WO2016098570A1 - Organic el element, curable resin composition, method for forming wavelength conversion unit, and organic el device - Google Patents
Organic el element, curable resin composition, method for forming wavelength conversion unit, and organic el device Download PDFInfo
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- WO2016098570A1 WO2016098570A1 PCT/JP2015/083636 JP2015083636W WO2016098570A1 WO 2016098570 A1 WO2016098570 A1 WO 2016098570A1 JP 2015083636 W JP2015083636 W JP 2015083636W WO 2016098570 A1 WO2016098570 A1 WO 2016098570A1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
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- H10K85/30—Coordination compounds
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Definitions
- the present invention relates to an organic EL element, a curable resin composition, a method for forming a wavelength conversion unit, and an organic EL device.
- the extremely small particles (dots) that can confine electrons three-dimensionally are called quantum dots and have attracted attention in recent years.
- the size of one quantum dot is several nanometers (nm) to several tens of nanometers (nm) in diameter.
- a wavelength conversion (color conversion) part including quantum dots as a wavelength conversion material When a wavelength conversion (color conversion) part including quantum dots as a wavelength conversion material is applied to, for example, an organic EL element, it is required to realize excellent luminance characteristics. Therefore, for example, it is desired to increase the content of quantum dots in the wavelength conversion section formed in a layered or film shape.
- a wavelength conversion unit including quantum dots there is a problem that patterning properties are deteriorated.
- a display device when a display device is configured using an organic EL element, it is required to form a wavelength conversion unit having a size corresponding to a display pixel size or pattern the wavelength conversion unit in a stripe shape having a desired size.
- an object of the present invention is to provide an organic EL element that has a wavelength conversion unit including quantum dots, suppresses a decrease in patterning property, and easily increases luminance.
- Another object of the present invention is to provide a curable resin composition that includes a quantum dot and provides a wavelength conversion part of an organic EL device by forming a cured film that exhibits excellent fluorescence characteristics and patterning properties. is there.
- Still another object of the present invention is to provide a method for forming a wavelength conversion part that forms a wavelength conversion part having excellent fluorescence characteristics at a desired location of an organic EL element.
- Still another object of the present invention is to provide an organic EL device that can easily display an image with high luminance and excellent image quality.
- a first aspect of the present invention is an organic EL element having a light emitting part and a wavelength converting part
- the wavelength converter is [A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms other than (a1) in the same or different polymer molecules
- [B] The present invention relates to an organic EL device characterized by being formed using a curable resin composition containing quantum dots.
- the [B] quantum dot is at least selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element. It is preferably made of a compound containing two kinds of elements.
- the [B] quantum dot is made of a compound containing In as a constituent component.
- the [B] quantum dot comprises an InP / ZnS compound, a CuInS 2 / ZnS compound, an AgInS 2 compound, a (ZnS / AgInS 2 ) solid solution / ZnS compound, a Zn-doped AgInS 2 compound, and an Si compound. It is preferably at least one selected from the group consisting of:
- the second aspect of the present invention is: [A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms in the same or different polymer molecules, and [B] a quantum dot A curable resin composition containing,
- the present invention relates to a curable resin composition that is used for forming the wavelength conversion part of the organic EL device according to the first aspect of the present invention.
- the [B] quantum dot is at least selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element. It is preferably made of a compound containing two kinds of elements.
- the [B] quantum dot is made of a compound containing In as a constituent component.
- the [B] quantum dot comprises an InP / ZnS compound, a CuInS 2 / ZnS compound, an AgInS 2 compound, a (ZnS / AgInS 2 ) solid solution / ZnS compound, a Zn-doped AgInS 2 compound, and an Si compound. It is preferably at least one selected from the group consisting of:
- a third aspect of the present invention is a method of forming a wavelength conversion unit that forms the wavelength conversion unit of an organic EL element having a light source unit that emits light containing at least blue light and a wavelength conversion unit, (1) The process of forming the coating film of the curable resin composition of the 2nd aspect of this invention on a base material, (2) A step of irradiating at least a part of the coating film formed in step (1), (3) The step of developing the coating film irradiated with radiation in the step (2), and (4) The step of exposing the coating film developed in the step (3). Regarding the method.
- the fourth aspect of the present invention relates to an organic EL device comprising the organic EL element of the first aspect of the present invention and used for image display.
- an organic EL element that has a wavelength conversion unit including quantum dots and suppresses a decrease in patterning property and easily increases luminance.
