WO2018043543A1 - 蛍光体含有フィルムおよびバックライトユニット - Google Patents
蛍光体含有フィルムおよびバックライトユニット Download PDFInfo
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- WO2018043543A1 WO2018043543A1 PCT/JP2017/031111 JP2017031111W WO2018043543A1 WO 2018043543 A1 WO2018043543 A1 WO 2018043543A1 JP 2017031111 W JP2017031111 W JP 2017031111W WO 2018043543 A1 WO2018043543 A1 WO 2018043543A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- 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
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
Definitions
- the present invention relates to a phosphor-containing film containing a phosphor that emits fluorescence when irradiated with excitation light, and a backlight unit including the phosphor-containing film as a wavelength conversion member.
- LCDs liquid crystal display devices
- LCDs liquid crystal display devices
- quantum dots also called QuantumDot, QD, and quantum dots
- a wavelength conversion layer containing a light emitting material (phosphor) a light emitting material
- a quantum dot is an electronic state in which the direction of movement is limited in all three dimensions, and when a semiconductor nanoparticle is three-dimensionally surrounded by a high potential barrier, the nanoparticle is quantum. It becomes a dot.
- Quantum dots exhibit various quantum effects. For example, the “quantum size effect” in which the density of states of electrons (energy level) is discretized appears. According to this quantum size effect, the absorption wavelength and emission wavelength of light can be controlled by changing the size of the quantum dot.
- quantum dots are dispersed in a resin or the like, and are used, for example, as a quantum dot film that performs wavelength conversion and disposed between a backlight and a liquid crystal panel.
- excitation light enters the film containing quantum dots from the backlight, the quantum dots are excited and emit fluorescence.
- white light can be realized by using quantum dots having different light emission characteristics and causing each quantum dot to emit light having a narrow half-value width of red light, green light, or blue light. Since fluorescence by quantum dots has a narrow half-value width, it is possible to make white light obtained by appropriately selecting a wavelength high brightness and to have a design excellent in color reproducibility.
- the wavelength conversion member protects the quantum dot layer by laminating a gas barrier film on both main surfaces of a resin layer (hereinafter also referred to as “quantum dot layer”) containing a quantum dot, which is a wavelength conversion layer containing quantum dots. Configured to do.
- quantum dot layer a resin layer
- Patent Document 1 discloses a quantum point including a quantum point that converts wavelength of excitation light to generate wavelength converted light, a wavelength conversion unit that includes a dispersion medium that disperses the quantum point, and a sealing member that seals the wavelength conversion unit.
- a point wavelength converter is described, a wavelength conversion part is arranged between two sealing sheets that are sealing members, and the wavelength conversion part is heated and thermally adhered around the wavelength conversion part of the sealing sheet. Sealing is described.
- Patent Document 2 discloses a color conversion layer (phosphor layer) that converts at least a part of the color light emitted from the light source part into another color light, and an impermeable sealing sheet that seals the color conversion layer. And a second bonding layer provided in a frame shape so as to surround the planar shape of the color conversion layer along the outer periphery of the phosphor layer.
- a color conversion sheet (phosphor sheet) is described in which the two bonding layers are made of an adhesive material having a water vapor barrier property to prevent water from entering the color conversion layer.
- the wavelength conversion layer including quantum dots used in the LCD is a thin film of about 50 ⁇ m to 350 ⁇ m. It was very difficult to coat the entire end face of such a very thin film with a sealing sheet such as a gas barrier film, and there was a problem that productivity was poor. Such a problem occurs not only in quantum dots but also in a phosphor-containing film including a phosphor that reacts with oxygen and deteriorates.
- a coating process and a curing process are sequentially performed on a long film by a roll-to-roll method, and laminated.
- a method of cutting to a desired size after forming the structure is preferred.
- the phosphor-containing layer is exposed to the outside air at the cut end face, and thus measures against oxygen intrusion from the cut end face are necessary. .
- Patent Document 3 a fluorescent material including two substrates, a sealing material that is stacked between the two substrates and forms a plurality of separated regions, and a fluorescent material that is disposed in the separated regions.
- An optical component having a member is described, and it is described that a sealed state of a fluorescent member can be maintained even when the optical component is cut by cutting at a sealing material portion.
- the present invention has been made in view of the above circumstances, and in a film containing a phosphor such as a quantum dot, it suppresses deterioration of the phosphor even when it is cut into a desired size after forming a laminated structure. It is an object of the present invention to provide a phosphor-containing film that can be used, and a backlight unit that includes the phosphor-containing film as a wavelength conversion member.
- the present inventors have discretely arranged a plurality of fluorescent regions including phosphors that react with oxygen and deteriorate when exposed to oxygen.
- a phosphor-containing layer in which a resin layer having an impermeability to oxygen is disposed between the plurality of fluorescent regions, a first base film laminated on one main surface of the phosphor-containing layer, and the other and a second base film which is laminated on the main surface, Knoop hardness of the resin layer is 115N / mm 2 ⁇ 285N / mm 2, and a creep recovery of not more than 22%, the elastic recovery of 60 %, It was found that the above-mentioned problems could be solved, and the present invention was completed. That is, it has been found that the above-described problem can be achieved by the following configuration.
- a plurality of fluorescent regions containing phosphors that react with oxygen to deteriorate when exposed to oxygen are discretely arranged, and oxygen impermeability is made between the plurality of discretely arranged fluorescent regions.
- Knoop hardness of the resin layer is 115N / mm 2 ⁇ 285N / mm 2, and a creep recovery of not more than 22%, the phosphor-containing film elastic recovery rate of 60% or more.
- a backlight unit comprising a wavelength conversion member comprising the phosphor-containing film according to any one of (1) to (5), and at least one of a blue light-emitting diode and an ultraviolet light-emitting diode.
- a phosphor-containing film capable of suppressing deterioration of the phosphor even when the laminate structure is cut and then cut into a desired size, and this A backlight unit including a phosphor-containing film as a wavelength conversion member can be provided.
- FIG. 8B is a sectional view taken along line BB in FIG. 8A. It is a top view which shows typically another example of the fluorescent substance containing film of this invention.
- FIG. 9B is a sectional view taken along line BB in FIG. 9A. It is a figure which shows the manufacturing process of a fluorescent substance containing film. It is a schematic diagram for demonstrating the preparation methods of the fluorescent substance containing film of this invention. It is a schematic diagram for demonstrating the preparation methods of the fluorescent substance containing film of this invention. It is schematic structure sectional drawing of the backlight unit provided with the fluorescent substance containing film as a wavelength conversion member. It is a schematic structure sectional view of a liquid crystal display provided with a back light unit.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the phosphor-containing film of the present invention is A plurality of fluorescent regions containing phosphors that react with oxygen to deteriorate when exposed to oxygen are discretely disposed, and a resin layer that is impervious to oxygen between the plurality of discretely disposed fluorescent regions A phosphor-containing layer in which is disposed, A first base film laminated on one main surface of the phosphor-containing layer and a second base film laminated on the other main surface, Knoop hardness of the resin layer is 115N / mm 2 ⁇ 285N / mm 2, the creep recovery rate is 22% or less, the elastic recovery rate is phosphor-containing film is 60% or more.
- FIG. 1 is a perspective view schematically showing an example of the phosphor-containing film 1 according to the present invention
- FIG. 2 is a plan view of FIG. 1
- FIG. 3 is a cross-sectional view of FIG.
- the 2nd base film 20 is shown with a broken line
- the fluorescent substance content layer 30 is shown with a continuous line for description.
- the phosphor-containing film 1 of the present embodiment includes a first substrate film 10 and a region 35 including a phosphor 31 that reacts with oxygen and deteriorates when exposed to oxygen on the first substrate film 10.
- the region 35 including the phosphor 31 may be referred to as a fluorescent region 35.
- the first base film On the first base film,... A plurality of regions including phosphors are discretely arranged” means that the first base is as shown in FIG. 1 and FIG.
- the plurality of fluorescent regions 35 are arranged in an isolated manner without contacting each other in the two-dimensional direction along the film surface of the first base film 10.
- the fluorescent region 35 has a cylindrical shape (disk shape), and is individually surrounded by a resin layer 38 that is impermeable to oxygen in a two-dimensional direction along the film surface of the first base film 10. It is isolated and the penetration
- region 35 is interrupted
- “having oxygen impermeability” means that the oxygen permeability is 10 cc / (m 2 ⁇ day ⁇ atm) or less.
- Oxygen permeability of the resin layer having impermeability to oxygen is more preferably at 1cc / (m 2 ⁇ day ⁇ atm) or less, more preferably, 10 -1 cc / (m 2 ⁇ day ⁇ atm) or less It is.
- “having impermeability” and “having barrier properties” are used synonymously. That is, in this specification, the gas barrier means impermeable to gas (gas), and the water vapor barrier means impermeable to water vapor. A layer that is impermeable to both oxygen and water vapor is referred to as a “barrier layer”.
- the fluorescent regions 35 are discretely arranged in the two-dimensional direction, as shown in FIG. 2, when the phosphor-containing film 1 is assumed to be part of a long film, As shown by the broken line, the fluorescent region 35 other than the fluorescent region 35 that is the cut portion can be kept surrounded by the resin layer 38 and sealed, regardless of where it is cut linearly.
- the fluorescent region 35 that has been cut and exposed to the outside air loses its original function as a phosphor, but the region that has lost the fluorescent property becomes a resin layer that protects the fluorescent region 35 that is not exposed to the outside air from the outside air.
- Knoop hardness of the resin layer is 115N / mm 2 ⁇ 285N / mm 2, the creep recovery rate is 22% or less, the elastic recovery rate is 60% or more .
- a coating process and a curing process are sequentially performed on a long film by a roll-to-roll method.
- a method of cutting to a desired size after forming the laminated structure is preferable.
- the phosphor-containing layer is exposed to the outside air at the cut end face, and therefore measures against oxygen intrusion from the cut end face are necessary. Therefore, phosphors such as quantum dots are discretely arranged in a plurality of regions, and a sealing material is arranged around the phosphors.
- the Knoop hardness of the resin layer is a sealant and 115N / mm 2 ⁇ 285N / mm 2, the creep recovery rate was 22% or less, the elastic recovery of 60 % Or more, it is possible to suppress cracking of the resin layer (sealing material) when cutting the phosphor-containing film, and to prevent moisture and oxygen from entering from the end face in the phosphor-containing film after cutting. Deterioration of the body can be suppressed.
- the Knoop hardness is preferably 140 N / mm 2 to 285 N / mm 2 .
- the Knoop hardness in the present invention is a value determined by the following method. Using a PICODETOR HM500p type hardness meter manufactured by Fisher Instruments Co., Ltd., a sample surface fixed to a glass substrate with a Knoop indenter is loaded for 10 sec, creep time at maximum load is 5 sec, unloading time is 10 sec, creep time after unloading Measured under conditions of 5 sec and maximum load of 20 mN. The hardness is calculated from the relationship between the contact area between the indenter and the sample obtained from the indentation depth and the maximum load, and the average value of these 10 points is taken as the Knoop hardness.
- the creep recovery rate indicates the recovery rate of the indentation depth after the Knoop indenter is pushed in and after unloading. This is the maximum indentation depth, which indicates the “elastic recovery amount” and “plasticity where the bond is broken (permanently). It corresponds to the deformation obtained by subtracting “) deformation” and corresponds to viscoelastic deformation.
- the creep recovery rate is preferably 20% or less.
- the creep recovery rate in the present invention is a value determined by the following method. Using a PICODETOR HM500p type hardness meter manufactured by Fisher Instruments Co., Ltd., a sample surface fixed to a glass substrate with a Knoop indenter is loaded for 10 sec, creep time at maximum load is 5 sec, unloading time is 10 sec, creep time after unloading Measured under conditions of 5 sec and maximum load of 20 mN. The ratio of creep recovery is calculated from the relationship between the indentation depth immediately after unloading and the depth after 5 seconds of unloading, and the average value of these 10 points is taken as the creep recovery rate.
- a resin layer having an elastic recovery rate of 60% or more on at least one surface, preferably on both surfaces, can exhibit good results in cutting.
- the elastic recovery rate represents the deformation recovery rate from the maximum load of the Knoop indenter to the time when the load becomes zero. Unlike creep recovery, it corresponds to the amount of deformation that recovers immediately after unloading. If the elastic recovery rate is small with respect to creep recovery, the deformation recovery due to indentation is delayed. Therefore, if the elastic recovery rate is too small, the shape recovery after cutting is delayed, resulting in film thickness unevenness, leading to brightness unevenness. From the viewpoint of further improving the cutting property, the elastic recovery rate is preferably 65% or more.
- the elastic recovery rate in the present invention is a value determined by the following method. Using a PICODETOR HM500p type hardness meter manufactured by Fisher Instruments Co., Ltd., a sample surface fixed to a glass substrate with a Knoop indenter is loaded for 10 sec, creep time at maximum load is 5 sec, unloading time is 10 sec, creep time after unloading Measured under conditions of 5 sec and maximum load of 20 mN.
- the resin layer may be easily cracked due to the difference in hardness between the resin layer and the fluorescent region, but the Knoop hardness of the resin layer, By setting the creep recovery rate and the elastic recovery rate within the above ranges, it is possible to suitably suppress cracking of the resin layer when cutting.
- the phosphor-containing film of the present invention can suitably suppress cracking of the resin layer even if it is cut across the resin layer and the fluorescent region, the cutting location can be freely selected, and the size and shape at the time of cutting can be selected. High degree of freedom.
- the phosphor-containing film When the resin layer and the fluorescent region are cut, the phosphor-containing film has a configuration in which the region that has lost the fluorescent characteristics and the resin layer are exposed at the end surface that is a cut surface. In addition, when a plurality of fluorescent regions are cut, the end face of the phosphor-containing film has a configuration in which the regions that have lost the fluorescent properties and the resin layers are alternately exposed.
- the fluorescent region 35 is configured by the phosphor 31 being dispersed in the binder 33.
- the effect of the present invention is particularly remarkable when the oxygen permeability of the binder 33 is greater than the permeability of the resin layer 38 filled between the fluorescent regions 35, that is, when the binder 33 is likely to transmit oxygen. is there.
- the 1st base film 10 and the 2nd base film have an impermeability with respect to oxygen, and as shown in FIG. 3, it supports a support film (11, 21) and oxygen. It may have a laminated structure with barrier layers (12, 22) having impermeability.
- the size and arrangement pattern of the fluorescent region 35 are not particularly limited, and may be appropriately designed according to desired conditions. In the design, consideration is given to a geometrical constraint for arranging the fluorescent regions apart from each other in plan view, an allowable value of the width of the non-light emitting region generated at the time of cutting, and the like. In addition, for example, when a printing method is used as one of the methods for forming a fluorescent region to be described later, there is a restriction that printing cannot be performed unless the individual occupied area (in plan view) is a certain size or more. Furthermore, the shortest distance between adjacent fluorescent regions needs to be a distance that can realize an oxygen permeability of 10 cc / (m 2 ⁇ day ⁇ atm) or less. In view of these, a desired shape, size, and arrangement pattern may be designed.
- the fluorescent region 35 is cylindrical and circular in plan view, but the shape of the fluorescent region 35 is not particularly limited.
- the fluorescent region 35 may be a polygonal column such as a quadrangle in a plan view as shown in FIG. 4 or a hexagon in a plan view as shown in FIG.
- the bottom surface of the cylinder or the polygonal column is disposed in parallel to the base film surface, but the bottom surface is not necessarily disposed in parallel to the base film surface.
- the shape of each fluorescent region 35 may be indefinite.
- the line connecting the points on the outer side (the side where the phosphor 31 is not arranged) of the phosphor 31e located at the outermost part of the area is the outline of the phosphor region 35 (the boundary between the phosphor region 35 and the resin layer 38) m. I will take care of it.
- the position of the phosphor can be specified. Can be identified.
- the sides of a cylinder or a polygonal column are allowed to meander as shown in the outline of FIG.
- the fluorescent regions 35 are periodically arranged in a pattern.
- the fluorescent regions 35 may be aperiodic as long as the desired performance is not impaired. There may be. It is preferable that the fluorescent region 35 is uniformly distributed over the entire region of the phosphor-containing layer 30 because the in-plane distribution of luminance is uniform.
- the phosphor 31 in the fluorescent region 35 may be one type or a plurality of types.
- the phosphor 31 in one fluorescent region 35 is one type, and among the plurality of fluorescent regions 35, a region containing the first phosphor and a region containing a second phosphor different from the first phosphor. May be arranged periodically or aperiodically. There may be three or more types of phosphors.
- the phosphor-containing layer 30 may be configured by laminating a plurality of fluorescent regions 35 in the thickness direction of the film. Such an example will be briefly described with reference to FIGS. 7A to 9B.
- symbol is attached
- FIG. 7A is a schematic plan view of another example of the phosphor-containing film
- FIG. 7B is a cross-sectional view taken along line BB in FIG. 7A
- FIG. 7C is a cross-sectional view taken along line CC in FIG. 7A. is there.
- the phosphor-containing film 3 shown in FIGS. 7A to 7C includes a first phosphor region 35a in which a first phosphor 31a is dispersed in a binder 33 and a first phosphor 31a in the binder 33 as a phosphor region. And a second fluorescent region 35b in which second phosphors 31b different from the above are dispersed.
- the first fluorescent regions 35a and the second fluorescent regions 35b are alternately arranged in a plan view, and are distributed at different positions in the film thickness direction.
- the first fluorescent region 35a is disposed on the main surface side adjacent to the second base film 20
- the second fluorescent region 35b is disposed on the main surface side adjacent to the first base film 10
- the first fluorescent region 35a and the second fluorescent region 35b are arranged so as not to overlap in plan view.
- the first phosphor 31a and the second phosphor 31b are phosphors having different emission center wavelengths.
