emitting diode
  • electroluminescent display for example.
  • Example 1 Production of optical film >> [Production of Optical Film 101] According to the following method, the optical film 101 which consists of a structure of Embodiment 1 as described in FIG. 2A was produced.
  • first unit (U1) Preparation of substrate A (2A)
  • substrate A (2A) As substrate A (2A), a polyethylene terephthalate film (Cosmo Shine, manufactured by Toyobo Co., Ltd.) having a thickness of 125 ⁇ m, which is a thermoplastic resin support and is easily bonded on both sides.
  • A4300 abbreviated as 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.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Co., Ltd. was applied to the easily adhesive surface of the substrate A (2A) with a wire bar so that the layer thickness after drying was 4 ⁇ m. Then, after drying at 80 ° C. for 3 minutes, curing was performed under a curing condition; 1.0 J / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere to form anchor coat layers on both sides. In this way, a substrate A (2A) was prepared.
  • the CVD apparatus (S1) shown in FIG. 4 is used to form the first gas barrier layer A (3A) on the substrate A (2A) by the following film formation conditions (plasma CVD conditions).
  • a first gas barrier layer A (3A) was formed to a thickness of 300 nm.
  • Resin 1 UV curable resin (epoxy acrylate DIC Corporation UV curable resin Unidic V-5500) 9.5 parts by mass Polymer having cyclic structural group: monofunctional acrylate monomer (ethoxylated o-phenylphenol acrylate, Shin-Nakamura Chemical Co., Ltd., product name: A-LEN-10) 0.29 parts by mass (added to resin 1: 3.0% by mass) Photopolymerization initiator: Irgacure 184 (manufactured by BASF Japan) 0.5 parts by mass Toluene 90.0 parts by mass (application of coating solution 1 for forming polymer layer A) The prepared coating solution 1 for forming the polymer layer A was applied on the first gas barrier layer A (3A) using a wireless bar under the condition that the film thickness after drying was 1.0 ⁇ m. Then, using a high pressure mercury lamp, it hardened
  • TOPO trioctylphosphine oxide
  • HDA 1-heptadecyl-octadecylamine
  • 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). Thereafter, the temperature was lowered to 100 ° C., zinc acetate dihydrate was added and stirred to dissolve, and then a trioctylphosphine solution of hexamethyldisilylthiane was added dropwise, stirring was continued for several hours to complete the reaction, and CdSe / ZnS (semiconductor nanoparticles) was obtained.
  • 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%.
  • the prepared coating solution 1 for forming a semiconductor nanoparticle layer is applied on the polymer layer A (7A) so that the dry layer thickness is 100 ⁇ m, and heated at 75 ° C. for 3 minutes to form the semiconductor nanoparticle layer (4). Formed. However, the curing process by ultraviolet irradiation is not performed at this stage.
  • the specific configuration of the first unit (U1) of the optical film 101 is shown in Table 1 described later.
  • first gas barrier layer B Formation of first gas barrier layer B (3B) In the same manner as the formation of the first gas barrier layer A (3A) of the first unit (U1), the first gas barrier layer is formed on the substrate B. Layer B (3B) was formed.
  • the polymer layer B (7B) is formed on the first gas barrier layer B (3B) in the same manner as the formation of the polymer layer A (7A) of the first unit (U1). Formed.
  • the specific configuration of the second unit (U2) of the optical film 101 is shown in Table 2 described later.
  • optical film 102 polystyrene was used in place of the monofunctional acrylate monomer (A-LEN-10) as the polymer having a cyclic structural group used for forming the polymer layer A (7A) and the polymer layer B (7B).
  • A-LEN-10 monofunctional acrylate monomer
  • the second gas barrier layer A (8A) is provided between the first gas barrier layer A (3A) and the polymer layer A (7A), and the first The optical film 104 was produced in the same manner except that the second gas barrier layer B (8B) was formed according to the following method between the gas barrier layer B (3B) and the polymer layer B (7B). .
  • a first gas barrier layer was prepared by using a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) as the second gas barrier layer forming coating solution.
  • the layer thickness after drying was applied to 180 nm and dried to form a polysilazane-containing layer.
  • the polysilazane-containing layer formed above was subjected to ultraviolet irradiation treatment using the following ultraviolet device to modify the polysilazane-containing layer, and the second gas barrier layers (8A and 8B) were formed by a coating method. .
  • Tables 1 and 2 show the structures of the optical films 101 to 107 produced as described above.
  • PET Polyethylene terephthalate film (Toyobo Co., Ltd., Cosmo Shine A4300, thickness: 125 ⁇ m)
  • HMDSO Hexamethyldisiloxane
  • Plasma CVD Plasma chemical vapor deposition equipment
  • PHPS Perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.)