- a curable resin composition that provides a wavelength conversion part of an organic EL element by forming a cured film that includes quantum dots and exhibits excellent fluorescence characteristics and patterning properties. Is done.
- a method for forming a wavelength conversion unit that forms a wavelength conversion unit with excellent fluorescence characteristics at a desired location of an organic EL element.
- an organic EL device that can easily display an image with high luminance and excellent image quality.
- FIG. 1 is a cross-sectional view schematically showing an organic EL element according to a first embodiment of the present invention. It is sectional drawing which shows schematically the organic EL element of 2nd Embodiment of this invention. It is sectional drawing of the base material explaining an example of the coating-film formation process in the formation method of the wavelength conversion part of 4th Embodiment of this invention. It is sectional drawing which illustrates typically an example of the radiation irradiation process in the formation method of the wavelength conversion part of 4th Embodiment of this invention. It is sectional drawing of the board
- FIG. 1 is a cross-sectional view schematically showing an organic EL element according to the first embodiment of the present invention.
- An organic EL element 100 shown in FIG. 1 includes a circuit substrate 10 that is a substrate on which a pixel circuit is formed, a second planarization film 20 formed on the circuit substrate 10, and a plurality of rows on the second planarization film 20.
- An organic EL element array 30 composed of a plurality of organic EL portions 31 arranged over a plurality of rows, a passivation layer 40 formed on the organic EL element array 30, and a wavelength conversion member 50 arranged on the passivation layer 40.
- An active matrix image display device is a circuit substrate 10 that is a substrate on which a pixel circuit is formed, a second planarization film 20 formed on the circuit substrate 10, and a plurality of rows on the second planarization film 20.
- An organic EL element array 30 composed of a plurality of organic EL portions 31 arranged over a plurality of rows, a passivation layer 40 formed on the organic EL element array 30, and a wavelength conversion member 50 arranged on the passivation layer 40.
- the organic EL element array 30 is a light emitting unit in the organic EL element 100 according to the first embodiment of the present invention, and constitutes a light source unit that emits light including at least blue light.
- the wavelength conversion member 50 is a light emitting part and is disposed opposite to the organic EL part 31 of the organic EL element array 30 serving as a light source, and converts the wavelength of light from the organic EL part 31.
- a conversion part it has red wavelength conversion layer 53R, green wavelength conversion layer 53G, and blue wavelength conversion layer 53B.
- Each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B of the wavelength conversion member 50 is configured to contain quantum dots.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B of the wavelength conversion member 50 each contain a quantum dot, and each serves as a wavelength conversion unit.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B are disposed to face the organic EL unit 31, and convert light from the organic EL unit 31 into red light, green light, or blue light. be able to. Therefore, the organic EL element 100 can form a color image and perform color display by controlling the amount of red light, green light, and blue light emitted from the wavelength conversion member 50.
- the circuit board 10 has a plurality of pixel circuits formed on a substrate 11 made of glass or resin through a buffer layer 12 made of, for example, spin-on-glass (SOG).
- each pixel circuit one switching circuit is formed for each of the plurality of organic EL units 31 constituting the organic EL element array 30, and these switching circuits are arranged in a plurality of rows and a plurality of columns in plan view. They are arranged in a matrix.
- Each switching circuit includes one thin film transistor for selection (hereinafter, the thin film transistor is abbreviated as “TFT”), one driving TFT, and a pair of capacitor (holding capacitor) electrodes.
- TFT thin film transistor for selection
- FIG. 1 a total of four selection TFTs 15 and one capacitor electrode 16 in each of the four pairs of capacitor electrodes appear, and the other capacitor electrode in each of the driving TFTs and the total of four pairs of capacitor electrodes appears. Absent.
- each selection TFT 15 The source 13 s and the drain 13 d in each selection TFT 15 are formed in the silicon layer 13 formed on the buffer layer 12, and the gate 14 in these selection TFT 15 is a gate insulating film (not shown) on the silicon layer 13. ).
- the source 13s of each selection TFT 15 constituting one row is connected to the data line 19 by a contact plug 17a, and the drain 13d of each of these selection TFTs 15 is connected to the data line 19 by a contact plug 17b. At the same time, it is connected to the gate of the corresponding driving TFT and one capacitor electrode 16 of the corresponding pair of capacitor electrodes.
- the gates 14 of these selection TFTs 15 are connected to one selection line (none is shown) by contact plugs.