- a phosphor having an emission center wavelength in the wavelength band of 600 to 680 nm is used as the first phosphor 31a
- a phosphor having an emission center wavelength in the wavelength band of 520 to 560 nm is used as the second phosphor 31b.
- the binders 33 of the first fluorescent region 35a and the second fluorescent region 35b are made of the same composition in this example, but may be made of different compositions.
- FIG. 8A is a plan view schematically showing another example of the phosphor-containing film of the present invention
- FIG. 8B is a sectional view taken along line BB of FIG. 8A.
- the phosphor-containing film 4 shown in FIGS. 8A and 8B partially overlaps when the first fluorescent region 35a and the second fluorescent region 35b arranged at different positions in the film thickness direction are viewed in plan view. Is different from the phosphor-containing film 3 shown in FIGS. 7A to 7C.
- the first fluorescent region 35a and the second fluorescent region 35b arranged at different positions in the film direction may have an overlap in plan view.
- FIG. 9A is a plan view schematically showing another example of the phosphor-containing film of the present invention
- FIG. 9B is a sectional view taken along line BB of FIG. 9A.
- the phosphor-containing film 6 shown in FIGS. 9A and 9B includes a step-like fluorescent region 35 in which square columnar regions are stacked with a half-cycle shift.
- the fluorescent region 35 is formed by dispersing a first phosphor 31 a and a second phosphor 31 b in a binder 33.
- the second phosphor 31b and the first phosphor 31a are dispersed in the lower step portion of the step-like fluorescent region 35 and the upper step portion, but the first phosphor 31a and the second phosphor portion 31a are dispersed.
- the phosphor 31b may be mixed in the entire upper and lower staircase portion in the fluorescent region 35.
- the phosphor-containing film of the present invention is not particularly limited in the shape of the fluorescent region 35 and the arrangement pattern thereof.
- the fluorescent region in the portion other than the cut end has oxygen in the direction along the film surface. Since it is enclosed and sealed with resin which does not permeate
- the phosphor-containing layer 30 is laminated on one film surface of the first substrate film 10, and the second substrate film 20 is laminated on the phosphor-containing layer 30.
- the phosphor-containing layer 30 is sandwiched between two base films 10 and 20.
- the phosphor-containing layer 30 includes a fluorescent region 35 including a plurality of phosphors 31 and a resin layer 38 that is filled between the fluorescent regions 35 and is impermeable to oxygen.
- the fluorescent region 35 is composed of a phosphor 31 and a binder 33 in which the phosphor 31 is dispersed, and is formed by applying and curing a phosphor region forming coating solution containing the phosphor 31 and a curable compound. Is done.
- phosphors can be used as the phosphor that reacts with oxygen and deteriorates when exposed to oxygen.
- phosphors in which semiconductor fine particles are doped with rare earth, and semiconductor nano particles (quantum dots, quantum rods) are also preferably used.
- Phosphors can be used alone, but in order to obtain a desired fluorescence spectrum, a plurality of phosphors having different wavelengths may be used in combination, or a combination of phosphors having different material configurations (for example, A combination of a rare earth-doped garnet and quantum dots may be used.
- being exposed to oxygen means being exposed to an oxygen-containing environment such as the atmosphere, and being deteriorated by reaction with oxygen means that the performance of the phosphor is caused by oxidation of the phosphor.
- the light emission performance is reduced as compared with that before reacting with oxygen.
- the photoelectric conversion efficiency is less than that of oxygen. It means that it is lower than before the reaction.
- a quantum dot is mainly described as an example of a phosphor that deteriorates due to oxygen.
- the phosphor of the present invention is not limited to quantum dots, and other fluorescent dyes that deteriorate due to oxygen, photoelectric conversion materials, and the like.
- the material is not particularly limited as long as it is a material that converts external energy into light or converts light into electricity.
- Quantum dot is a fine particle of a compound semiconductor having a size of several nanometers to several tens of nanometers, and at least is excited by incident excitation light to emit fluorescence.
- the phosphor of the present embodiment includes at least one kind of quantum dot and can also include two or more kinds of quantum dots having different emission characteristics.
- Known quantum dots include a quantum dot (A) having an emission center wavelength in a wavelength range of 600 nm to 680 nm, a quantum dot (B) having an emission center wavelength in a wavelength range of 500 nm to less than 600 nm, There is a quantum dot (C) having an emission center wavelength in a wavelength band of 400 nm or more and less than 500 nm.
- the quantum dot (A) is excited by excitation light to emit red light, the quantum dot (B) emits green light, The dot (C) emits blue light.
- red light emitted from the quantum dots (A) and light emitted from the quantum dots (B) are emitted.
- White light can be embodied by green light and blue light transmitted through the phosphor-containing layer.
- ultraviolet light incident on the phosphor-containing layer including the quantum dots (A), (B), and (C) as excitation light, red light emitted from the quantum dots (A), quantum dots (B ) And green light emitted by the quantum dots (C) and white light can be realized.
- quantum dots for example, JP 2012-169271 A paragraphs 0060 to 0066 can be referred to, but are not limited to those described here.
- the quantum dots commercially available products can be used without any limitation.
- the emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.
- Quantum dots can be added in an amount of, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the coating solution.
- Quantum dots may be added in the form of particles in the coating liquid, or may be added in the form of a dispersion dispersed in an organic solvent.
- the addition in the state of a dispersion is preferable from the viewpoint of suppressing the aggregation of the quantum dot particles.
- the organic solvent used for dispersing the quantum dots is not particularly limited.
- quantum dots for example, core-shell type semiconductor nanoparticles are preferable from the viewpoint of improving durability.
- the core II-VI semiconductor nanoparticles, III-V semiconductor nanoparticles, multi-component semiconductor nanoparticles, and the like can be used. Specific examples include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, InP, InAs, and InGaP, but are not limited thereto. Among these, CdSe, CdTe, InP, and InGaP are preferable from the viewpoint of emitting visible light with high efficiency.
- the shell CdS, ZnS, ZnO, GaAs, and a composite thereof can be used, but the shell is not limited thereto.
- the emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.
- the quantum dots may be spherical particles, may be rod-like particles called quantum rods, and may be tetrapod-type particles. From the viewpoint of narrowing the half width of light emission (full width at half maximum, FWHM) and expanding the color reproduction range of the liquid crystal display device, spherical quantum dots or rod-like quantum dots (that is, quantum rods) are preferable.
- a ligand having a Lewis basic coordinating group may be coordinated on the surface of the quantum dot. It is also possible to use quantum dots already coordinated with such a ligand.
- Lewis basic coordinating groups include amino groups, carboxy groups, mercapto groups, phosphine groups, and phosphine oxide groups. Specific examples include hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, and trioctylphosphine oxide. Of these, hexadecylamine, trioctylphosphine, and trioctylphosphine oxide are preferable, and trioctylphosphine oxide is particularly preferable.
- Quantum dots coordinated with these ligands can be produced by a known synthesis method. For example, C.I. B. Murray, D.M. J. et al. Norris, M.M. G. Bawendi, Journal American Chemical Society, 1993, 115 (19), pp 8706-8715, or The Journal Physical Chemistry, 101, pp 9463-9475, 1997.
- the quantum dot which the ligand coordinated can use a commercially available thing without a restriction
- Lumidot manufactured by Sigma Aldrich
- the content of the quantum dot coordinated with the ligand is preferably 0.01 to 10% by mass with respect to the total mass of the polymerizable compound contained in the quantum dot-containing composition serving as the fluorescent region. More preferably, the content is 05 to 5% by mass. It is desirable to adjust the concentration according to the thickness of the phosphor-containing film.
- Quantum dots may be added in the form of particles to the quantum dot-containing composition, or may be added in the form of a dispersion dispersed in a solvent.
- the addition in the state of a dispersion is preferable from the viewpoint of suppressing the aggregation of the quantum dot particles.
- the solvent used here is not particularly limited.
- the ligand in the quantum dot-containing composition can be synthesized by a known synthesis method. For example, it can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2007-277514.
- the curable compound those having a polymerizable group can be widely employed.
- the compound which has a photopolymerizable functional group is preferable.
- it is preferably a (meth) acrylate group, a vinyl group or an epoxy group, more preferably a (meth) acrylate group, and still more preferably an acrylate group.
- each polymeric group may be the same and may differ.
- (meth) acrylate compounds such as monofunctional or polyfunctional (meth) acrylate monomers, polymers thereof, prepolymers, and the like are preferable.
- description with "(meth) acrylate” shall be used by the meaning of at least one of an acrylate and a methacrylate, or either. The same applies to “(meth) acryloyl” and the like.
- Monofunctional- Monofunctional (meth) acrylate monomers include acrylic acid and methacrylic acid, derivatives thereof, and more specifically, monomers having one polymerizable unsaturated bond ((meth) acryloyl group) of (meth) acrylic acid in the molecule Can be mentioned. Specific examples thereof include the following compounds, but the present embodiment is not limited thereto.
- the amount of the monofunctional (meth) acrylate monomer used is 10 parts by mass or more from the viewpoint of adjusting the viscosity of the coating liquid to a preferable range with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. It is preferably 10 to 80 parts by mass.
- polymerizable monomer having two polymerizable groups include a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups.
- Bifunctional polymerizable unsaturated monomers are suitable for reducing the viscosity of the composition.
- (meth) acrylate compounds that are excellent in reactivity and have no problems such as residual catalyst are preferable.
- the amount of the bifunctional (meth) acrylate monomer used is 5 parts by mass or more from the viewpoint of adjusting the viscosity of the coating liquid to a preferable range with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. It is preferably 10 to 80 parts by mass.
- polymerizable monomer having three or more polymerizable groups examples include polyfunctional polymerizable unsaturated monomers having three or more ethylenically unsaturated bond-containing groups. These polyfunctional polymerizable unsaturated monomers are excellent in terms of imparting mechanical strength. In the present embodiment, (meth) acrylate compounds that are excellent in reactivity and have no problems such as residual catalyst are preferable.
- ECH Epichlorohydrin modified glycerol tri (meth) acrylate
- EO ethylene oxide modified glycerol tri (meth) acrylate
- PO propylene oxide modified glycerol tri (meth) acrylate
- pentaerythritol triacrylate pentaerythritol Tetraacrylate
- EO-modified phosphate triacrylate trimethylolpropane tri (meth) acrylate
- tris (acryloxyethyl) isocyanurate dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) a Chlorate
- EO-modified glycerol tri (meth) acrylate PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferably used in the present invention.
- the amount of the polyfunctional (meth) acrylate monomer used is 5 parts by mass or more from the viewpoint of the coating strength of the fluorescent-containing layer after curing with respect to 100 parts by mass of the total amount of the curable compound contained in the coating liquid. It is preferable that it is 95 mass parts or less from a viewpoint of gelatinization suppression of a coating liquid.
- the (meth) acrylate monomer is preferably an alicyclic acrylate.
- monofunctional (meth) acrylate monomers include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
- bifunctional (meth) acrylate monomer include tricyclodecane dimethanol di (meth) acrylate.
- the total amount of the polymerizable compound in the curable composition forming the binder is preferably 70 to 99 parts by mass with respect to 100 parts by mass of the curable composition from the viewpoint of handling and curing of the composition. 85 to 97 parts by mass is more preferable.
- -Epoxy compounds, etc.- examples include compounds having a cyclic group such as a cyclic ether group capable of ring-opening polymerization such as an epoxy group and an oxetanyl group. More preferable examples of such a compound include compounds having an epoxy group-containing compound (epoxy compound).
- epoxy compound By using a compound having an epoxy group or an oxetanyl group in combination with a (meth) acrylate compound, the adhesion with the barrier layer tends to be improved.
- Examples of the compound having an epoxy group include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.
- the compound having an epoxy group that can be preferably used include, for example, an aliphatic cyclic epoxy compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols
- aliphatic cyclic epoxy compounds bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.
- UVR-6216 manufactured by Union Carbide
- glycidol AOEX24
- Cyclomer A200 Celoxide 2021P
- Celoxide 8000 aboveve, Daicel Chemical Industries, Ltd.
- 4-vinylcyclohexene dioxide manufactured by Sigma Aldrich
- Epicoat 828 Epicoat 812
- Epicoat 1031 Epicoat 872
- Epicoat CT508 aboveve, manufactured by Yuka Shell Co., Ltd.
- KRM-2400, KRM-2410, KRM -2408, KRM-2490, KRM-2720, KRM-2750 aboveve, manufactured by Asahi Denka Kogyo Co., Ltd.
- these compounds having an epoxy group or oxetanyl group may be produced by any method.
- Maruzen KK Publishing Co., Ltd., 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. By Alfred Hasfner The chemistry OF heterocyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.
- a vinyl ether compound may be used as the curable compound used in the present embodiment.
- known compounds can be appropriately selected. For example, those described in paragraph No. 0057 of JP-A-2009-73078 can be preferably used.
- vinyl ether compounds are, for example, the method described in Stephen C. Lapin, Polymers Paint Paint, Journal 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.
- a silsesquioxane compound having a reactive group described in JP-A-2009-73078 can be used from the viewpoint of reducing the viscosity and increasing the hardness.
- (meth) acrylate compounds are preferable from the viewpoint of composition viscosity and photocurability, and acrylates are more preferable.
- a polyfunctional polymerizable compound having two or more polymerizable functional groups is preferred.
- the blending ratio of the monofunctional (meth) acrylate compound and the polyfunctional (meth) acrylate compound is preferably 80/20 to 0/100, more preferably 70/30 to 0/100 by weight, / 60 to 0/100 is preferable. By selecting an appropriate ratio, sufficient curability can be obtained and the composition can have a low viscosity.
- the ratio of the bifunctional (meth) acrylate to the trifunctional or higher functional (meth) acrylate is preferably 100/0 to 20/80, more preferably 100/0. To 50/50, more preferably 100/0 to 70/30. Since the trifunctional or higher functional (meth) acrylate has a higher viscosity than the bifunctional (meth) acrylate, the more bifunctional (meth) acrylate is more impermeable to oxygen in the present invention. This is preferable because the viscosity of the curable compound can be lowered.
- the polymerizable compound preferably contains a compound containing a substituent having an aromatic structure and / or an alicyclic hydrocarbon structure from the viewpoint of increasing the impermeability to oxygen.
- the aromatic structure and / or alicyclic carbonization is preferred.
- the polymerizable compound having a hydrogen structure is contained in an amount of 50% by mass or more, and more preferably 80% by mass or more.
- a (meth) acrylate compound having an aromatic structure is preferable.
- Examples of the (meth) acrylate compound having an aromatic structure include monofunctional (meth) acrylate compounds having a naphthalene structure, such as 1- or 2-naphthyl (meth) acrylate, 1- or 2-naphthylmethyl (meth) acrylate, 1 Particularly preferred are-or 2-naphthylethyl (meth) acrylate, monofunctional acrylates such as benzyl acrylate having a substituent on the aromatic ring, and bifunctional acrylates such as catechol diacrylate and xylylene glycol diacrylate.
- Polymerizable compounds having an alicyclic hydrocarbon structure include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and adamantyl (meth).
- Preferred are acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate and the like.
- acrylate is preferred to methacrylate from the viewpoint of excellent curability.
- the curable compound may contain a thixotropic agent.
- the thixotropic agent is an inorganic compound or an organic compound.
- thixotropic agent is a thixotropic agent of an inorganic compound.
- an acicular compound, a chain compound, a flat compound, or a layered compound can be preferably used. Of these, a layered compound is preferable.
- talc kaolinite (kaolin clay), pyrophyllite (waxite clay), sericite (sericite), bentonite, smectite vermiculites (montmorillonite, beidellite, Nontronite, saponite, etc.), organic bentonite, organic smectite and the like.
- layered compounds include, for example, crown clay, Burgess clay # 60, Burgess clay KF, OptiWhite (manufactured by Shiraishi Kogyo Co., Ltd.), kaolin JP-100, NN kaolin clay, ST kaolin.
- Clay Hardsil (above, manufactured by Tsuchiya Kaolin Industry Co., Ltd.), ASP-072, Satinton Plus, Translink 37, Hydras Delami NCD (above, manufactured by Angelhard Co., Ltd.), SY Kaolin, OS clay, HA clay MC hard clay (above, manufactured by Maruo Calcium Co., Ltd.), Lucentite SWN, Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN (above manufactured by Coop Chemical Co.), Smecton (produced by Kunimine Industries), Wenger, Wenger FW, S , Sven 74, Organite, Organite T (above, Hojun Co., Ltd.), Hotaka, Olven, 250M, Benton 34, Benton 38 (above, Wilber Ellis), Laponite, Laponite RD, Laponite RDS (Nippon Silica Industry Co., Ltd.). These compounds may be dispersed in a solvent.
- silicate compounds represented by xM (I) 2 O ⁇ ySiO 2 (M (II) O, M (III having an oxidation number of 2 or 3) are used.
- M (II) O M (III having an oxidation number of 2 or 3
- x and y represent positive numbers
- more preferred compounds are swellable layered clay minerals such as hectorite, bentonite, smectite and vermiculite.
- a layered (clay) compound modified with an organic cation a cation compound obtained by exchanging an interlayer cation such as sodium of a silicate compound with an organic cation compound
- an organic cation a cation compound obtained by exchanging an interlayer cation such as sodium of a silicate compound with an organic cation compound
- sodium silicate / magnesium (hectorite) In which the sodium ion is exchanged with the following ammonium ion.
- ammonium ions include monoalkyltrimethylammonium ions having 6 to 18 carbon atoms, dialkyldimethylammonium ions, trialkylmethylammonium ions, and dipolyoxyethylene coconut oil alkyls having 4 to 18 oxyethylene chains.
- Examples include methylammonium ion, bis (2-hydroxyethyl) coconut oil alkylmethylammonium ion, and polyoxypropylenemethyldiethylammonium ion having an oxopropylene chain of 4 to 25. These ammonium ions can be used alone or in combination of two or more.