  • Epoxy Epoxy acrylate (UV curable resin unidic V-5500 manufactured by DIC Corporation)
  • A-LEN-10 Monomer having a cyclic structure group (monofunctional acrylate monomer (ethoxylated o-phenylphenol acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)) ⁇ Evaluation of optical film >> The following evaluations were performed on each of the produced optical films.
  • Dark spot generation ratio [Dark spot generation area / Optical film area (7.5 ⁇ 15 cm)] ⁇ 100 (%) About the dark spot generation
  • MCPD-7000 manufactured by Otsuka Electronics Co., Ltd. was used.
  • the relative luminous efficiency was calculated when the luminous efficiency of the optical film 107 was 100, and the relative luminous efficiency was evaluated according to the following criteria.
  • Relative luminous efficiency is 145 or more.
  • O Relative luminous efficiency is 130 or more and less than 145.
  • O Relative luminous efficiency is 110 or more and less than 130.
  • ⁇ Relative luminous efficiency is 90 or more. Less than 110 x: Relative luminous efficiency is less than 90 [Evaluation of end adhesion]
  • Each of the produced optical films was cut into a size of 10 cm ⁇ 10 cm with a double-blade type punching machine, and then the presence or absence of film peeling between the four cut surfaces (10 cm ⁇ 4 surfaces) was checked with a loupe. Observed and evaluated end adhesion according to the following criteria.
  • Slight film peeling occurs in 2 to 4 places in the entire end area, but the quality is practically good.
  • ⁇ Strong film peeling occurs at 5 or more locations in the entire end region. This is a quality that is a problem in practical use. 3 shows.
  • the optical film of the present invention in which a polymer layer containing a polymer having a cyclic structure group is provided between the gas barrier layer and the semiconductor nanoparticle layer is compared with the comparative example. It can be seen that they are excellent in fault tolerance, luminous efficiency and end adhesion. Furthermore, it turns out that the effect is more excellent by using a polystyrene as a polymer which has cyclic structure group.
  • Example 2 [Production of Optical Film 201] According to the following method, the optical film 201 which consists of a structure of Embodiment 2 as described in FIG. 3A was produced.
  • the first gas barrier layer A (3A) is formed on the substrate A in the same manner as the formation of the first gas barrier layer A (3A) in the production of the optical film 101 of Example 1. Gas barrier layer A (3A) was formed.
  • a photopolymerization initiator Irgacure 184 (manufactured by BASF Japan) is added to the UV curable resin Unidic V-5500 manufactured by Epoxy Acrylate DIC Co., Ltd. at a solid content ratio (mass%) of resin / initiator: 95/5.
  • a monomer having a cyclic structure group tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-DCP), which is a bifunctional acrylate monomer, is used as an ultraviolet curable resin. An amount of 2.5% by mass was added to the epoxy acrylate.
  • the above prepared semiconductor nanoparticles were added under the condition that the content rate was 1.0% by mass 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 gas barrier layer A (3A) using a wireless bar so that the dry layer thickness was 100 ⁇ m, and heated at 75 ° C. for 3 minutes, A semiconductor nanoparticle layer (4) was formed. However, the curing process by ultraviolet irradiation is not performed at this stage.
  • Base material B (2B) was prepared like base material A (2A) used by the 1st unit (U1).
  • first gas barrier layer B Formation of the first gas barrier layer B (3B) In the same manner as the formation of the first gas barrier layer A (3A) of the first unit (U1), the first gas barrier layer is formed on the substrate B. Layer B (3B) was formed.
  • optical films 202 to 208 In the production of the optical film 201, the type of the polymer (monomer) having a cyclic structure group constituting the semiconductor nanoparticle layer and the content relative to the epoxy acrylate that is the resin 1 are changed to the configuration shown in Table 4. Similarly, optical films 202 to 208 were produced.
  • the second gas barrier layer (8A and 8B) is provided between the first gas barrier layer (3A and 3B) and the semiconductor nanoparticle layer (4).
  • the optical film 209 was produced in the same manner except that the second gas barrier layers (8A and 8B) were formed by the same method as used for producing the optical film 104 of Example 1.
  • optical film 211 In the production of the optical film 201, as a configuration of the semiconductor nanoparticle layer (4), instead of epoxy acrylate (abbreviation: epoxy), lauryl methacrylate (Blemmer LMA, manufactured by NOF Corporation, abbreviation: LMA) is used. Instead of A-DCP which is a polymer having a cyclic structural group, polyisobutylene which is an acyclic polymer (manufactured by JX Nippon Oil & Energy Corporation, abbreviated as PIB) was used at a ratio of 2.0% by mass with respect to LMA. An optical film 211 was produced in the same manner except for the above.