- each driving TFT constituting one column is connected to one power supply line, and the drain of each of these driving TFTs is connected to the pixel electrode 31a of the corresponding organic EL section 31 and a corresponding pair.
- the capacitor electrode is connected to the other capacitor electrode.
- Each selection TFT 15 and each driving TFT are covered with, for example, a first planarization film 18 formed of an inorganic material.
- the data line 19 is formed on the first planarization film 18.
- the selection line and the power supply line are formed on the buffer layer 12 and covered with the first planarization film 18.
- the second planarization film 20 is formed of an inorganic material or an organic material and covers the data line 19.
- the organic EL element array 30 has a plurality of organic EL portions 31 arranged in a plurality of rows and columns, and a lattice shape so as to surround each organic EL portion 31 when the organic EL element array 30 is viewed in plan view. And a partition wall portion 32 formed on the surface.
- Each organic EL unit 31 includes a pixel electrode 31a disposed on the second planarization film 20, an organic light emitting layer 31b stacked on the pixel electrode 31a, an upper surface of each organic light emitting layer 31b, and an upper portion of the partition wall 32. And a region on the organic light emitting layer 31b in one common electrode 31c covering the same.
- These organic EL portions 31 are top emission type light emitting elements that emit white light from the common electrode 31c side.
- the individual organic light emitting layers 31b are, for example, a red organic light emitting layer that emits red light, a green organic light emitting layer that emits green light, and a blue organic light emitting layer that emits blue light in any order and adjacent in the vertical direction. It can be formed by sequentially laminating on the pixel electrode 31a with the charge generation layer interposed between the organic light emitting layers. Alternatively, the yellow organic light emitting layer that emits yellow light and the blue organic light emitting layer are arranged in any order, and the charge generation layer is interposed between the yellow organic light emitting layer and the blue organic light emitting layer, and sequentially on the pixel electrode 31a. It can be formed by stacking. The organic light emitting layer 31b can emit white light by combining the light from each color organic light emitting layer by the above stacking.
- the partition wall 32 of the organic EL element array 30 is cured by, for example, patterning the resin layer after forming the resin layer, or applying the resin material to a predetermined shape by an ink jet method or a printing method. Can be formed.
- the passivation layer 40 is formed of, for example, a transparent organic material and covers the common electrode 31c.
- the wavelength conversion member 50 includes a substrate 51 formed using a transparent inorganic material or a transparent organic material, and a red color filter 52R, a green color filter 52G, and a blue color filter 52B regularly arranged on the substrate 51.
- the red color filter 52R, the green color filter 52G, and the blue color filter 52B constitute a color filter in the organic EL element 100. That is, the color filter included in the organic EL element 100 includes the red color filter 52R, the green color filter 52G, and the blue color filter 52B.
- the substrate 51 is made of, for example, glass, quartz, or transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).
- Each of the red color filter 52R, the green color filter 52G, and the blue color filter 52B is formed of a resin material colored in red, green, or blue according to a known method. For example, a stripe pattern, a mosaic pattern, It is arranged under a desired pattern such as a Bayer pattern.
- the wavelength conversion member 50 includes a red wavelength conversion layer 53R formed on the red color filter 52R when viewed from the substrate 51, a green wavelength conversion layer 53G formed on the green color filter 52G, and a blue color filter 52B. And a blue wavelength conversion layer 53B formed on the substrate.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B are cured films formed by using the curable resin composition of the third embodiment of the present invention described later, each containing quantum dots. Configured.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B each include, for example, light in a predetermined wavelength range such as blue light contained in white light from the organic EL unit 31 in red.
- the wavelength conversion unit converts light, green light, or blue light.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B may be collectively referred to as wavelength conversion layers 53R, 53G, and 53B.
- the red wavelength conversion layer 53R emits red fluorescence when irradiated with excitation light, specifically, excitation light from the organic EL unit 31. That is, the red wavelength conversion layer 53R converts light from the organic EL unit 31 into red light.
- the green wavelength conversion layer 53G emits green fluorescence when irradiated with excitation light. That is, the green wavelength conversion layer 53G converts light from the organic EL unit 31 into green light.
- the blue wavelength conversion layer 53B emits blue fluorescence when irradiated with excitation light. That is, the blue wavelength conversion layer 53B converts light from the organic EL unit 31 into blue light.