- the sodium silicate / magnesium is dispersed in water and sufficiently stirred, and then allowed to stand for 16 hours or more. Adjust the dispersion. While stirring the dispersion, 30 to 200% by mass of a desired ammonium salt is added to sodium magnesium silicate. After the addition, cation exchange occurs, and hectorite containing an ammonium salt between layers becomes insoluble in water and precipitates. Therefore, the precipitate is collected by filtration and dried. During the preparation, heating may be performed in order to accelerate dispersion.
- alkylammonium-modified silicate minerals examples include Lucentite SAN, Lucentite SAN-316, Lucentite STN, Lucentite SEN, Lucentite SPN (manufactured by Coop Chemical Co., Ltd.), or a single type or two or more types. Can be used in combination.
- silica, alumina, silicon nitride, titanium dioxide, calcium carbonate, zinc oxide, or the like can be used as a thixotropic agent for inorganic compounds. If necessary, these compounds can be subjected to a treatment for adjusting hydrophilicity or hydrophobicity on the surface.
- thixotropic agent a thixotropic agent of an organic compound can be used.
- thixotropic agents for organic compounds include polyolefin oxide and modified urea.
- the above-mentioned oxidized polyolefin may be prepared in-house or a commercially available product may be used.
- commercially available products include Disparon 4200-20 (trade name, manufactured by Enomoto Kasei Co., Ltd.), Flownon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
- the aforementioned modified urea is a reaction product of an isocyanate monomer or its adduct and an organic amine.
- the above-mentioned modified urea may be prepared in-house or a commercially available product may be used.
- BYK410 made by Big Chemie
- lifted for example.
- the content of the thixotropic agent is preferably 0.15 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the curable compound in the coating solution, and 0.2 It is particularly preferred that the amount be ⁇ 8 parts by mass.
- brittleness tends to be improved when it is 20 mass or less with respect to 100 mass parts of the curable compound.
- the coating solution may contain a known polymerization initiator as a polymerization initiator.
- a polymerization initiator for example, paragraph 0037 of JP2013-043382A can be referred to.
- the polymerization initiator is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of the curable compound contained in the coating solution.
- the total curable composition excluding the volatile organic solvent preferably contains 0.1% by mass to 10% by mass, and more preferably 0.2% by mass to 8% by mass.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen preferably contains a photopolymerization initiator.
- a photopolymerization initiator any compound can be used as long as it is a compound that generates an active species that polymerizes the above-described polymerizable compound by light irradiation.
- the photopolymerization initiator include a cationic polymerization initiator and a radical polymerization initiator, and a radical polymerization initiator is preferred.
- a plurality of photopolymerization initiators may be used in combination.
- the content of the photopolymerization initiator is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass, and more preferably 0.2 to 7% by mass in the entire composition excluding the solvent. %.
- the total amount becomes the said range.
- the content of the photopolymerization initiator is 0.01% by mass or more because sensitivity (fast curability) and coating film strength tend to be improved.
- the content of the photopolymerization initiator is 15% by mass or less, light transmittance, colorability, handleability and the like tend to be improved, which is preferable.
- dyes and / or pigments may act as radical trapping agents, affecting photopolymerization and sensitivity.
- the amount of the photopolymerization initiator added is optimized in these applications.
- dyes and / or pigments are not essential components, and the optimal range of the photopolymerization initiator may be different from that in the field of curable compositions for liquid crystal display color filters. is there.
- radical photopolymerization initiator for example, a commercially available initiator can be used.
- these examples for example, those described in paragraph No. 0091 of JP-A No. 2008-105414 can be preferably used.
- acetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred from the viewpoints of curing sensitivity and absorption characteristics.
- acetophenone compound examples include hydroxyacetophenone compounds, dialkoxyacetophenone compounds, and aminoacetophenone compounds.
- Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, preferably available from BASF as a hydroxyacetophenone compound
- Irgacure® 184 (1-hydroxycyclohexyl phenyl ketone
- Irgacure® 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone
- Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl)
- Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane-1-o) available from BASF is preferable.
- Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane-1-o) available from BASF
- Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
- Irgacure (registered trademark) 379 (available from BASF Corporation) is preferable.
- EG (2-dimethylamino-2- (4methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one
- Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinopropan-1-one.
- acylphosphine oxide-based compound preferably Irgacure (registered trademark) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure (registered trademark) 1800 (bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethyl) available from BASF Benzoylphenylethoxyphosphine oxide).
- Irgacure (registered trademark) 819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- Irgacure (registered trademark) 1800 bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide
- Irgacure registered trademark
- OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)
- Irgacure registered trademark
- BASF oxime ester compound
- OXE02 ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
- sulfonium salt compounds As the cationic photopolymerization initiator, sulfonium salt compounds, iodonium salt compounds, oxime sulfonate compounds and the like are preferable, and 4-methylphenyl [4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate (PI2074 manufactured by Rhodea)] 4-methylphenyl [4- (2-methylpropyl) phenyliodonium hexafluorophosphate (IRGACURE250 manufactured by BASF), IRGACURE PAG103, 108, 121, 203 (manufactured by BASF) and the like.
- the photopolymerization initiator needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so that the mold has to be frequently washed, and the photocurable composition is deformed in the mold to cause problems such as deterioration of the transfer pattern accuracy.
- the curable composition for forming the resin layer 38 that is impermeable to oxygen may include a polymer.
- the polymer include poly (meth) acrylate, poly (meth) acrylamide, polyester, polyurethane, polyurea, polyamide, polyether, and polystyrene.
- the fluorescent region forming coating solution may contain a viscosity modifier, a silane coupling agent, a surfactant, an antioxidant, an oxygen getter agent, a polymerization inhibitor, inorganic particles, and the like.
- the coating solution for forming the fluorescent region may contain a viscosity modifier as necessary. They can be adjusted to the desired viscosity by adding viscosity modifiers.
- the viscosity modifier is preferably a filler having a particle size of 5 nm to 300 nm.
- the viscosity modifier may be a thixotropic agent.
- the thixotropic property refers to the property of reducing the viscosity with respect to the increase in shear rate in the liquid composition
- the thixotropic agent includes the liquid composition by including it. It refers to a material having a function of imparting thixotropic properties to the composition.
- thixotropic agents include fumed silica, alumina, silicon nitride, titanium dioxide, calcium carbonate, zinc oxide, talc, mica, feldspar, kaolinite (kaolin clay), pyrophyllite (waxite clay), and sericite.
- sericite bentonite, smectite vermiculites (montmorillonite, beidellite, nontronite, saponite, etc.), organic bentonite, organic smectite and the like.
- the phosphor-containing layer formed from the coating solution containing the silane coupling agent has strong adhesion to the adjacent layer due to the silane coupling agent, it can exhibit excellent durability.
- the phosphor-containing layer formed from the coating solution containing the silane coupling agent has a relationship of the adhesion force A between the support film under the adhesion condition and the barrier layer ⁇ the adhesion force B between the phosphor-containing layer and the barrier layer. This is also preferable. This is mainly due to the fact that the silane coupling agent contained in the phosphor-containing layer forms a covalent bond with the surface of the adjacent layer and the constituent components of this phosphor-containing layer by a hydrolysis reaction or a condensation reaction.
- the silane coupling agent has a reactive functional group such as a radical polymerizable group
- the monomer component constituting the phosphor-containing layer may form a cross-linked structure, or the phosphor-containing layer may be closely adhered to the adjacent layer. It can contribute to improvement of performance.
- silane coupling agent a known silane coupling agent can be used without any limitation.
- a silane coupling agent represented by the following general formula (1) described in JP2013-43382A can be exemplified.
- R 1 to R 6 are each independently a substituted or unsubstituted alkyl group or an aryl group, provided that at least one of R 1 to R 6 is a radical polymerizable group. This is a substituent containing a carbon-carbon double bond.
- R 1 to R 6 are preferably an unsubstituted alkyl group or an unsubstituted aryl group, except in the case of a substituent containing a radically polymerizable carbon-carbon double bond.
- alkyl group an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
- aryl group a phenyl group is preferable.
- R 1 to R 6 are particularly preferably a methyl group.
- At least one of R 1 ⁇ R 6 is a radical polymerizable carbon - having a substituent containing a carbon double bond, two are radically polymerizable carbon of R 1 ⁇ R 6 - carbon double bonds A substituent is preferred. Further, among R 1 to R 3 , the number of those having a substituent containing a radical polymerizable carbon-carbon double bond is 1, and among R 4 to R 6 , the radical polymerizable carbon-carbon It is particularly preferred that the number of those having a substituent containing a double bond is 1.
- the substituents in which the silane coupling agent represented by the general formula (1) includes two or more radically polymerizable carbon-carbon double bonds may be the same or different. The same is preferable.
- the substituent containing a radically polymerizable carbon-carbon double bond is preferably represented by —XY.
- X is a single bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group, preferably a single bond, a methylene group, an ethylene group, a propylene group, or a phenylene group.
- Y is a radically polymerizable carbon-carbon double bond group, and is preferably an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a propenyl group, a vinyloxy group, or a vinylsulfonyl group.
- An acryloyloxy group is more preferred.
- R 1 to R 6 may have a substituent other than a substituent containing a radically polymerizable carbon-carbon double bond.
- substituents include alkyl groups (eg, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group).
- aryl groups eg phenyl group, naphthyl group etc.
- halogen atoms eg fluorine, chlorine, bromine, iodine
- acyl groups eg acetyl group, benzoyl group, formyl group, pivaloyl group etc.
- acyloxy Groups for example, acetoxy group, acryloyloxy group, methacryloyloxy group, etc.
- alkoxycarbonyl groups for example, methoxycarbonyl group, ethoxycarbonyl group, etc.
- aryloxycarbonyl groups for example, phenyloxycarbonyl group, etc.
- sulfonyl groups For example, methanesulfonyl group, benzene Honiru group
- the silane coupling agent is preferably contained in the coating solution in the range of 1 to 30% by mass, more preferably 3 to 30% by mass. More preferably, it is 5 to 25% by mass.
- the coating solution for forming a fluorescent region may contain at least one surfactant containing 20% by mass or more of fluorine atoms.
- the surfactant preferably contains 25% by mass or more of fluorine atoms, and more preferably contains 28% by mass or more.
- the upper limit is not particularly defined, but is, for example, 80% by mass or less, and preferably 70% by mass or less.
- the surfactant used in the present invention is preferably a compound having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
- An alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
- the cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
- the cycloalkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
- An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom.
- Examples of the aryl group include a phenyl group and a naphthyl group.
- the aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.
- the molecular weight of the surfactant is preferably 300 to 10,000, and more preferably 500 to 5,000.
- the content of the surfactant in the entire composition excluding the solvent is, for example, 0.01 to 10% by mass, preferably 0.1 to 7% by mass, and more preferably 0.5 to 4% by mass. It is. When using 2 or more types of surfactant, the total amount becomes the said range.
- surfactants examples include the product names Florard FC-430 and FC-431 (manufactured by Sumitomo 3M), the product name Surflon "S-382" (manufactured by Asahi Glass), EFTOP "EF-122A, 122B, 122C, EF- 121, EF-126, EF-127, MF-100 ”(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 (all OMNOVA), trade names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), trade names Megafuck 171, 172, 173, 178K, 178A (all manufactured by DIC Corporation), trade names X-70-090, X-70-091, X-70-0 2, X-70-093, (all manufactured by Shin-Etsu Chemical
- the curable compound that forms the resin layer 38 that is impermeable to oxygen preferably contains a known antioxidant.
- the antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NOx, and SOx (X is an integer).
- X is an integer.
- the antioxidant is preferably 0.2% by mass or more, and preferably 1% by mass or more, based on the total mass of the curable compound.
- antioxidants may be altered by interaction with oxygen.
- the altered antioxidant may induce decomposition of the quantum dot-containing polymerizable composition, resulting in decreased adhesion, poor brittleness, and reduced quantum dot luminous efficiency. From the viewpoint of preventing these, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
- the antioxidant is preferably at least one of a radical inhibitor, a metal deactivator, a singlet oxygen scavenger, a superoxide scavenger, or a hydroxy radical scavenger.
- antioxidants include phenolic antioxidants, hindered amine antioxidants, quinone antioxidants, phosphorus antioxidants, and thiol antioxidants.
- phenolic antioxidants examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4- Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl- m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-
- phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos.
- thiol antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and pentaerythritol tetra ( ⁇ -alkylmercaptopropionic acid) ester And the like.
- the hindered amine antioxidant is also referred to as HALS (Hidered amine lightstableizers), and has a structure in which all hydrogen atoms on carbons at the 2-position and 6-position of piperidine are substituted with methyl groups, preferably a group represented by the following formula 1.
- X in Formula 1 represents a hydrogen atom or an alkyl group.
- 2,2,6,6-tetramethyl-4-piperidyl group in which X is a hydrogen atom, or 1,2,2,6,6- in which X is a methyl group HALS having a pentamethyl-4-piperidyl group is particularly preferably employed.
- Many HALS having a structure in which a group represented by the formula 1 is bonded to a —COO— group, that is, a group represented by the following formula 2 are commercially available.
- HALS that can be preferably used in the present invention include those represented by the following formulas.
- 2,2,6,6-tetramethyl-4-piperidyl group is represented by R
- 1,2,2,6,6-pentamethyl-4-piperidyl group is represented by R ′.
- CH 2 (COOR ′) CH (COOR ′) CH (COOR ′) CH 2 COOR ′ compounds represented by Formula 3, and the like.
- Tinuvin 123 Tinuvin 144, Tinuvin 765, Tinuvin 770, Tinuvin 622, Chimassorb 944, Chimassorb 119 (all of which are trade names of Ciba Specialty Chemicals), Adeka Stub LA52, Adeka Stub LA57 , Adeka Stub LA62, Adeka Stub LA67, Adeka Stub LA82, Adeka Stub LA87, Adeka Stub LX335 (all of which are trade names of Asahi Denka Kogyo Co., Ltd.) and the like, but are not limited thereto.
- HALS those having relatively small molecules are preferable because they easily diffuse from the resin layer to the fluorescent region.
- Preferred HALS from this viewpoint includes a compound represented by ROC ( ⁇ O) (CH 2 ) 8 C ( ⁇ O) OR, R′OC ( ⁇ O) C (CH 3 ) ⁇ CH 2 .
- the antioxidant is at least one of a hindered phenol compound, a hindered amine compound, a quinone compound, a hydroquinone compound, a triferol compound, an aspartic acid compound, or a thiol compound, and a citric acid compound, More preferably, it is at least one of an ascorbic acid compound and a tocopherol compound.
- these compounds are not particularly limited, but hindered phenol, hindered amine, quinone, hydroquinone, triferol, aspartic acid, thiol, citric acid, tocopheryl acetic acid, and tocopheryl phosphate itself, or a salt or ester compound thereof. Etc. are preferable.
- oxygen getter agent a known substance used as a getter agent for an organic EL element can be used, and either an inorganic getter agent or an organic getter agent may be used, and a metal oxide, a metal halide, a metal sulfate, It is preferable to include at least one compound selected from metal perchlorate, metal carbonate, metal alkoxide, metal carboxylate, metal chelate, or zeolite (aluminosilicate).
- Such oxygen getter agents include calcium oxide (CaO), barium oxide (BaO), magnesium oxide (MgO), strontium oxide (SrO), lithium sulfate (Li 2 SO 4 ), sodium sulfate (Na 2 SO 4 ), sulfuric acid.
- the organic getter agent is not particularly limited as long as it is a material that takes in water by a chemical reaction and does not become opaque before and after the reaction.
- the organometallic compound means a compound having a metal-carbon bond, a metal-oxygen bond, a metal-nitrogen bond, or the like.
- the aforementioned bond is broken by the hydrolysis reaction to form a metal hydroxide.
- hydrolytic polycondensation may be performed after the reaction with the metal hydroxide to increase the molecular weight.
- an organic metal compound that has good reactivity with water that is, a metal atom that easily breaks various bonds with water.
- a metal atom that easily breaks various bonds with water include aluminum, silicon, titanium, zirconium, silicon, bismuth, strontium, calcium, copper, sodium, and lithium.
- cesium, magnesium, barium, vanadium, niobium, chromium, tantalum, tungsten, chromium, indium, iron, and the like can be given.
- a desiccant of an organometallic compound having aluminum as a central metal is preferable in terms of dispersibility in a resin and reactivity with water.
- Organic groups include unsaturated hydrocarbons such as methoxy group, ethoxy group, propoxy group, butoxy group, 2-ethylhexyl group, octyl group, decyl group, hexyl group, octadecyl group, stearyl group, saturated hydrocarbon, branched unsaturated carbon Examples include ⁇ -diketonato groups such as alkoxy groups, carboxyl groups, aceethylacetonato groups, and dipivaloylmethanato groups containing hydrogen, branched saturated hydrocarbons, and cyclic hydrocarbons. Among these, aluminum ethyl acetoacetates having 1 to 8 carbon atoms represented by the following chemical formula are preferably used because they can form a sealing composition having excellent transparency.
- R 5 to R 8 represent an organic group including an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, a cycloalkyl group, and an acyl group, and M represents a trivalent metal atom.
- R 5 to R 8 may be the same or different organic groups.
- the aluminum ethyl acetoacetates having 1 to 8 carbon atoms are commercially available from, for example, Kawaken Fine Chemical Co., Ltd. and Hope Pharmaceutical Co., Ltd.
- the oxygen getter agent is in the form of particles or powder.
- the average particle diameter of the oxygen getter agent may be usually in the range of less than 20 ⁇ m, preferably 10 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1 ⁇ m or less.
- the average particle size of the oxygen getter agent is preferably 0.3 to 2 ⁇ m, and more preferably 0.5 to 1.0 ⁇ m.
- the average particle diameter here refers to the average value of the particle diameters calculated from the particle size distribution measured by the dynamic light scattering method.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen preferably contains a polymerization inhibitor.