  • epoxy epoxy acrylate
  • LMA lauryl methacrylate
  • A-DCP which is a polymer having a cyclic structural group
  • polyisobutylene which is an acyclic polymer (manufactured by JX Nippon Oil & Energy Corporation, abbreviated as PIB) was used
  • the optical film 212 was produced according to the method described in Japanese Patent No. 4579065.
  • a cycloolefin resin (ZEONEA, manufactured by Nippon Zeon Co., Ltd.) with a thickness of 100 ⁇ m was formed thereon as a non-water-permeable material layer, thereby producing an optical film 212.
  • Table 4 shows the structures of the optical films 201 to 212 produced above.
  • A-DCP Bifunctional acrylate monomer Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-DCP)
  • UVA-5080 UV-absorbing polymer (vanadylene UVA-5080, a (meth) acrylic ester copolymer, Shin-Nakamura Chemical Co., Ltd.)
  • LMA Lauryl methacrylate (Blemmer LMA, manufactured by NOF Corporation)
  • PIB Polyisobutylene (manufactured by JX Nippon Oil & Energy Corporation) ⁇ Evaluation of optical film >> About each produced optical film, it carried out similarly to the method of Example 1, and evaluated failure tolerance, luminous efficiency, and edge part adhesiveness, and Table 5 shows the result obtained.
  • the optical film of the present invention provided with a semiconductor nanoparticle layer containing a polymer having a cyclic structure group has a failure resistance, luminous efficiency, and end adhesion with respect to the comparative example. It turns out that it is excellent in. Furthermore, it turns out that the effect is more excellent by using a polystyrene as a polymer which has cyclic structure group.
  • the optical film of the present invention can suppress degradation of semiconductor nanoparticles due to infiltration of oxygen, water, etc. over a long period of time, and has excellent resistance to failure (dark spot resistance) and end film peeling resistance (adhesion) at the time of punching,
  • it is an optical film with high luminous efficiency, and can be suitably used in fields such as biomarkers, solar power generation, catalysis, biological imaging, light emitting diodes (LEDs), general spatial illumination, and electroluminescent displays. .

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  • Laminated Bodies (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention a pour objet de produire un film optique avec lequel la détérioration de nanoparticules en semiconducteur due à l'infiltration par de l'oxygène ou de l'eau peut être réduite au minimum pendant une longue période, et qui possède une excellente résistance de défaut (résistance DS) et résistance au détachement de film de bordure (cohésion) pendant un processus de gravure au poinçon, ainsi qu'un rendement lumineux élevé ; et un procédé de fabrication de celui-ci. Le film optique selon l'invention est caractérisé en ce qu'il possède au moins un matériau de base A, une première couche de barrière contre les gaz A comprenant un oxyde métallique, une couche de nanoparticules en semiconducteur contenant des nanoparticules en semiconducteur et une résine durcissable aux UV, une première couche de barrière contre les gaz B, et un matériau de base B, dans cet ordre, et en ce qu'il contient en outre un composé polymère ayant un groupe à structure cyclique.
PCT/JP2015/081301 2014-11-11 2015-11-06 Film optique et procédé de fabrication d'un film optique WO2016076219A1 (fr)

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JP2019536653A (ja) * 2016-09-12 2019-12-19 ナノコ テクノロジーズ リミテッド 半導体ナノ粒子用のガスバリアコーティング

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WO2015037733A1 (fr) * 2013-09-13 2015-03-19 凸版印刷株式会社 Feuille de conversion de longueur d'onde et unité de rétroéclairage
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JP2012169271A (ja) * 2011-02-11 2012-09-06 Lg Innotek Co Ltd 表示装置
JP2013032516A (ja) * 2011-07-05 2013-02-14 Dexerials Corp 蛍光体シート形成用樹脂組成物
WO2014163062A1 (fr) * 2013-04-02 2014-10-09 コニカミノルタ株式会社 Procédé de fabrication d'un film barrière aux gaz, film barrière aux gaz, et dispositif électronique
WO2015037733A1 (fr) * 2013-09-13 2015-03-19 凸版印刷株式会社 Feuille de conversion de longueur d'onde et unité de rétroéclairage
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JP2017129743A (ja) * 2016-01-20 2017-07-27 大日本印刷株式会社 量子ドットシート、バックライト及び液晶表示装置
JP2019536653A (ja) * 2016-09-12 2019-12-19 ナノコ テクノロジーズ リミテッド 半導体ナノ粒子用のガスバリアコーティング

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