- the thicknesses of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B of the wavelength conversion member 50 are each preferably about 100 nm to 100 ⁇ m, and more preferably 1 ⁇ m to 100 ⁇ m. If the thickness is less than 100 nm, the excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, so that there is a problem that the luminance of the display element cannot be sufficiently secured. Furthermore, in order to increase the absorption of excitation light and sufficiently secure the luminance of the display element, the thickness is preferably 1 ⁇ m or more.
- Each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B has substantially the same size as one organic EL unit 31 or one organic EL unit 31 in plan view.
- One wavelength conversion layer 53R, 53G, 53B is located above one organic EL unit 31.
- the organic EL unit 31 and each of the wavelength conversion layers 53R, 53G, and 53B having the same size are disposed to face each other, and convert light from the organic EL unit 31 into red light, green light, or blue light. .
- the organic EL unit 31 corresponding to each of the wavelength conversion layers 53R, 53G, and 53B is viewed in plan from the wavelength conversion layer 53R, 53G, and 53B side, the organic EL unit 31 includes the corresponding wavelength conversion layer 53R. , 53G, 53B does not substantially protrude outward.
- the wavelength conversion layers 53R, 53G, and 53B corresponding to the color filters 52R, 52G, and 52B are viewed in plan from the color filter side, the wavelength conversion layers 53R, 53G, and 53B correspond to the color filters. It does not substantially protrude outward from 52R, 52G, and 52B.
- the color filter is provided on the anti-organic EL element side of the wavelength conversion layers 53R, 53G, and 53B disposed to face the organic EL unit 31. That is, the color filter is provided above the wavelength conversion unit, and is disposed on the side opposite to the side on which the light source unit including the organic EL unit 31 is disposed with the wavelength conversion unit interposed therebetween.
- the wavelength conversion member 50 has a black matrix 54 formed on the substrate 51 by an inorganic material or an organic material having a light shielding property.
- the black matrix 54 surrounds the color filters 52R, 52G, and 52B and also surrounds the wavelength conversion layers 53R, 53G, and 53B in plan view.
- the black matrix 54 can be formed by patterning according to a known method using a known light-shielding material. Note that the black matrix 54 is not an essential component in the wavelength conversion member 50, and the wavelength conversion member 50 may be configured without the black matrix 54.
- the wavelength conversion member 50 is bonded onto the passivation layer 40 after the wavelength conversion member 50 is formed alone, for example.
- the color conversion layers 53R, 53G, and 53B, the color filters 52R, 52G, and 52B, and the black matrix 54 are sequentially formed on the passivation layer 40, and then the color filters 52R, 52G, and 52B, and the black matrix 54, respectively. It can be formed by bonding the substrate 51 on the upper surface of the substrate.
- the white light from the organic EL element array 30 is used as excitation light, and the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B of the wavelength conversion member 50 respectively Excitation light can be converted into red light, green light, and blue light. Further, the organic EL element 100 converts the red light, the green light, and the blue light emitted from each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B of the wavelength conversion member 50 into each color. High color purity can be achieved by transmitting the filters 52R, 52G, and 52B.
- the organic EL element 100 Furthermore, in the organic EL element 100, light from the organic EL unit 31 of the organic EL element array 30 passes through the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, or the blue wavelength conversion layer 53B, and is not wavelength-converted. When emitted, each of the color filters 52R, 52G, and 52B of the wavelength conversion member 50 is used so that the wavelength characteristics of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue wavelength conversion layer 53B are assisted. Adjustments can be made. And in the organic EL element 100, it can reduce that the light of an undesired color is radiate
- each of the wavelength conversion layers 53R, 53G, and 53B containing quantum dots is formed by the curable resin composition of the third embodiment of the present invention described later. Yes. For this reason, each of the wavelength conversion layers 53R, 53G, and 53B exhibits excellent fluorescence characteristics, specifically, wavelength conversion efficiency due to the inclusion of quantum dots. Further, since it is difficult for a residue to occur when each of the wavelength conversion layers 53R, 53G, and 53B is formed, color mixing between pixels due to the occurrence of the residue of the wavelength conversion layers 53R, 53G, and 53B in an undesired portion is also unlikely to occur. . As a result of these, the organic EL element 100 can be used for the configuration of an organic EL device that can easily increase the luminance, and can display an image with high luminance and high image quality.
- FIG. 2 is a cross-sectional view schematically showing an organic EL element according to the second embodiment of the present invention.