- the content of the polymerization inhibitor is 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, and still more preferably 0.008 to 0.
- the polymerization inhibitor may be added during production of the polymerizable monomer, or may be added later to the cured composition.
- Preferred polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, phenothiazine, phenoxazine, 4-methoxynaphthol, 2,2,6,6-tetramethyl Examples include piperidine-1-oxyl free radical, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, nitrobenzene, dimethylaniline and the like.
- p-benzoquino 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, phenothiazine.
- These polymerization inhibitors suppress the generation of polymer impurities not only during the production of the polymerizable monomer but also during storage of the cured composition, and suppress the deterioration of pattern formation during imprinting.
- the resin layer 38 that is impermeable to oxygen is formed by applying and curing a resin-forming coating solution containing the curable compound described above.
- the oxygen permeability at the shortest distance between the fluorescent regions 35 adjacent to each other in the resin layer 38 preferably satisfies 10 cc / (m 2 ⁇ day ⁇ atm) or less. More preferably an oxygen permeability in the shortest distance between adjacent fluorescent regions 35 of the resin layer 38 is 1cc / (m 2 ⁇ day ⁇ atm) or less, 10 -1 cc / (m 2 ⁇ day ⁇ atm) or less More preferably.
- the necessary minimum distance between the fluorescent regions 35 differs.
- the shortest distance between the fluorescent regions 35 adjacent to each other in the resin layer 38 means the shortest distance in the film plane between the resin and the phosphor region when observed from the phosphor-containing film main surface.
- the shortest distance between the fluorescent regions 35 adjacent to each other in the resin layer 38 may be referred to as the width of the resin layer.
- the minimum required distance between the phosphor regions 35 varies depending on the composition of the resin layer 38.
- the minimum distance between the adjacent fluorescent regions 35 of the resin layer 38 that is, the width of the resin layer is 0.001 mm or more. 3 mm or less is preferable, 0.01 mm or more and 2 mm or less is more preferable, and 0.03 mm or more and 2 mm or less is particularly preferable. If the width of the resin layer is too short, it is difficult to ensure the necessary oxygen permeability, and if the width of the resin layer is too long, luminance unevenness of the display device is deteriorated, which is not preferable.
- the ratio of the volume Vp of the fluorescent region to the volume Vb of the resin layer can be any ratio, but the ratio of the volume Vp of the fluorescent region to the volume of the entire phosphor-containing layer (Vp + Vb) is 0.1 ⁇ Vp / (Vp + Vb) ⁇ 0.9 is preferable, 0.2 ⁇ Vp / (Vp + Vb) ⁇ 0.85 is more preferable, and 0.3 ⁇ Vp / (Vp + Vb) ⁇ 0.8 is particularly preferable.
- the region Vp containing the phosphor and the region Vb of the oxygen-impermeable resin layer are defined as the product of the area and the thickness when observed from the phosphor-containing film main surface.
- a compound having a bifunctional or higher photopolymerizable crosslinking group is preferable.
- an alicyclic (meth) acrylate such as urethane (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.
- (Meth) acrylates having hydroxyl groups such as pentaerythritol triacrylate, aromatic (meth) acrylates such as modified bisphenol a di (meth) acrylate, dipentaerythritol di (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And (meth) acrylate, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bisphenol a-type epoxy and the like.
- aromatic (meth) acrylates such as modified bisphenol a di (meth) acrylate, dipentaerythritol di (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And (meth) acrylate, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bisphenol a-type epoxy and the like.
- a compound having a polar functional group such as a urethane bond, a hydroxyl group, or a carboxyl group
- an interaction between molecules is enhanced, and a resin layer having high oxygen impermeability is obtained.
- a compound having the same polymerizable crosslinking group as the fluorescent region is included from the viewpoint of excellent adhesion between the resin layer and the fluorescent region.
- the resin layer includes at least a (meth) acrylate compound.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen of the present invention contains, as a polymerizable compound, a (meth) acrylate compound having an aromatic structure and / or an alicyclic hydrocarbon structure and a fluorine atom. Both (meth) acrylates may be included.
- a compounding ratio 80% by mass or more of the total polymerizable compound component is a (meth) acrylate compound having an aromatic structure and / or an alicyclic hydrocarbon structure, and 0.1 to 10% by mass has a fluorine atom ( A meth) acrylate is preferred.
- a blend system in which a (meth) acrylate compound having an aromatic structure and / or an alicyclic hydrocarbon structure is a liquid at 1 atm 25 ° C., and a (meth) acrylate having a fluorine atom is a solid at 1 atm 25 ° C. preferable.
- the total content of the polymerizable compound in the curable compound that forms the resin layer 38 that is impervious to oxygen is from the viewpoint of improving curability and improving the viscosity of the curable compound. 50 to 99.5 mass% is preferable, 70 to 99 mass% is more preferable, and 90 to 99 mass% is particularly preferable.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen relates to the polymerizable compound component, and more preferably the content of the polymerizable compound having a viscosity of 3 to 2000 mPa ⁇ s at 25 ° C. is totally polymerized.
- the amount of the polymerizable compound is preferably 80% by mass or more, more preferably 5 to 1000 mPa ⁇ s polymerizable compound, and more preferably 80% by mass or more, and 7 to 500 mPa ⁇ s polymerizable compound is 80% by mass or more. It is particularly preferable that the polymerizable compound of 10 to 300 mPa ⁇ s is 80% by mass or more.
- the polymerizable compound contained in the curable compound that forms the resin layer 38 that is impermeable to oxygen it is determined that the polymerizable compound that is liquid at 25 ° C. is 50% by mass or more in the total polymerizable compound. It is preferable from the viewpoint of stability.
- the curable compound that forms the resin layer 38 impermeable to oxygen is a radical in which the polymerizable compound is a radical polymerizable compound and the photopolymerization initiator is a radical polymerization initiator that generates radicals upon light irradiation. It is preferably a polymerizable curable composition.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen may contain at least one surfactant containing 20% by mass or more of fluorine atoms.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen preferably contains a known oxygen getter agent.
- the oxygen getter agent is preferably 0.1 to 20% by mass relative to the total mass of the curable compound.
- the content is more preferably 15 to 15% by mass, and further preferably 0.1 to 10% by mass.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen preferably contains inorganic particles.
- the impermeability to oxygen can be increased by containing inorganic particles.
- the inorganic particles include silica particles, alumina particles, zirconium oxide particles, zinc oxide particles, titanium oxide particles, and inorganic layered compounds such as mica and talc.
- a mold release agent for the curable compound that forms the resin layer 38 that is impermeable to oxygen, in addition to the above-mentioned components, a mold release agent, a silane coupling agent, an ultraviolet absorber, a light stabilizer, and an anti-aging agent as necessary.
- the method for preparing the curable composition for forming the resin layer 38 that is impermeable to oxygen is not particularly limited, and may be performed according to a general procedure for preparing a curable composition.
- the 1st base film 10 and the 2nd base film 20 are films which have a function which suppresses permeation
- it has the structure provided with the barrier layers 12 and 22 on one surface of the support films 11 and 21, respectively.
- the presence of the support films 11 and 21 improves the strength of the phosphor-containing film, and enables easy film formation.
- the base film may be comprised only by the support body which has sufficient barrier property.
- the first base film 10 and the second base film 20 preferably have a total light transmittance of 80% or more in the visible light region, and more preferably 85% or more.
- the visible light region refers to a wavelength region of 380 to 780 nm, and the total light transmittance indicates an average value of light transmittance over the visible light region.
- the oxygen permeability of the 1st base film 10 and the 2nd base film 20 is 1.00 cc / (m ⁇ 2 > * day * atm) or less.
- the oxygen permeability is more preferably 0.1 cc / (m 2 ⁇ day ⁇ atm) or less, further preferably 0.01 cc / (m 2 ⁇ day ⁇ atm) or less, and particularly preferably 0.001 cc / (M 2 ⁇ day ⁇ atm) or less.
- the oxygen permeability is a value measured using an oxygen gas permeability measuring apparatus (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%. is there.
- the first base film 10 and the second base film 20 preferably have a function of blocking moisture (water vapor) in addition to a gas barrier function of blocking oxygen.
- the moisture permeability (water vapor permeability) of the first substrate film 10 and the second substrate film 20 is preferably 0.10 g / (m 2 ⁇ day ⁇ atm) or less, and 0.01 g / (m 2 ⁇ Day ⁇ atm) or less.
- a flexible belt-like support that is transparent to visible light is preferable.
- transparent to visible light means that the linear transmittance in the visible light region is 80% or more, preferably 85% or more.
- the light transmittance used as a measure of transparency is measured by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device. It can be calculated by subtracting the rate.
- the support film preferably has a barrier property against oxygen and moisture.
- Preferred examples of the support film include a polyethylene terephthalate film, a film made of a polymer having a cyclic olefin structure, and a polystyrene film.
- the thickness of the support film is within the range of 10 to 500 ⁇ m, particularly within the range of 15 to 300 ⁇ m, particularly within the range of 15 to 120 ⁇ m, more particularly within the range of 15 to 100 ⁇ m, from the viewpoints of gas barrier properties, impact resistance, etc. Furthermore, it is preferably 25 to 110 ⁇ m, more preferably 25 to 60 ⁇ m.
- the support films 11 and 21 preferably have an in-plane retardation Re (589) at a wavelength of 589 nm of 1000 nm or less. More preferably, it is 500 nm or less, and further preferably 200 nm or less.
- Re (589) of the support is in the above range because foreign matters and defects can be more easily found during inspection using a polarizing plate.
- Re (589) can be measured by making light having an input wavelength of 589 nm incident in the normal direction of the film using AxoScan OPMF-1 (manufactured by Optoscience).
- the barrier layers 12, 22 including at least one inorganic layer formed in contact with the surface of the support films 11, 21 on the phosphor-containing layer 30 side. It is preferable to provide.
- the barrier layers 12 and 22 may include at least one inorganic layer and at least one organic layer. Laminating a plurality of layers in this manner is preferable from the viewpoint of improving light resistance because the barrier property can be further enhanced.
- the number of layers to be stacked increases, the light transmittance of the base film tends to decrease. Therefore, it is desirable to increase the number of layers within a range in which good light transmittance can be maintained.
- the barrier layers 12 and 22 preferably have a total light transmittance in the visible light region of 80% or more and an oxygen permeability of 1.00 cc / (m 2 ⁇ day ⁇ atm) or less. It is preferable.
- the oxygen permeability of the barrier layers 12 and 22 is more preferably 0.1 cc / (m 2 ⁇ day ⁇ atm) or less, particularly preferably 0.01 cc / (m 2 ⁇ day ⁇ atm) or less, and particularly preferably. Is 0.001 cc / (m 2 ⁇ day ⁇ atm) or less. The lower the oxygen permeability, the better, and the higher the total light transmittance in the visible light region, the better.
- the inorganic layer is a layer mainly composed of an inorganic material, preferably a layer formed only from an inorganic material.
- the inorganic layer is preferably a layer having a gas barrier function of blocking oxygen.
- the oxygen permeability of the inorganic layer is preferably 1.00 cc / (m 2 ⁇ day ⁇ atm) or less.
- the oxygen permeability of the inorganic layer can be obtained by attaching a wavelength conversion layer to the detection part of an oxygen meter made by Orbis Fair Laboratories via silicon grease and converting the oxygen permeability from the equilibrium oxygen concentration value. It is also preferable that the inorganic layer has a function of blocking water vapor.
- Two or more inorganic layers may be included in the barrier layer.
- the thickness of the inorganic layer may be 1 to 500 nm, preferably 5 to 300 nm, particularly preferably 10 to 150 nm. This is because when the film thickness of the inorganic layer is within the above-described range, it is possible to suppress reflection in the inorganic layer while providing good barrier properties, and to provide a laminated film with higher light transmittance. .
- the base film preferably includes at least one inorganic layer adjacent to the phosphor-containing layer.
- the inorganic material constituting the inorganic layer is not particularly limited, and for example, various inorganic compounds such as metals or inorganic oxides, nitrides, oxynitrides, and the like can be used.
- silicon, aluminum, magnesium, titanium, tin, indium and cerium are preferable, and one or two or more of these may be included.
- Specific examples of the inorganic compound include silicon oxide, silicon oxynitride, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, silicon nitride, aluminum nitride, and titanium nitride.
- a metal film such as an aluminum film, a silver film, a tin film, a chromium film, a nickel film, or a titanium film may be provided.
- the inorganic layer having the barrier property is particularly preferably an inorganic layer containing at least one compound selected from silicon nitride, silicon oxynitride, silicon oxide, and aluminum oxide. Since the inorganic layer made of these materials has good adhesion to the organic layer, even when the inorganic layer has pinholes, the organic layer can effectively fill the pinholes and suppress breakage. In addition, it is possible to form an extremely excellent inorganic layer film even in a case where an inorganic layer is further laminated, and to further increase the barrier property.
- the method for forming the inorganic layer is not particularly limited, and for example, various film forming methods capable of evaporating or scattering the film forming material and depositing it on the deposition surface can be used.
- Examples of the method for forming the inorganic layer include a vacuum evaporation method in which an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced.
- an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced.
- Oxidation reaction vapor deposition method for oxidizing and vapor deposition sputtering method using inorganic material as target raw material, introducing argon gas and oxygen gas and performing sputtering; plasma generated on inorganic material with plasma gun
- chemical vapor deposition physical vapor deposition method, PVD method
- ion plating method which is heated by a beam for vapor deposition, or a silicon oxide vapor deposition film is formed
- a plasma chemical vapor phase using an organosilicon compound as a raw material Growth method (Chemical Vapor Deposition method, CV Law), and the like.
- the organic layer is a layer mainly composed of an organic material, and preferably refers to a layer in which the organic material occupies 50% by mass or more, more preferably 80% by mass or more, particularly 90% by mass or more.
- JP, 2007-290369, A paragraphs 0020-0042 and JP, 2005-096108, A paragraphs 0074-0105 can be referred to as an organic layer.
- an organic layer contains a cardo polymer within the range which satisfies said adhesive force conditions.
- the adhesiveness between the organic layer and the adjacent layer, particularly the adhesiveness with the inorganic layer is improved, and a further excellent gas barrier property can be realized.
- the thickness of the organic layer is preferably in the range of 0.05 to 10 ⁇ m, and more preferably in the range of 0.5 to 10 ⁇ m.
- the thickness of the organic layer is preferably in the range of 0.5 to 10 ⁇ m, and more preferably in the range of 1 to 5 ⁇ m. Further, when formed by a dry coating method, it is preferably in the range of 0.05 to 5 ⁇ m, more preferably in the range of 0.05 to 1 ⁇ m. This is because when the film thickness of the organic layer formed by the wet coating method or the dry coating method is within the above-described range, the adhesion with the inorganic layer can be further improved.
- the organic layer may be laminated between the support film and the inorganic layer as a base layer of the inorganic layer, and is laminated between the inorganic layer and the phosphor-containing layer as a protective layer of the inorganic layer. May be. Moreover, when it has two or more inorganic layers, the organic layer may be laminated
- the base films 10 and 20 may include a concavo-convex imparting layer that imparts a concavo-convex structure on the surface opposite to the surface on the phosphor-containing layer 30 side. It is preferable that the base films 10 and 20 have a concavity and convexity providing layer because the blocking property and slipperiness of the base film can be improved.
- the unevenness providing layer is preferably a layer containing particles. Examples of the particles include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles. Moreover, although it is preferable that the uneven
- the phosphor laminated film can have a light scattering function in order to efficiently extract the fluorescence of the quantum dots to the outside.
- the light scattering function may be provided inside the phosphor-containing layer 30, or a layer having a light scattering function may be separately provided as the light scattering layer.
- the light scattering layer may be provided on the surface of the base material films 10 and 20 on the phosphor-containing layer 30 side, or provided on the surface of the base material films 10 and 20 opposite to the phosphor-containing layer 30. It may be.
- the unevenness providing layer is preferably a layer that can also be used as a light scattering layer.
- a fluorescent region forming coating liquid containing quantum dots (or quantum rods) as a phosphor is prepared. Specifically, components such as quantum dots, curable compounds, polymer dispersants, polymerization initiators, and silane coupling agents dispersed in an organic solvent are mixed in a tank, etc., to form a fluorescent region. Prepare the solution.
- the fluorescent region forming coating solution may not contain an organic solvent.
- a resin layer coating liquid to be filled between the fluorescent regions is prepared.
- a resin layer coating solution is applied onto the first base film 10, and a mold (mold) having a concavo-convex pattern is pressed against the applied resin layer coating solution to form a predetermined pattern having a recess. Then, the resin layer coating solution is cured to form a laminated film 59 in which a resin layer 38 having a plurality of recesses is laminated on the first base film 10 as shown in FIG.
- a fluorescent region forming coating solution is applied in the recesses of the resin layer 38 of the laminated film 59, and the second substrate film 20 is bonded before the fluorescent region forming coating solution is cured.
- the region forming coating solution is cured to form the fluorescent region 35, and a phosphor-containing film in which the first base film 10, the phosphor-containing layer 30, and the second base film 20 are laminated is produced. To do.
- the curing treatment in the fluorescent region forming step and the resin layer forming step may be appropriately selected according to the coating solution, such as heat curing or photocuring with ultraviolet rays.
- the irradiation amount of ultraviolet rays is preferably 100 to 10,000 mJ / cm 2 .
- the resin layer 38 is cured by thermosetting, it is preferably heated to 20 to 100 ° C.
- the method to produce a fluorescent substance containing film by RtoR was demonstrated, you may perform the process of each process by what is called a sheet-fed type using a cut sheet-like base film.
- the resin layer 38 is formed and then wound up into a roll shape to form the fluorescent region 35.
- the present invention is not limited thereto, and the resin layer 38 is formed.
- the fluorescent region 35 may be formed by continuously conveying.
- the resin layer forming step is performed before the fluorescent region forming step, that is, when the resin layer 38 that is impervious to oxygen is formed before the fluorescent region, the resin layer 38 is formed.
- a method for forming a pattern (in particular, a fine uneven pattern) using a curable compound will be described.
- pattern formation a step of applying a curable compound that forms a resin layer 38 that is impermeable to oxygen onto a substrate or a support (base material), and a step of pressing a mold against the surface of the coating layer
- a so-called photoimprint method in which a fine uneven pattern is formed through a step of irradiating light to the curable compound and a step of peeling the mold can be used.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen may be poured between the substrate and the mold, and may be photocured while pressing the mold. Furthermore, after light irradiation, it may be further heated and cured.
- Such optical imprint lithography can be laminated and multiple patterned, and can be used in combination with thermal imprint. Moreover, pattern formation can also be performed by an inkjet method or a dispenser method.
- a curable compound is applied on a substrate.
- a method for applying the curable compound on the substrate generally known application methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, and extrusion coating are used.
- a spin coating method, a slit scanning method, a casting method, an ink jet method, or the like a coating film or droplets can be applied on the substrate.
- the curable compound that forms the resin layer 38 that is impermeable to oxygen is suitable for the gravure coating method and the casting method.
- the film thickness of the pattern forming layer (coating layer for forming a pattern) made of a curable compound is about 1 to 150 ⁇ m, although it varies depending on the intended use.
- the curable compound may be applied by multiple coating.
- you may form other organic layers, such as a planarization layer, for example between a base material and a pattern formation layer.
- the substrate (substrate or support) for applying the curable compound can be selected depending on various applications, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, Ni, Metal substrate such as Cu, Cr, Fe, paper, SOG (Spin On Glass), polymer substrate such as polyester film, polycarbonate film, polyimide film, TFT (thin film transistor) array substrate, PDP (plasma display panel) electrode plate
- Metal substrate such as Cu, Cr, Fe, paper, SOG (Spin On Glass)
- polymer substrate such as polyester film, polycarbonate film, polyimide film, TFT (thin film transistor) array substrate, PDP (plasma display panel) electrode plate
- transparent plastic substrates conductive substrates such as ITO (Indium Tin Oxide) and metals
- conductive substrates such as ITO (Indium Tin Oxide) and metals
- insulating substrates semiconductor fabrication substrates such as
- the shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Further, as described later, a light-transmitting or non-light-transmitting material can be selected as the base material depending on the combination with the mold or the like.
- a mold is pressed against the surface of the pattern forming layer.
- a curable compound may be applied to a mold having a pattern and the substrate may be pressed.
- a light transmissive material is selected for at least one of the molding material and / or the base material.
- a curable compound is applied onto a substrate to form a pattern forming layer, a light-transmitting mold is pressed against the surface of the pattern forming layer, and light is irradiated from the back surface of the mold. Curing the curable compound.
- a curable compound can be applied on a light-transmitting substrate, a mold can be pressed against the surface of the coating layer, and light can be irradiated from the back surface of the substrate to cure the curable compound.
- the light irradiation may be performed with the mold attached or after the mold is peeled off, but is preferably performed with the mold in close contact.
- a mold having a pattern to be transferred is used as the mold.
- the pattern on the mold can be formed according to desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited.
- the light-transmitting mold material is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film such as SUS are exemplified.
- the non-light-transmitting mold material used when a light-transmitting base material is used is not particularly limited as long as it has a predetermined strength.
- Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. Is done.
- the shape of the mold is not particularly limited, and may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.
- the mold may be a mold that has been subjected to a release treatment in order to improve the peelability between the curable compound and the mold surface.
- molds include those that have been treated with a silicon-based or fluorine-based silane coupling agent, such as OPTOOL DSX manufactured by Daikin Industries, Ltd., Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.
- the mold pressure it is usually preferable to perform the mold pressure at 10 atm or less.
- the mold pressure it is preferable to select a region in which the uniformity of mold transfer can be ensured within a range in which the residual film of the curable compound on the mold convex portion is reduced.
- the irradiation amount of light irradiation in the step of irradiating the pattern forming layer with light may be sufficiently larger than the irradiation amount necessary for curing.
- the irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition and the tackiness of the cured film.
- the substrate temperature during light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
- a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubbles from being mixed, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition. May be.
- a preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁇ 1 Pa to 1 atm.
- the light used for curing the curable compound is not particularly limited, and examples thereof include high energy ionizing radiation, light or radiation having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared, and the like.
- the high-energy ionizing radiation source for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used.
- an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron
- radiation such as ⁇ rays, X rays, ⁇ rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used.
- the ultraviolet ray source examples include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a solar lamp, and an LED (light-emitting diode).
- the radiation includes, for example, microwaves and EUV (extreme ultraviolet).
- laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic lights, or may be lights having different wavelengths (mixed lights).
- the exposure illuminance is preferably in the range of 1 mW / cm 2 to 50 mW / cm 2 .
- the exposure dose is preferably in the range of 5 mJ / cm 2 to 1000 mJ / cm 2 . If it is less than 5 mJ / cm 2 , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur.
- the permanent film may be deteriorated due to decomposition of the composition.
- an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.
- the pattern formation method may include a step of further curing by applying heat to the cured pattern as necessary after curing the pattern formation layer by light irradiation.
- the heat for heat-curing the composition of the present invention after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
- the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
- the pattern to be formed can take any form, for example, a lattice mesh pattern in which concave or convex portions are regular tetragons, a honeycomb pattern in which concave or convex portions are regular hexagons, or concave or convex portions.
- a sea island pattern etc. which are circular are mentioned.
- a honeycomb pattern having a phosphor-containing layer in the regular hexagonal part and a resin layer in the peripheral part is particularly preferable from the viewpoint of effectively blocking oxygen to the phosphor layer with respect to any cutting form of the present invention.
- FIG. 13 is a schematic diagram illustrating a schematic configuration of the backlight unit.
- the backlight unit 102 includes a light source 101A that emits primary light (blue light L B ) and a light guide plate 101B that guides and emits the primary light emitted from the light source 101A.
- the reflecting plate 102A, the light guide plate 101B, the wavelength conversion member 100, and the retroreflective member 102B are shown separated from each other, but actually, they may be formed in close contact with each other. Good.
- Wavelength conversion member 100 at least a portion of the primary light L B emitted from the surface light source 101C as excitation light, emits fluorescence, secondary light comprising this fluorescence (green light L G, the red light L R) and it is intended to emit primary light L B having passed through the wavelength conversion member 100.
- the wavelength conversion member 100, the blue light L irradiating the green light L phosphor-containing layer containing quantum dots that emit quantum dots and the red light L R for emitting G is first base film and the by the B It is a fluorescent substance containing film comprised by being pinched
- L B , L G , and L R emitted from the wavelength conversion member 100 are incident on the retroreflective member 102B, and each incident light is transmitted between the retroreflective member 102B and the reflector 102A. The reflection is repeated and passes through the wavelength conversion member 100 many times.
- a sufficient amount of excitation light blue light L B
- the phosphor 31 here, quantum dots
- a necessary amount of fluorescence L G , L R
- white light L W is embodied and emitted from the retroreflective member 102B.
- a backlight unit that is a multi-wavelength light source.
- blue light having an emission center wavelength in a wavelength band of 430 to 480 nm and a peak of emission intensity having a half width of 100 nm or less, and an emission center wavelength in a wavelength band of 500 to 600 nm and having a half width of It is preferable to emit green light having an emission intensity peak of 100 nm or less and red light having an emission center wavelength in a wavelength band of 600 nm to 680 nm and a emission intensity peak having a half width of 100 nm or less.
- the wavelength band of blue light emitted from the backlight unit is more preferably 440 nm to 460 nm.
- the wavelength band of the green light emitted from the backlight unit is preferably 520 nm to 560 nm, and more preferably 520 nm to 545 nm.
- the wavelength band of red light emitted from the backlight unit is more preferably 610 nm to 650 nm.
- the half-value widths of the emission intensity of blue light, green light, and red light emitted from the backlight unit are all preferably 80 nm or less, more preferably 50 nm or less, and 40 nm or less. More preferably, it is more preferably 30 nm or less. Among these, it is particularly preferable that the half-value width of each emission intensity of blue light is 25 nm or less.
- the light source 101A is a blue light emitting diode that emits blue light having a light emission center wavelength in a wavelength band of 430 nm to 480 nm, for example, but an ultraviolet light emitting diode that emits ultraviolet light may be used.
- the ultraviolet light-emitting diode is a light-emitting diode having an emission center exceeding a wavelength band of 350 nm to 400 nm, for example.
- a laser light source other than a light emitting diode can be used as the light source 101A.
- a phosphor that emits blue light when irradiated with ultraviolet light in the wavelength conversion layer (phosphor-containing layer) of the wavelength conversion member, a phosphor that emits blue light when irradiated with ultraviolet light, a phosphor that emits green light, and A phosphor that emits red light may be included.
- the planar light source 101C may be a planar light source including a light source 101A and a light guide plate 101B that guides and emits primary light emitted from the light source 101A.
- a planar light source that is arranged side by side in a plane parallel to the wavelength conversion member 100 and includes a diffusion plate instead of the light guide plate 101B may be used.
- the former planar light source is generally called an edge light system, and the latter planar light source is generally called a direct type.
- a planar light source is used as the light source has been described as an example.
- a light source other than the planar light source can be used as the light source.
- the retroreflective member 102B may be configured by a known diffusion plate, diffusion sheet, prism sheet (for example, BEF series manufactured by Sumitomo 3M), a light guide, or the like.
- the configuration of the retroreflective member 102B is described in Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated in the present invention.
- the liquid crystal display device 104 includes the backlight unit 102 according to the above-described embodiment and the liquid crystal cell unit 103 disposed to face the retroreflective member side of the backlight unit.
- the liquid crystal cell unit 103 has a configuration in which the liquid crystal cell 110 is sandwiched between polarizing plates 120 and 130.
- the polarizing plates 120 and 130 have both main surfaces of the polarizers 122 and 132, respectively.
- the polarizing plate protective films 121 and 123 and 131 and 133 are used for the protection.
- liquid crystal cell 110 there are no particular limitations on the liquid crystal cell 110, the polarizing plates 120 and 130, and the components of the liquid crystal display device 104, and those manufactured by known methods and commercially available products can be used without any limitation. It is of course possible to provide a known intermediate layer such as an adhesive layer between the layers.
- the drive mode of the liquid crystal cell 110 is not particularly limited, and is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). ) And other modes can be used.
- the liquid crystal cell is preferably VA mode, OCB mode, IPS mode, or TN mode, but is not limited thereto.
- the configuration shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2008-262161 is given as an example.
- the specific configuration of the liquid crystal display device is not particularly limited, and a known configuration can be adopted.
- the liquid crystal display device 104 further includes an accompanying functional layer such as an optical compensation member that performs optical compensation as necessary, and an adhesive layer.
- an accompanying functional layer such as an optical compensation member that performs optical compensation as necessary, and an adhesive layer.
- an optical compensation member that performs optical compensation as necessary
- an adhesive layer In addition to (or instead of) color filter substrates, thin layer transistor substrates, lens films, diffusion sheets, hard coat layers, antireflection layers, low reflection layers, antiglare layers, etc., forward scattering layers, primer layers, antistatic layers Further, a surface layer such as an undercoat layer may be disposed.
- the backlight side polarizing plate 120 may have a retardation film as the polarizing plate protective film 123 on the liquid crystal cell 110 side.
- a retardation film a known cellulose acylate film or the like can be used.
- the backlight unit 102 and the liquid crystal display device 104 include a wavelength conversion member made of a phosphor-containing film in which oxygen deterioration of the present invention is suppressed. Therefore, the backlight unit and the liquid crystal display device having the same effects as those of the phosphor-containing film of the present invention and having a light emission intensity of the wavelength conversion layer including the quantum dots are hardly reduced.
- Example 1 ⁇ Preparation of phosphor-containing film> A phosphor-containing film having a phosphor-containing layer was prepared using a coating liquid containing quantum dots as the phosphor.
- Base film As the first base film and the second base film, a barrier layer made of an inorganic layer is formed on a support film made of polyethylene terephthalate (PET), and an organic layer obtained by coating the following composition on the barrier layer is formed.
- a base film was prepared.
- the material for forming the inorganic layer was silicon nitride (Si 3 N 4 ), and the thickness was 30 nm.
- OX-TRAN 2/20 manufactured by MOCON it was 4.0 ⁇ 10 ⁇ 3 cc / (m 2 ⁇ day ⁇ atm) or less.
- composition on the barrier layer of the support film After coating the composition on the barrier layer of the support film so as to have a thickness of 1 ⁇ m, it was dried at 60 ° C. for 1 minute, and ultraviolet rays were applied from the coated surface using a 200 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics). It was cured by irradiation with 400 mJ / cm 2 to form an organic layer.
- the coating solution 1 for forming the phosphor-containing layer As the coating solution 1 for forming the phosphor-containing layer, components such as quantum dots, curable compounds, thixotropic agents, polymerization initiators, and silane coupling agents are mixed in a tank or the like to prepare a coating solution.
- the coating solution 1 for forming the phosphor-containing layer As the coating solution 1 for forming the phosphor-containing layer, components such as quantum dots, curable compounds, thixotropic agents, polymerization initiators, and silane coupling agents are mixed in a tank or the like to prepare a coating solution.
- a quantum dot dispersion liquid having the following composition was prepared and designated as coating liquid 1.
- -Toluene dispersion of quantum dots 1 (luminescence maximum: 520 nm) 10 parts by mass-Toluene dispersion of quantum dots 2 (luminescence maximum: 630 nm) 1 part by weight-Lauryl methacrylate 2.4 parts by weight-Trimethylolpropane triacrylate 0.
- 54 parts by mass / photopolymerization initiator Irgacure 819 (manufactured by BASF Corporation)) 0.009 parts by mass
- Quantum dot 1 INP530-10 (manufactured by NN-labs)
- Quantum dot 2 INP620-10 (manufactured by NN-labs)
- a coating solution for forming a resin layer having the following composition was prepared and used as coating solution 2.
- urethane (meth) acrylate U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.))-25 parts by mass of tricyclodecane dimethanol diacrylate (A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)) ⁇ 1,6 hexanediol diacrylate (Light Acrylate 1.6HA-A (manufactured by Kyoeisha Chemical Co., Ltd.)) 25 parts by mass ⁇ Photopolymerization initiator (Irgacure 819 (manufactured by BASF)) 1 part by mass
- the resin layer was formed on the 1st base film with the photoimprint method shown below.
- a SUS mold having a honeycomb pattern produced by a photo-etching method (a concave line width of 0.5 mm, a convex regular hexagonal diagonal of 1 mm, a concave depth of 50 ⁇ m), and an organic layer side of the first base film
- the coating liquid 2 for resin formation is poured by a dispenser, pressed by a pressure of 0.3 MPa with a rubber roller, the excessive coating liquid is discharged, and a mold filled with the coating liquid on the first base film is formed. It was set as the pasted form.
- the phosphor layer-containing film was filled in between the resin layers on the first base film and bonded to the second base film by the procedure shown below.
- the phosphor-containing layer coating liquid 1 is poured with a dispenser between the resin layer side of the first base film formed with the resin layer created in the above step and the organic layer side of the second base film, The excess coating liquid was discharged by pressing with a rubber roller at a pressure of 0.3 MPa, and the phosphor-containing layer coating liquid was filled between the first base film, the resin layer, and the second base film.
- the obtained phosphor-containing film had a resin layer width of 0.5 mm, a phosphor layer width of 1 mm, and a resin layer and a phosphor layer thickness of 50 ⁇ m.
- Example 2 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 1 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 2 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 3 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 3 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- ⁇ Composition of Coating Solution 6 for Forming Resin Layer> ⁇ Tricyclodecane dimethanol diacrylate (A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)) 99 parts by mass ⁇ Photopolymerization initiator (Irgacure 819 (manufactured by BASF)) 1 part by mass
- Example 4 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 4 A phosphor-containing film was produced in the same manner as in Example 1 except that the composition described below was used as the coating solution for forming the resin layer.
- Example 5 A phosphor-containing film was produced in the same manner as in Example 1 except that the total amount of irradiation with ultraviolet rays for curing the resin layer was 50000 mJ / cm 2 .
- Example 6 Example 1 except that the total amount of UV irradiation when the resin layer was cured was 500 mJ / cm 2. In the same manner, a phosphor-containing film was produced.
- Example 7 A phosphor-containing film was produced in the same manner as in Example 1 except that the first base film and the second base film were made Clarista CI (manufactured by Kuraray Co., Ltd.). When the oxygen permeability of this base film was measured using OX-TRAN 2/20 manufactured by MOCON, it was 1.0 ⁇ 10 ⁇ 1 cc / (m 2 ⁇ day ⁇ atm) or less.
- Knoop hardness, creep recovery rate, and elastic recovery rate of resin layer were measured as follows.
- the water vapor transmission rate was measured by a calcium corrosion method (a method described in JP-A-2005-283561).
- the conditions of the constant temperature and humidity treatment were a temperature of 40 ° C. and a relative humidity of 90% RH.
- the oxygen permeability is a value measured using an oxygen gas permeability measuring apparatus (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%. is there.
- the phosphor-containing films prepared in the examples and comparative examples are wavelength conversion members, and changes with time in the light emission performance of the wavelength conversion members were measured and evaluated as follows.
- the initial luminance (Y) of the wavelength conversion member of each example and comparative example was measured by the following procedure. First, each wavelength conversion member was cut into a 1-inch square using a Thomson blade MIR-CI23 manufactured by Nakayama Corporation. Each side of the cut wavelength conversion member straddles the resin layer and the fluorescent region. Meanwhile, a commercially available tablet device (Amazon, Kindle (registered trademark) Fire HDX 7 ”) was disassembled and the backlight unit was taken out. After removing the wavelength conversion member attached to the taken out backlight unit. Then, the phosphor-containing film prepared as described above was placed on the light guide plate, and two prism sheets with the directions orthogonal to each other were placed on the light guide plate.
- a commercially available tablet device Amazon, Kindle (registered trademark) Fire HDX 7
- the luminance at a position 1 mm inside from the cut surface is a position in the direction of 740 mm perpendicular to the surface of the light guide plate
- a luminance meter SR3, manufactured by TOPCON Co., Ltd.
- the evaluation standard of the initial luminance (Y) is shown below. If the evaluation result is B or more, it can be determined that the luminous efficiency is maintained well.
- each wavelength conversion member is placed on a commercially available blue light source (OPSM-H150X142B manufactured by OPTEX-FA Co., Ltd.) in a room kept at 85 ° C., and the blue light is continuously irradiated to the wavelength conversion member for 2000 hours. did. After 1000 hours and 2000 hours, the wavelength conversion member was taken out and the luminance was measured in the same procedure as described above. The brightness of the high temperature test for 1000 hours and the brightness of the high temperature test for 2000 hours were measured.
- OPSM-H150X142B manufactured by OPTEX-FA Co., Ltd.
- the average value (G) of the Gray value and the standard deviation ⁇ were obtained and evaluated according to the following criteria: If the evaluation results were A and B, the luminance unevenness was good. Although the evaluation result C is acceptable in practice, the evaluation result C is not acceptable.
- Example 2 From the comparison between Example 2 and Comparative Example 1, it can be seen that if the Knoop hardness is too small, it deteriorates early. This is presumably because if the Knoop hardness is too small, micro flaws are generated in a direction different from the direction to be cut and cracks occur. In addition, it can be seen from the comparison between Example 1 and Comparative Example 2 that if the Knoop hardness is too large, uncut portions are generated. This is considered because the load by the cutting blade is insufficient when the Knoop hardness is too large. Further, it can be seen from the comparison between Example 3 and Comparative Example 3 that if the elastic recovery rate is too small, the cut surface is crushed, the initial luminance is lowered, and luminance unevenness occurs.
- the Knoop hardness, creep recovery rate, and elastic recovery rate can be adjusted by appropriately setting the irradiation amount of ultraviolet rays when the resin layer is cured.
- the value of the initial luminance can be adjusted by appropriately setting the value of oxygen permeability.
- the phosphor-containing film of the present invention has been described by taking the wavelength conversion member as an example in the above-described embodiment, but by appropriately selecting the type of the phosphor, the organic electroluminescence layer in the organic electroluminescence element, the organic solar cell It can be applied to an organic photoelectric conversion layer and the like, and an effect of suppressing performance degradation can be obtained.
Abstract
Description
バックライトから量子ドットを含むフィルムに励起光が入射すると、量子ドットが励起され蛍光を発光する。ここで異なる発光特性を有する量子ドットを用い、各量子ドットに赤色光、緑色光もしくは青色光の半値幅の狭い光を発光させることにより白色光を具現化することができる。量子ドットによる蛍光は半値幅が狭いため、波長を適切に選択することで得られる白色光を高輝度にすること、および色再現性に優れる設計にすることが可能である。
しかしながら、量子ドット層の両主面をガスバリアフィルムで保護するのみでは、ガスバリアフィルムで保護されていない端面から水分や酸素が入り込み、量子ドットが劣化するという問題がある。
そのため、量子ドット層の周囲全部をバリアフィルムで保護することが提案されている。
このような問題は、量子ドットに限らず、酸素と反応して劣化する蛍光体を備える蛍光体含有フィルムで同様に生じる。
しかし、この長尺フィルムから所望サイズの蛍光体含有フィルムを裁断して得る際、やはり切断端面において蛍光体含有層が外気に曝露されるため、切断端面からの酸素の侵入に対する対策が必要である。
すなわち、以下の構成により上記課題を達成することができることを見出した。
蛍光体含有層の一方の主面に積層される第1の基材フィルムおよび他方の主面に積層される第2の基材フィルムと、を有し、
樹脂層のヌープ硬度が115N/mm2~285N/mm2であり、クリープ回復率が22%以下であり、弾性回復率が60%以上である蛍光体含有フィルム。
(2) 蛍光体含有フィルムの端面において、蛍光特性を失った領域と樹脂層とが露出している(1)に記載の蛍光体含有フィルム。
(3) 樹脂層の酸素透過度が10cc/(m2・day・atm)以下である(1)または(2)に記載の蛍光体含有フィルム。
(4) 第1の基材フィルムおよび第2の基材フィルムの酸素透過度が1cc/(m2・day・atm)以下である(1)~(3)のいずれかに記載の蛍光体含有フィルム。
(5) 樹脂層に含まれる樹脂が、光重合性官能基又は熱重合性官能基を有する化合物を含有する組成物から成る(1)~(4)のいずれかに記載の蛍光体含有フィルム。
(6) (1)~(5)のいずれかに記載の蛍光体含有フィルムからなる波長変換部材と、青色発光ダイオードおよび紫外線発光ダイオードの少なくとも一方とを含むバックライトユニット。
本発明の蛍光体含有フィルムは、
酸素に暴露されると酸素と反応して劣化する蛍光体を含む蛍光領域が複数、離散的に配置され、離散的に配置された複数の蛍光領域間に、酸素に対する不透過性を有する樹脂層が配置されてなる蛍光体含有層と、
蛍光体含有層の一方の主面に積層される第1の基材フィルムおよび他方の主面に積層される第2の基材フィルムと、を有し、
樹脂層のヌープ硬度が115N/mm2~285N/mm2であり、クリープ回復率が22%以下であり、弾性回復率が60%以上である蛍光体含有フィルムである。
本実施形態の蛍光体含有フィルム1は、第1の基材フィルム10と、第1の基材フィルム10上において、酸素に暴露されると酸素と反応して劣化する蛍光体31を含む領域35が複数、離散的に配置され、離散的に配置された蛍光体31を含む領域35間に、酸素に対する不透過性を有する樹脂層38が配置されてなる蛍光体含有層30と、蛍光体含有層30上に配置される第2の基材フィルム20とを備えている。以下において、蛍光体31を含む領域35を蛍光領域35と称する場合がある。
そこで、量子ドットなどの蛍光体を複数の領域に離散的に配置し、蛍光体の周囲にシール材を配置する構成として、蛍光体含有フィルムを裁断する際にシール材の部分で裁断することで、光学部品を裁断しても蛍光部材の密閉状態を維持することが考えられている。
しかしながら、蛍光体を離散的に配置し、シール材で密閉する構成とした場合でも、蛍光体含有フィルムを裁断する際に、シール材に割れが生じて水分や酸素が侵入しやすくなってしまうという問題があることがわかった。
裁断性の更なる向上の観点からは、ヌープ硬度は140N/mm2~285N/mm2であることが好ましい。
フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定する。押し込み深さから求められる圧子とサンプルとの接触面積と最大荷重の関係より硬度を算出し、この10点の平均値をヌープ硬度とする。
裁断性の更なる向上の観点からは、クリープ回復率は20%以下であることが好ましい。
フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定する。除荷直後の押し込み深さと除荷5秒後の深さの関係よりクリープ回復の割合を算出し、この10点の平均値をクリープ回復率とする。
裁断性の更なる向上の観点からは、弾性回復率は65%以上であることが好ましい。
フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定する。横軸押し込み深さ、縦軸荷重にとったグラフにおいて[クリープ時間後の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、荷重ゼロ]、[除荷直後の押し込み深さ、荷重ゼロ]の3点で囲まれる面積(除荷時に解放される弾性変形エネルギーEに相当)と、原点、[クリープ時間前の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、荷重ゼロ]の4点で囲まれる面積(負荷(およびクリープ)に要した総エネルギーE合計に相当)との関係より弾性回復の割合を算出し、この10点の平均値を弾性回復率とする。
また、本発明の蛍光体含有フィルムは、樹脂層と蛍光領域をまたいで裁断しても樹脂層の割れを好適に抑制できるので、裁断箇所を自由に選択でき、裁断する際のサイズや形状の自由度が高い。
また、樹脂層と蛍光領域をまたいで裁断した場合には、蛍光体含有フィルムは、切断面である端面において、蛍光特性を失った領域と樹脂層とが露出した構成となる。また、蛍光領域を複数またいで裁断した場合には、蛍光体含有フィルムの端面において、蛍光特性を失った領域と樹脂層とが交互に露出した構成となる。
側)の点を結ぶ線を蛍光領域35の輪郭(蛍光領域35と樹脂層38の境界)mと看做すこととする。励起光を蛍光体含有層に照射して蛍光体を発光させ、たとえば、共焦点レーザー顕微鏡などで観察することにより、蛍光体の位置を特定することができ、これにより蛍光領域35の輪郭mを特定することができる。本明細書において、円柱や多角柱の辺は図6の輪郭のように蛇行しているものを許容するものとする。
また、上記実施形態においては、蛍光領域35は周期的にパターン配置されているが、複数の蛍光領域35が離散的に配置されていれば所望の性能が損なわれない限りにおいて、非周期的であってもよい。蛍光領域35は、蛍光体含有層30の全域に亘って均一に分布していることが輝度の面内分布が均等になるため好ましい。
蛍光領域35中の蛍光体31は1種であってもよいし、複数種であってもよい。また、1つの蛍光領域35中の蛍光体31は1種として、複数の蛍光領域35のうち、第1の蛍光体を含む領域と第1の蛍光体とは異なる第2の蛍光体を含む領域とが周期的にあるいは非周期的に配置されていてもよい。蛍光体の種類は3種以上であっても構わない。
図7A~図7Cに示す蛍光体含有フィルム3は、蛍光領域として、バインダ33中に第1の蛍光体31aが分散されてなる第1の蛍光領域35aとバインダ33中に第1の蛍光体31aとは異なる第2の蛍光体31bが分散されてなる第2の蛍光領域35bとを備えている。第1の蛍光領域35aと第2の蛍光領域35bは、平面視において交互に配置されており、フィルム厚み方向において、互いに異なる位置に分散配置されている。第1の蛍光領域35aが第2の基材フィルム20に隣接する主面側に配置され、第2の蛍光領域35bが第1の基材フィルム10に隣接する主面側に配置されており、第1の蛍光領域35aと第2の蛍光領域35bとは平面視において重ならないように配置されている。
第1の蛍光領域35aと第2の蛍光領域35bのバインダ33は本例において同一の組成からなるものとしているが、異なる組成からなるものであってもよい。
図8Aおよび図8Bに示す蛍光体含有フィルム4は、フィルム厚み方向に異なる位置に配置されている第1の蛍光領域35aと第2の蛍光領域35bとがフィルム面を平面視したとき一部重なりを有している点で、図7A~図7Cに示す蛍光体含有フィルム3と異なる。このように、フィルム方向において異なる位置に配置されている第1の蛍光領域35aと第2の蛍光領域35bとが平面視において重なりを有していても構わない。
図9Aおよび図9Bに示す蛍光体含有フィルム6は、四角柱状の領域が半周期ずれて積層された階段状の蛍光領域35を備えている。蛍光領域35は、第1の蛍光体31a、第2の蛍光体31bがバインダ33中に分散されてなる。本例では、階段状の蛍光領域35の下階段部に第2の蛍光体31bが、上階段部に第1の蛍光体31aが分散されているが、第1の蛍光体31a、第2の蛍光体31bが蛍光領域35内の上下階段部全体に混在していても構わない。
蛍光体含有層30は、複数の蛍光体31を含む蛍光領域35と、蛍光領域35間に充填される、酸素に対して不透過性を有する樹脂層38とを備える。
蛍光領域35は、蛍光体31と蛍光体31が分散されてなるバインダ33とから構成されるものであり、蛍光体31および硬化性化合物を含む蛍光領域形成用塗布液を塗布、硬化して形成される。
酸素に暴露されると酸素と反応して劣化する蛍光体としては、公知の各種蛍光体を用いることができる。例えば、希土類ドーピングガーネット、ケイ酸塩、アルミン酸塩、リン酸塩、セラミックス蛍光体、硫化物蛍光体、窒化物蛍光体等の無機蛍光体、および、有機蛍光染料および有機蛍光顔料を始めとする有機蛍光物質などである。また、半導体微粒子に希土類をドープした蛍光体、および、半導体のナノ微粒子(量子ドット、量子ロッド)も好適に用いられる。蛍光体は1種単独で用いることもできるが、所望の蛍光スペクトルが得られるように、異なる波長のものを複数混ぜて使用してもよいし、異なる素材構成の蛍光体同士の組み合わせ(例えば、希土類ドーピングガーネットと量子ドットとの組み合わせ)として用いてもよい。
ここで、酸素に暴露されるとは、大気中など酸素を含む環境下に曝されることを意味し、酸素と反応して劣化するとは、蛍光体が酸化されることによりその蛍光体の性能が劣化(低下)することを意味し、主として発光性能が酸素と反応する前と比較して低下することをいうが、蛍光体を光電変換体として利用する場合には、光電変換効率が酸素と反応する前と比較して低下することを意味する。
以下においては、酸素により劣化する蛍光体として、主に量子ドットを例として説明するが、本発明の蛍光体としては、量子ドットに限らず、その他の酸素により劣化する蛍光色素、光電変換材料など、外部からのエネルギーを光に変換する、あるいは光を電気に変換する材料であれば特に限定はされない。
量子ドットは、数nm~数十nmの大きさをもつ化合物半導体の微粒子であり、少なくとも、入射する励起光により励起され蛍光を発光する。
量子ドット含有組成物における配位子は、公知の合成法によって合成することができる。例えば、特許文献特開2007-277514に記載の方法によって合成することができる。
硬化性化合物としては、重合性基を有するものが広く採用できる。重合性基の種類は、特に限定されないが、光又は熱重合性官能基を有する化合物が好ましい。また、好ましくは、(メタ)アクリレート基、ビニル基またはエポキシ基であり、より好ましくは、(メタ)アクリレート基であり、さらに好ましくは、アクリレート基である。また、2つ以上の重合性基を有する重合性単量体は、それぞれの重合性基が同一であってもよいし、異なっていても良い。
硬化後の硬化被膜の透明性、密着性等の観点からは、単官能または多官能(メタ)アクリレートモノマー等の(メタ)アクリレート化合物や、そのポリマー、プレポリマー等が好ましい。なお本発明および本明細書において、「(メタ)アクリレート」との記載は、アクリレートとメタクリレートとの少なくとも一方、または、いずれかの意味で用いるものとする。「(メタ)アクリロイル」等も同様である。
単官能(メタ)アクリレートモノマーとしては、アクリル酸およびメタクリル酸、それらの誘導体、より詳しくは、(メタ)アクリル酸の重合性不飽和結合((メタ)アクリロイル基)を分子内に1個有するモノマーを挙げることができる。それらの具体例として以下に化合物を挙げるが、本実施形態はこれに限定されるものではない。
重合性基を2つ有する重合性単量体として、エチレン性不飽和結合含有基を2個有する2官能重合性不飽和単量体を挙げることができる。2官能の重合性不飽和単量体は組成物を低粘度にするのに適している。本実施形態では、反応性に優れ、残存触媒などの問題の無い(メタ)アクリレート系化合物が好ましい。
重合性基を3つ以上有する重合性単量体として、エチレン性不飽和結合含有基を3個以上有する多官能重合性不飽和単量体を挙げることができる。これら多官能の重合性不飽和単量体は機械的強度付与の点で優れる。本実施形態では、反応性に優れ、残存触媒などの問題の無い(メタ)アクリレート系化合物が好ましい。
本実施の形態で用いる重合性単量体として、エポキシ基、オキセタニル基等の開環重合可能な環状エーテル基等の環状基を有する化合物を挙げることができる。そのような化合物としてより好ましくは、エポキシ基を有する化合物(エポキシ化合物)を有する化合物を挙げることができる。エポキシ基やオキセタニル基を有する化合物を、(メタ)アクリレート系化合物と組み合わせて使用することにより、バリア層との密着性が向上する傾向にある。
ビニルエーテル化合物は公知のものを適宜選択することができ、例えば、特開2009-73078号公報の段落番号0057に記載のものを好ましく採用することができる。
また、重合性化合物として、(メタ)アクリレートを用いる場合、硬化性に優れる観点からメタアクリレートよりも、アクリレートの方が好ましい。
硬化性化合物はチキソトロピー剤を含有してもよい。
チキソトロピー剤は、無機化合物または有機化合物である。
チキソトロピー剤の好ましい1つの態様は無機化合物のチキソトロピー剤であり、例えば針状化合物、鎖状化合物、扁平状化合物、層状化合物を好ましく用いることができる。なかでも、層状化合物であることが好ましい。
チキソトロピー剤は、有機化合物のチキソトロピー剤を用いることができる。
有機化合物のチキソトロピー剤としては、酸化ポリオレフィン、変性ウレア等が挙げられる。
チキソトロピー剤の含有量は、塗布液中、硬化性化合物100質量部に対して0.15~20質量部であることが好ましく、0.2~10質量部であることがより好ましく、0.2~8質量部であることが特に好ましい。特に無機化合物のチキソトロピー剤の場合、硬化性化合物100質量部に対して20質量以下であると、脆性が良化方向にある。
上記塗布液は、重合開始剤としては、公知の重合開始剤を含むことができる。重合開始剤については、例えば、特開2013-043382号公報の段落0037を参照できる。重合開始剤は、塗布液に含まれる硬化性化合物の全量の0.1モル%以上であることが好ましく、0.5~2モル%であることがより好ましい。また、揮発性有機溶媒を除いた全硬化性組成物中に質量%として、0.1質量%~10質量%含むことが好ましく、さらに好ましくは0.2質量%~8質量%である。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物は、光重合開始剤を含むことが好ましい。光重合開始剤としては、光照射により上述の重合性化合物を重合する活性種を発生する化合物であればいずれのものでも用いることができる。光重合開始剤としては、カチオン重合開始剤、ラジカル重合開始剤が挙げられ、ラジカル重合開始剤が好ましい。また、本発明において、光重合開始剤は複数種を併用してもよい。
光重合開始剤の含有量が0.01質量%以上であると、感度(速硬化性)、塗膜強度が向上する傾向にあり好ましい。一方、光重合開始剤の含有量を15質量%以下とすると、光透過性、着色性、取り扱い性などが向上する傾向にあり、好ましい。染料および/または顔料を含む系では、これらがラジカルトラップ剤として働くことがあり、光重合性、感度に影響を及ぼす。その点を考慮して、これらの用途では、光重合開始剤の添加量が最適化される。一方で、本発明に用いられる組成物では、染料および/または顔料は必須成分でなく、光重合開始剤の最適範囲が液晶ディスプレイカラーフィルタ用硬化性組成物等の分野のものとは異なる場合がある。
酸素に対して不透過性を有する樹脂層38を形成する硬化性組成物は、ポリマーを含んでもよい。ポリマーとしては、例えば、ポリ(メタ)アクリレート、ポリ(メタ)アクリルアミド、ポリエステル、ポリウレタン、ポリウレア、ポリアミド、ポリエーテル、およびポリスチレンを挙げることができる。
蛍光領域形成用塗布液は、粘度調整剤、シランカップリング剤、界面活性剤、酸化防止剤、酸素ゲッター剤、重合禁止剤、無機粒子等を含有してもよい。
蛍光領域形成用塗布液は、必要に応じて粘度調整剤を含んでもよい。粘度調整剤を添加することによって、それらを所望の粘度に調整することが可能である。粘度調整剤は、粒径が5nm~300nmであるフィラーであることが好ましい。また、粘度調整剤はチキソトロピー剤であってもよい。なお、本発明および本明細書中、チキソトロピー性とは、液状組成物において、せん断速度の増加に対して粘性を減じる性質を指し、チキソトロピー剤とは、それを液状組成物に含ませることによって、組成物にチキソトロピー性を付与する機能を有する素材のことを指す。チキソトロピー剤の具体例としては、ヒュームドシリカ、アルミナ、窒化珪素、二酸化チタン、炭酸カルシウム、酸化亜鉛、タルク、雲母、長石、カオリナイト(カオリンクレー)、パイロフィライト(ろう石クレー)、セリサイト(絹雲母)、ベントナイト、スメクタイト・バーミキュライト類(モンモリロナイト、バイデライト、ノントロナイト、サポナイトなど)、有機ベントナイト、有機スメクタイト等が挙げられる。
シランカップリング剤を含む塗布液から形成される蛍光体含有層は、シランカップリング剤により隣接する層との密着性が強固なものとなるため、優れた耐久性を示すことができる。また、シランカップリング剤を含む塗布液から形成される蛍光体含有層は、密着力条件の支持フィルムとバリア層の密着力A<蛍光体含有層とバリア層との密着力Bの関係を形成する上でも好ましい。これは主に、蛍光体含有層に含まれるシランカップリング剤が、加水分解反応や縮合反応により、隣接する層の表面やこの蛍光体含有層の構成成分と共有結合を形成することによるものである。また、シランカップリング剤がラジカル重合性基等の反応性官能基を有する場合、蛍光体含有層を構成するモノマー成分と架橋構造を形成することも、蛍光体含有層と隣接する層との密着性向上に寄与し得る。
一般式(1)で表されるシランカップリング剤が2つ以上のラジカル重合性の炭素-炭素二重結合を含む置換基は、それぞれの置換基は同じであってもよいし、異なっていてもよく、同じであることが好ましい。
蛍光領域形成用塗布液は、フッ素原子を20質量%以上含有する少なくとも1種の界面活性剤を含んでいても良い。
このような構造を有することによって表面偏在能が良好となり、また重合体との部分的な相溶が生じて相分離が抑制されると考えられる。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物には、公知の酸化防止剤を含有することが好ましい。酸化防止剤は、熱や光照射による退色およびオゾン、活性酸素、NOx、SOx(Xは整数)などの各種の酸化性ガスによる退色を抑制するものである。特に本発明では、酸化防止剤を添加することにより、硬化膜の着色防止や、分解による膜厚減少を低減できるという利点がある。
また、酸化防止剤として2種類以上の酸化防止剤を用いてもよい。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物において、酸化防止剤は、硬化性化合物の全質量に対し、0.2質量%以上であることが好ましく、1質量%以上であることがより好ましく、2質量%以上であることがさらに好ましい。一方、酸化防止剤は酸素との間での相互作用により変質することがある。変質した酸化防止剤は量子ドット含有重合性組成物の分解を誘引することがあり、密着性低下、脆性悪化、量子ドット発光効率低下をもたらす。これらを防止する観点から20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることがさらに好ましい。
ROC(=O)(CH2)8C(=O)OR、ROC(=O)C(CH3)=CH2、R’OC(=O)C(CH3)=CH2、CH2(COOR)CH(COOR)CH(COOR)CH2COOR、CH2(COOR’)CH(COOR’)CH(COOR’)CH2COOR’、式3で表わされる化合物等。
酸素ゲッター剤としては、有機EL素子のゲッター剤として用いられる公知の物質を用いることができ、無機系ゲッター剤又は有機系ゲッター剤のいずれでもよく、金属酸化物、金属ハロゲン化物、金属硫酸塩、金属過塩素酸塩、金属炭酸塩、金属アルコキシド、金属カルボキシレート、金属キレート、またはゼオライト(アルミノケイ酸塩)の中から選ばれた少なくとも1種の化合物を含むことが好ましい。
かかる酸素ゲッター剤としては、酸化カルシウム(CaO)、酸化バリウム(BaO)、酸化マグネシウム(MgO)、酸化ストロンチウム(SrO)、硫酸リチウム(Li2SO4)、硫酸ナトリウム(Na2SO4)、硫酸カルシウム(CaSO4)、硫酸マグネシウム(MgSO4)、硫酸コバルト(CoSO4)、硫酸ガリウム(Ga2(SO4)3)、硫酸チタン(Ti(SO4)2)、硫酸ニッケル(NiSO4)等が挙げられる。
有機系ゲッター剤としては、化学反応により水を取り込み、その反応前後で不透明化しない材料であれば特に制限されない。ここで、有機金属化合物とは、金属-炭素結合や金属-酸素結合、金属-窒素結合等を有する化合物を意味する。水と有機金属化合物とが反応すると加水分解反応により、前述の結合が切れて金属水酸化物になる。金属によっては金属水酸化物に反応後に加水分解重縮合を行い高分子量化してもよい。
金属アルコキシド、金属カルボキシレート、及び金属キレートの金属としては、有機金属化合物として水との反応性が良いもの、すなわち、水により各種結合と切れやすい金属原子を用いることが好ましい。具体的には、アルミニウム、ケイ素、チタン、ジルコニウム、ケイ素、ビスマス、ストロンチウム、カルシウム、銅、ナトリウム、リチウムが挙げられる。また、セシウム、マグネシウム、バリウム、バナジウム、ニオブ、クロム、タンタル、タングステン、クロム、インジウム、鉄などが挙げられる。特にアルミニウムを中心金属として持つ有機金属化合物の乾燥剤が樹脂中への分散性や水との反応性の点で好適である。有機基は、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、2-エチルヘキシル基、オクチル基、デシル基、ヘキシル基、オクタデシル基、ステアリル基などの不飽和炭化水素、飽和炭化水素、分岐不飽和炭化水素、分岐飽和炭化水素、環状炭化水素を含有したアルコキシ基やカルボキシル基、アセエチルアセトナト基、ジピバロイルメタナト基などのβ-ジケトナト基が挙げられる。
中でも、下記化学式に示す、炭素数が1~8のアルミニウムエチルアセトアセテート類が、透明性に優れた封止組成物を形成できる点から好適に用いられる。
酸素ゲッター剤は粒子状又は粉末状である。酸素ゲッター剤の平均粒子径は通常20μm未満の範囲とすれば良く、好ましくは10μm以下、より好ましくは2μm以下、更に好ましくは1μm以下である。散乱性の観点から、酸素ゲッター剤の平均粒子径は、0.3~2μmであることが好ましく、0.5~1.0μmであることがより好ましい。ここでいう平均粒径とは、動的光散乱法によって測定した粒度分布から算出した、粒子径の平均値をいう。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物には、重合禁止剤を含有することが好ましい。重合禁止剤の含有量としては、全重合性単量体に対し、0.001~1質量%であり、より好ましくは0.005~0.5質量%、さらに好ましくは0.008~0.05質量%である、重合禁止剤を適切な量配合することで高い硬化感度を維持しつつ経時による粘度変化が抑制できる。重合禁止剤は重合性単量体の製造時に添加してもよいし、硬化組成物に後から添加してもよい。好ましい重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、tert-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン第一セリウム塩、フェノチアジン、フェノキサジン、4-メトキシナフトール、2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル、2,2,6,6-テトラメチルピペリジン、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル、ニトロベンゼン、ジメチルアニリン等が挙げられ、好ましくはp-ベンゾキノン、2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル、フェノチアジンである。これら重合禁止剤は重合性単量体の製造時だけでなく、硬化組成物の保存時においてもポリマー不純物の生成を抑制し、インプリント時のパターン形成性の劣化を抑制する。
酸素に対して不透過性を有する樹脂層38は、既述の硬化性化合物を含む樹脂形成用塗布液を塗布し、硬化して形成される。樹脂層38の隣接する蛍光領域35間の最短距離における酸素透過度が10cc/(m2・day・atm)以下を満たすことが好ましい。樹脂層38の隣接する蛍光領域35間の最短距離における酸素透過度は1cc/(m2・day・atm)以下であることがより好ましく、10-1cc/(m2・day・atm)以下であることがさらに好ましい。樹脂層38の組成により、蛍光領域35間の必要最短距離は異なる。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物に含まれる重合性化合物は、25℃において液体である重合性化合物が全重合性化合物中50質量%以上であることが経時安定性の観点で好ましい。
酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物において、酸素ゲッター剤は、硬化性化合物の全質量に対し、0.1~20質量%であることが好ましく、0.1~15質量%であることがより好ましく、0.1~10質量%であることがさらに好ましい。
第1の基材フィルム10および第2の基材フィルム20は、酸素の透過を抑制する機能を有するフィルムであることが好ましい。上記の実施形態では、支持フィルム11,21の一面にバリア層12,22をそれぞれ備えた構成を有している。かかる態様では、支持フィルム11,21の存在により、蛍光体含有フィルムの強度が向上され、且つ、容易に製膜を実施することが可能となる。なお、本実施形態では支持フィルム11,21一面にバリア層12,22を備える構成であるが、バリア性を充分有する支持体のみにより基材フィルムが構成されていてもよい。
支持フィルム11,21としては、可視光に対して透明である可撓性を有する帯状の支持体が好ましい。ここで可視光に対して透明とは、可視光領域における線透過率が、80%以上、好ましくは85%以上であることをいう。透明の尺度として用いられる光線透過率は、JIS-K7105に記載された方法、すなわち積分球式光線透過率測定装置を用いて全光線透過率および散乱光量を測定し、全光線透過率から拡散透過率を引いて算出することができる。可撓性を有する支持体については、特開2007-290369号公報段落0046~0052、特開2005-096108号公報段落0040~0055を参照できる。
支持フィルムの厚さは、ガスバリア性、耐衝撃性等の観点から、10~500μmの範囲内、中でも15~300μmの範囲内、特に15~120μmの範囲内、より特に15~100μmの範囲内、さらには25~110μm、よりさらには25~60μmであることが好ましい。
蛍光体含有フィルムを作製した後、異物や欠陥の有無を検査する際、2枚の偏光板を消光位に配置し、その間に蛍光体含有フィルムを差し込んで観察することで、異物や欠陥を見つけやすい。支持体のRe(589)が上記範囲であると、偏光板を用いた検査の際に、異物や欠陥をより見つけやすくなるため、好ましい。
ここで、Re(589)は、AxoScan OPMF-1(オプトサイエンス社製)を用いて、入力波長589nmの光をフィルム法線方向に入射させることにより測定することができる。
第1の基材フィルム10および第2の機材フィルム20としては、支持フィルム11、21の蛍光体含有層30側の面に接して形成されてなる少なくとも一層の無機層を含むバリア層12、22を備えていることが好ましい。バリア層12、22としては、少なくとも無機層1層と少なくとも1層の有機層を含むものであってもよい。このように複数の層を積層することは、より一層バリア性を高めることができるため、耐光性向上の観点からは好ましい。他方、積層する層の数が増えるほど、基材フィルムの光透過率は低下する傾向があるため、良好な光透過率を維持し得る範囲で、積層数を増やすことが望ましい。
酸素透過度は低いほど好ましく、可視光領域における全光線透過率は高いほど好ましい。
基材フィルム10、20は、蛍光体含有層30側の面と反対側の面に、凹凸構造を付与する凹凸付与層を備えていてもよい。基材フィルム10、20が凹凸付与層を有していると、基材フィルムのブロッキング性、滑り性を改良することができるため、好ましい。凹凸付与層は粒子を含有する層であることが好ましい。粒子としては、シリカ、アルミナ、酸化金属等の無機粒子、あるいは架橋高分子粒子等の有機粒子等が挙げられる。また、凹凸付与層は、基材フィルムの蛍光体含有層とは反対側の表面に設けられることが好ましいが、両面に設けられていてもよい。
次に、上記の如く構成された本発明の実施形態の蛍光体含有フィルムの製造工程の一例について図11~図12を参照して説明する。
第1の塗布液調製工程では、蛍光体として量子ドット(または量子ロッド)を含む蛍光領域形成用塗布液を調製する。具体的には、有機溶媒中に分散された量子ドット、硬化性化合物、高分子分散剤、重合開始剤、および、シランカップリング剤などの各成分をタンクなどにより混合し、蛍光領域形成用塗布液を調製する。なお、蛍光領域形成用塗布液には有機溶媒を含んでいなくても構わない。
次に、第1の基材フィルム10上に樹脂層用塗布液を塗布し、塗布した樹脂層用塗布液に凹凸パターンを有する型(モールド)を圧接して凹部を有する所定パターンを形成して、樹脂層用塗布液を硬化させて、図11に示すような、第1の基材フィルム10上に、複数の凹部を有する樹脂層38が積層された積層フィルム59を形成する。
次に、積層フィルム59の樹脂層38の凹部内に蛍光領域形成用塗布液を塗布し、蛍光領域形成用塗布液を硬化させる前に、第2の基材フィルム20を貼り合せた後、蛍光領域形成用塗布液を硬化させて蛍光領域35を形成して、第1の基材フィルム10、蛍光体含有層30、および、第2の基材フィルム20が積層された蛍光体含有フィルムを作製する。
紫外線による光硬化により樹脂層38を硬化させる場合には、紫外線の照射量は、100~10000mJ/cm2とするのが好ましい。
熱硬化により樹脂層38を硬化させる場合には、20~100℃に加熱するのが好ましい。
以上の工程をロール・トゥ・ロール方式の装置において行うことにより、連続した(長尺の)蛍光体含有フィルムを得ることができる。得られた蛍光体含有フィルムは、必要により切断機により裁断(切断)される。
また、上記例では、樹脂層38を形成した後、一旦、ロール状に巻き取って、蛍光領域35の形成等を行う構成としたが、これに限定はされず、樹脂層38を形成した後、連続的に搬送して、蛍光領域35の形成等を行う構成としてもよい。
パターンの形成には、酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物を基板または支持体(基材)上に塗布する工程と、塗布層表面にモールドを圧接する工程と、硬化性化合物に光を照射する工程と、モールドを剥離する工程と、を経て微細な凹凸パターンを形成する、いわゆる光インプリント法を用いることができる。
ここで、酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物は基材とモールドの間に流しこみ、モールドを圧接しながら光硬化しても良い。さらに、光照射後にさらに加熱して硬化させても良い。このような光インプリントリソグラフィは、積層化や多重パターニングもでき、熱インプリントと組み合わせて用いることもできる。
また、インクジェット法、ディスペンサー法でパターン形成をすることもできる。
まず、硬化性化合物を基材上に塗布する。硬化性化合物を基材上に塗布する方法としては、一般によく知られた適用方法、例えば、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スピンコート方法、スリットスキャン法、キャスト法あるいはインクジェット法などを用いることで基材上に塗膜あるいは液滴を適用することができる。酸素に対して不透過性を有する樹脂層38を形成する硬化性化合物はグラビアコート法、キャスト法に適している。また、硬化性化合物からなるパターン形成層(パターンを形成するための塗布層)の膜厚は、使用する用途によって異なるが、1~150μm程度である。また硬化性化合物を、多重塗布により塗布してもよい。さらに、基材とパターン形成層との間には、例えば平坦化層等の他の有機層などを形成してもよい。これにより、パターン形成層と基板とが直接接しないことから、基板に対するごみの付着や基板の損傷等を防止することができる。
光照射は、モールドを付着させた状態で行ってもよいし、モールド剥離後に行ってもよいが、モールドを密着させた状態で行なうのが好ましい。
光透過性のモールド材は、特に限定されないが、所定の強度、耐久性を有するものであればよい。具体的には、ガラス、石英、PMMA、ポリカーボネート樹脂などの光透明性樹脂、透明金属蒸着膜、ポリジメチルシロキサンなどの柔軟膜、光硬化膜、SUS等の金属膜が例示される。
また、光インプリントリソグラフィにおいては、光照射の際の基板温度は、通常、室温で行われるが、反応性を高めるために加熱をしながら光照射してもよい。光照射の前段階として、真空状態にしておくと、気泡混入防止、酸素混入による反応性低下の抑制、モールドと硬化性組成物との密着性向上に効果があるため、真空状態で光照射してもよい。また、パターン形成方法中、光照射時における好ましい真空度は、10-1Paから1気圧の範囲である。
さらに、露光に際しては、酸素によるラジカル重合の阻害を防ぐため、窒素やアルゴンなどの不活性ガスを流して、酸素濃度を100mg/L未満に制御してもよい。
図面を参照して、本発明の蛍光体含有フィルムの一実施形態としての波長変換部材を備えたバックライトユニットについて説明する。図13は、バックライトユニットの概略構成を示す模式図である。
同様の観点から、バックライトユニットが発光する緑色光の波長帯域は、520nm~560nmであることが好ましく、520nm~545nmであることがより好ましい。
また、同様の観点から、バックライトユニットが発光する赤色光の波長帯域は、610nm~650nmであることがより好ましい。
なお、本実施形態では、光源として面状光源を用いた場合を例に説明したが、光源としては面状光源以外の光源も使用することができる。
バックライトユニットの構成としては、図13では、導光板や反射板などを構成部材とするエッジライト方式について説明したが、直下型方式であっても構わない。導光板としては、公知のものを何ら制限なく使用することができる。
上述のバックライトユニット102は液晶表示装置に応用することができる。図14に示されるように、液晶表示装置104は上記実施形態のバックライトユニット102とバックライトユニットの再帰反射性部材側に対向配置された液晶セルユニット103とを備えてなる。
<蛍光体含有フィルムの作製>
蛍光体として量子ドットを含有する塗布液を用いて蛍光体含有層を有する蛍光体含有フィルムを作製した。
第1の基材フィルムおよび第2の基材フィルムとして、ポリエチレンテレフタレート(PET)からなる支持フィルム上に無機層からなるバリア層及びそのバリア層上に下記組成物を塗工した有機層が形成されてなる基材フィルムを用意した。なお、無機層の形成材料は窒化ケイ素(Si3N4)で、厚みは30nmであった。この基材フィルムの酸素透過度をMOCON社製 OX-TRAN2/20を用いて計測したところ、4.0×10-3cc/(m2・day・atm)以下であった。
・ウレタンアクリレート(大成ファイルケミカル(株)社製 アクリット8BR-500) 30質量部
・光重合開始剤(イルガキュア184(BASF(株)製) 3質量部
・メチルイソブチルケトン 67質量部
蛍光体含有層形成用の塗布液1として、量子ドット、硬化性化合物、チキソトロピー剤、重合開始剤、および、シランカップリング剤などの各成分をタンクなどにより混合し、塗布液を調製する。
蛍光体含有層形成用の塗布液1として、量子ドット、硬化性化合物、チキソトロピー剤、重合開始剤、および、シランカップリング剤などの各成分をタンクなどにより混合し、塗布液を調製する。
下記の組成の量子ドット分散液を調製し、塗布液1とした。
・量子ドット1のトルエン分散液(発光極大:520nm) 10質量部
・量子ドット2のトルエン分散液(発光極大:630nm) 1質量部
・ラウリルメタクリレート 2.4質量部
・トリメチロールプロパントリアクリレート 0.54質量部
・光重合開始剤(イルガキュア819(BASF(株)製))
0.009質量部
・量子ドット1:INP530-10(NN-labs社製)
・量子ドット2:INP620-10(NN-labs社製)
下記の組成の樹脂層形成用の塗付液を調製し、塗布液2とした。
・ウレタン(メタ)アクリレート(U-4HA(新中村化学工業(株)製)) 49質量部
・トリシクロデカンジメタノールジアクリレート(A-DCP(新中村化学工業(株)製)) 25質量部
・1,6ヘキサンジオールジアクリレート(ライトアクリレート1.6HA-A(共栄社化学(株)製)) 25質量部
・光重合開始剤(イルガキュア819(BASF(株)製)) 1質量部
以下に示す光インプリント法で第1の基材フィルム上に樹脂層を形成した。まず、フォトエッチング法で作製したハニカム状パターンを有するSUSモールド(凹部の線幅0.5mm、凸部正六角形の対角線1mm、凹部深さ50μm)と、第1の基材フィルムの有機層側の間に上記樹脂形成用の塗布液2をディスペンサーで流し込み、ゴムローラで0.3MPaの圧力で圧接して、過剰な塗布液を排出し、第1の基材フィルム上に塗布液を充填したモールドを貼合させた形態とした。続いて、200W/cmの空冷メタルハライドランプ(アイグラフィックス社製)を用いて、紫外線を第一の基材フィルム側より500mJ/cm2照射して室温25℃で硬化させた後、モールドを剥離し、樹脂層が形成された第1の基材フィルムを得た。
以下に示す手順で、第一基材フィルム上の樹脂層間に充填され、第二基材フィルムと貼合された蛍光体層含有フィルムを作成した。まず、上記工程で作成した樹脂層が形成された第1の基材フィルムの樹脂層側と第2の基材フィルムの有機層側の間に蛍光体含有層の塗布液1をディスペンサーで流し込み、ゴムローラで0.3MPaの圧力で圧接して、過剰な塗布液を排出し、蛍光体含有層の塗布液を第1の基材フィルム、樹脂層、第2の基材フィルム間に充填した。続いて、200W/cmの空冷メタルハライドランプ(アイグラフィックス社製)を用いて、紫外線を第1の基材フィルム側より2500mJ/cm2照射して室温25℃で硬化し、蛍光体含有フィルムを作製した。得られた蛍光体含有フィルムは樹脂層の幅0.5mm、蛍光体層幅1mm、樹脂層及び蛍光体層の膜厚は50μmであった。
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液3の組成>
・1,6ヘキサンジオールジアクリレート(ライトアクリレート1.6HA-A(共栄社化学(株) 製)) 99質量部
・光重合開始剤(イルガキュア819(BASF(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液4の組成>
・1,9-ノナンジオールジアクリレート(1,9NDA(共栄社化学(株)社製) 99質量部
・光重合開始剤(イルガキュア819(BASF(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液4の組成>
・ジペンタエリスリトールヘキサアクリレート(DPHA(ダイセル・サイテック(株)社製)) 99質量部
・光重合開始剤(イルガキュア2022(BASF(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液5の組成>
・ウレタン(メタ)アクリレート(U-4HA(新中村化学工業(株)製)) 48質量部
・エポキシメタクリレート(サイクロマーM100((株)ダイセル社製)) 25質量部
・トリシクロデカンジメタノールジアクリレート(A-DCP(新中村化学工業(株)製)) 25質量部
・光重合開始剤(イルガキュア819(BASF(株)製) 1質量部
・光重合開始剤(CPI-100P(サンアプロ(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液6の組成>
・トリシクロデカンジメタノールジアクリレート(A-DCP(新中村化学工業(株)製)) 99質量部
・光重合開始剤(イルガキュア819(BASF(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液8の組成>
・ウレタン(メタ)アクリレート(U-4HA(新中村化学工業(株)製)) 99質量部
・光重合開始剤(イルガキュア2022(BASF(株)製) 1質量部
樹脂層形成用の塗布液として、以下に記載する組成物を使用した以外は実施例1と同様にして蛍光体含有フィルムを作製した。
<樹脂層形成用の塗布液7の組成>
・トリメチロールプロパントリアクリレート(A-TMPT(新中村化学(株)社製)) 99質量部
・光重合開始剤(イルガキュア819(BASF(株)製) 1質量部
樹脂層を硬化する際の紫外線の照射総量を50000mJ/cm2とした以外は、実施例1と同様にして蛍光体含有フィルムを作製した。
樹脂層を硬化する際の紫外線の照射総量を500mJ/cm2とした以外は、実施例1
と同様にして蛍光体含有フィルムを作製した。
第一基材フィルムと第二基材フィルムをクラリスタCI(株式会社クラレ製)とした以外は、実施例1と同様にして蛍光体含有フィルムを作製した。この基材フィルムの酸素透過度をMOCON社製 OX-TRAN 2/20を用いて計測したところ、1.0×10-1cc/(m2・day・atm)以下であった。
各実施例および比較例で作製した蛍光体含有フィルムの樹脂層のヌープ硬度、クリープ回復率および弾性回復率をそれぞれ下記のようにして測定した。
各実施例および比較例で作製した蛍光体含有フィルムの樹脂層と同様のサンプルを作製した。フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定した。押し込み深さから求められる圧子とサンプルとの接触面積と最大荷重の関係より硬度を算出し、この10点の平均値をヌープ硬度とした。
フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定した。除荷直後の押し込み深さと除荷5秒後の深さの関係よりクリープ回復の割合を算出し、この10点の平均値をクリープ回復率とした。
フィッシャーインスツルメンツ(株)社製PICODENTOR HM500p型硬度計を用い、ヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、最大荷重でのクリープ時間5sec、除荷時間10sec、除荷後のクリープ時間5sec、最大荷重20mNの条件で測定する。横軸押し込み深さ、縦軸荷重にとったグラフにおいて[クリープ時間後の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、荷重ゼロ]、[除荷直後の押し込み深さ、荷重ゼロ]の3点で囲まれる面積(除荷時に解放される弾性変形エネルギーEに相当)と、原点、[クリープ時間前の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、最大荷重]、[クリープ時間後の押し込み深さ、荷重ゼロ]の4点で囲まれる面積(負荷(およびクリープ)に要した総エネルギーE合計に相当)との関係より弾性回復の割合を算出し、この10点の平均値を弾性回復率とする。
各実施例および比較例で作製した蛍光体含有フィルムの樹脂層の水蒸気透過率および含水率を樹脂層のサンプルを用いてそれぞれ下記のようにして測定した。
水蒸気透過率は、カルシウム腐食法(特開2005-283561号公報に記載される方法)によって測定した。恒温恒湿処理の条件は、温度40℃、相対湿度90%RHとした。
酸素透過度は、SI単位として、fm/(s・Pa)を用いることができる。1fm/(s・Pa)=8.752cc/(m2・day・atm)で換算することが可能である。fmはフェムトメートルと読み、1fm=10-15mを表わす。
ここで、酸素透過度は、測定温度23℃、相対湿度90%の条件下で、酸素ガス透過率測定装置(MOCON社製、OX-TRAN 2/20:商品名)を用いて測定した値である。
実施例および比較例で作製した蛍光体含有フィルムは波長変換部材であり、この波長変換部材の発光性能の経時変化を以下のように測定し、評価した。
各実施例および比較例の波長変換部材の初期輝度(Y)を、以下の手順で測定した。
まず、各波長変換部材を、(株)ナカヤマ社製トムソン刃MIR-CI23を使って1インチ角の正方形に裁断した。裁断された波長変換部材の各辺は、樹脂層および蛍光領域をまたいでいる。
一方で、市販のタブレット端末(Amazon社製、Kindle(登録商標) Fire HDX 7”)を分解し、バックライトユニットを取り出した。取り出したバックライトユニットに付属している波長変換部材を取り外した上で、導光板上に上記のようにして作製した蛍光体含有フィルムを置き、その上に、向きが直交した2枚のプリズムシートを重ね置いた。青色光源から発し、蛍光体含有フィルムおよび2枚のプリズムシートを透過した光の輝度のうち、裁断面から1mm内側の位置(但し、裁断面に位置する蛍光領域以外の蛍光領域)における輝度を、導光板の面に対して垂直方向740mmの位置に設置した輝度計(SR3、TOPCON社製)にて測定し、初期の輝度(Y)とした。
初期輝度(Y)の評価基準を以下に示す。評価結果がB以上であれば、発光効率が良好に維持されていると判断することができる。
AA; 14000[cd/m2]<Y
A; 12000[cd/m2]<Y≦14000[cd/m2]
B; 10000[cd/m2]<Y≦12000[cd/m2]
C; 8000[cd/m2]<Y≦10000[cd/m2]
D; 8000[cd/m2]≧Y
次に、85℃に保たれた部屋で、市販の青色光源(OPTEX-FA株式会社製OPSM-H150X142B)上に各波長変換部材を置き、波長変換部材に対して青色光を2000時間連続で照射した。1000時間及び2000時間後、波長変換部材を取り出し、上記と同様の手順で輝度を測定した。高温試験1000時間の輝度、高温試験2000時間の輝度)をそれぞれ測定した。試験後の輝度をY’としたとき、
下記式
α=Y’/Y
によって、初期の輝度値(Y)に対する、試験後の輝度(Y’)の変化率(α)を算出し、輝度変化の指標として、以下の基準で評価した。評価結果がAおよびBであれば、発光効率が良好に維持されていると判断することができる。なお、評価結果Cは実用上許容されるが、評価結果Dは許容できない。以下の劣化評価においても、初期の輝度値に対する試験後の輝度の変化率の評価基準は同様とする。
A; 0.95<α
B; 0.7<α≦0.95
C; 0.5<α≦0.7
D; 0.5≧α
なお、比較例2および比較例4では切り残りが発生したため端部の劣化評価は行っていない。
(株)ナカヤマ社製トムソン刃MIR-CI23を使って50mm角に裁断した各実施例および比較例の波長変換部材、市販のタブレット端末(Amazon社製、Kindle(登録商標) Fire HDX 7”)に搭載された2枚のプリズムシートを市販の青色光源(OPTEX-FA株式会社製OPSM-H150X142B)上に載せ、青光を照射した状態を一眼レフデジカメ(Nikon製D-7200)で撮影した。得られた画像のサンプル中心より40mm角の範囲において、Gray値の平均値(G)および標準偏差σを求め、以下の基準で評価した。評価結果がAおよびBであれば、輝度ムラが良好であると判断することができる。なお、評価結果Cは実用上許容されるが、評価結果Cは許容できない。
A:0%≦σ/G<3%
B:3%≦σ/G<10%
C:10%≦σ/G<20%
D:20%≧σ/G
各波長変換部材を、(株)ナカヤマ社製トムソン刃MIR-CI23を使って1インチ角の正方形に裁断し、その端面を光学顕微鏡Nikon社製DS-Ri2により正方形の四辺を撮影し、以下の基準で評価した。
A:隔壁へのひびなし、面つぶれなし
B:四辺の内一つでも隔壁にひびが発生
C:四辺の内一つでも面つぶれあり
各波長変換部材を、(株)ナカヤマ社製トムソン刃MIR-CI23を使って1インチ角の正方形に裁断し、切り残りの有無を評価した。
結果を表1に示す。
また、実施例3と比較例3との対比から、弾性回復率が小さすぎると、裁断面がつぶれてしまい、初期輝度が低下し、また、輝度ムラが発生してしまうことがわかる。これは弾性回復率が小さすぎると裁断後の形状回復が遅れて膜厚ムラとなり輝度ムラにつながると考えられる。
また、実施例4と比較例4との対比から、クリープ回復率が大きすぎると、切り残りが発生してしまうことがわかる。これはクリープ回復率が大きすぎると、粘弾性挙動が現れ、切れ残りがでると考えられる。
10、20 基材フィルム
11、21 支持フィルム
12、22 バリア層
30 蛍光体含有層
31、31a、31b、31e 蛍光体
32 蛍光領域形成用塗布液
33 バインダ
35、35a、35b 蛍光体を含む領域(蛍光領域)
37 樹脂層用塗布液
38 酸素に対する不透過性を有する樹脂層
50 転送ローラ
52、58、62、68 バックアップローラ
54、64 塗布部
56、66 硬化部
59 積層フィルム
60 ラミネートローラ
100 波長変換部材
101A 光源
101B 導光板
101C 面状光源
102 バックライトユニット
102A 反射板
102B 再帰反射性部材
103 液晶セルユニット
104 液晶表示装置
110 液晶セル
120、130 偏光板
121、123、131、133 偏光板保護フィルム
122、132 偏光子
Claims (6)
- 酸素に暴露されると酸素と反応して劣化する蛍光体を含む蛍光領域が複数、離散的に配置され、離散的に配置された複数の前記蛍光領域間に、酸素に対する不透過性を有する樹脂層が配置されてなる蛍光体含有層と、
前記蛍光体含有層の一方の主面に積層される第1の基材フィルムおよび他方の主面に積層される第2の基材フィルムと、を有し、
前記樹脂層のヌープ硬度が115N/mm2~285N/mm2であり、クリープ回復率が22%以下であり、弾性回復率が60%以上である蛍光体含有フィルム。 - 前記蛍光体含有フィルムの端面において、蛍光特性を失った領域と前記樹脂層とが露出している請求項1に記載の蛍光体含有フィルム。
- 前記樹脂層の酸素透過度が10cc/(m2・day・atm)以下である請求項1または2に記載の蛍光体含有フィルム。
- 前記第1の基材フィルムおよび前記第2の基材フィルムの酸素透過度が1cc/(m2・day・atm)以下である請求項1~3のいずれか一項に記載の蛍光体含有フィルム。
- 前記樹脂層に含まれる樹脂が、光重合性官能基又は熱重合性官能基を有する化合物を含有する組成物から成る請求項1~4のいずれか一項に記載の蛍光体含有フィルム。
- 請求項1~5のいずれか一項に記載の蛍光体含有フィルムからなる波長変換部材と、青色発光ダイオードおよび紫外線発光ダイオードの少なくとも一方とを含むバックライトユニット。
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Cited By (3)
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CN113825641A (zh) * | 2019-05-13 | 2021-12-21 | 大日本印刷株式会社 | 阻隔膜、使用其的波长转换片以及使用其的显示装置 |
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Also Published As
Publication number | Publication date |
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JPWO2018043543A1 (ja) | 2019-07-18 |
CN109661598A (zh) | 2019-04-19 |
KR102150930B1 (ko) | 2020-09-02 |
US20190194530A1 (en) | 2019-06-27 |
US11136496B2 (en) | 2021-10-05 |
KR20190031556A (ko) | 2019-03-26 |
JP6675008B2 (ja) | 2020-04-01 |
CN109661598B (zh) | 2021-04-27 |
US20210388258A1 (en) | 2021-12-16 |
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