- the organic EL element 200 of the second embodiment shown in FIG. 2 uses blue light as excitation light, and the wavelength conversion member 150 includes a red wavelength conversion layer 53R, a green wavelength conversion layer 53G, and a blue diffusion layer 151, except that It has the same structure as the organic EL element 100 of one embodiment. Therefore, in the organic EL element 200 of the second embodiment shown in FIG. 2, the same reference numerals are given to the same constituent elements as those of the organic EL element 100 of FIG.
- An organic EL element 200 shown in FIG. 2 includes a circuit substrate 10 on which a pixel circuit is formed, a second planarization film 20 formed on the circuit substrate 10, and a plurality of rows and columns on the second planarization film 20.
- An organic EL element array 130 composed of a plurality of organic EL portions 131 arranged over the organic EL element 131, a passivation layer 40 formed on the organic EL element array 130, and a wavelength conversion member 150 disposed on the passivation layer 40. This is an active matrix drive type image display element.
- the organic EL part 131 of the organic EL element array 130 can emit blue light as will be described later. That is, the organic EL element array 130 is a light emitting unit in the organic EL element 200 of the second embodiment of the present invention, and constitutes a light source unit that emits blue light.
- the wavelength conversion member 150 is a light emitting part and is disposed opposite to the organic EL part 131 of the organic EL element array 130 serving as a light source, and converts the wavelength of light from the organic EL part 131.
- the wavelength conversion member 150 has red wavelength conversion layer 53R and green wavelength conversion layer 53G.
- the wavelength conversion member 150 includes a blue diffusion layer 151 as a light diffusion layer that is disposed opposite to the organic EL unit 131 and diffuses and emits light from the organic EL unit 131.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G of the wavelength conversion member 150 are each configured to contain quantum dots. That is, in the organic EL element 200, the red wavelength conversion layer 53R and the green wavelength conversion layer 53G of the wavelength conversion member 150 each contain a quantum dot, and each serves as a wavelength conversion unit.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G are disposed to face the organic EL unit 131, and can convert blue light from the organic EL unit 131 into red light or green light.
- the blue diffusion layer 151 of the wavelength conversion member 150 can diffuse and emit the blue light from the organic EL unit 131 with the same wavelength (color) characteristics without converting the wavelength. Therefore, the organic EL element 200 can form a color image and perform color display by controlling the amount of red light, green light, and blue light emitted from the wavelength conversion member 150.
- the circuit board 10 has a plurality of pixel circuits formed on a substrate 11 made of glass or resin through a buffer layer 12 made of, for example, spin-on-glass (SOG).
- each pixel circuit one switching circuit is formed for each of the plurality of organic EL units 131 constituting the organic EL element array 130, and these switching circuits are arranged in a plurality of rows and a plurality of columns in plan view. They are arranged in a matrix.
- Each switching circuit includes one thin film transistor for selection (hereinafter, the thin film transistor is abbreviated as “TFT”), one driving TFT, and a pair of capacitor (holding capacitor) electrodes.
- TFT thin film transistor for selection
- FIG. 2 a total of four selection TFTs 15 and one capacitor electrode 16 in each of the four pairs of capacitor electrodes appear, and the other capacitor electrode in each of the driving TFTs and the total of four pairs of capacitor electrodes appears. Absent.
- each selection TFT 15 The source 13 s and the drain 13 d in each selection TFT 15 are formed in the silicon layer 13 formed on the buffer layer 12, and the gate 14 in these selection TFT 15 is a gate insulating film (not shown) on the silicon layer 13. ).
- the source 13s of each selection TFT 15 constituting one row is connected to the data line 19 by a contact plug 17a, and the drain 13d of each of these selection TFTs 15 is connected to the data line 19 by a contact plug 17b. At the same time, it is connected to the gate of the corresponding driving TFT and one capacitor electrode 16 of the corresponding pair of capacitor electrodes.
- the gates 14 of these selection TFTs 15 are connected to one selection line (none is shown) by contact plugs.
- each driving TFT constituting one column is connected to one power supply line, and the drain of each of these driving TFTs is connected to the pixel electrode 31a of the corresponding organic EL unit 131 and the corresponding pair of pixels.
- the capacitor electrode is connected to the other capacitor electrode.
- Each selection TFT 15 and each driving TFT are covered with, for example, a first planarization film 18 formed of an inorganic material.
- the data line 19 is formed on the first planarization film 18.
- the selection line and the power supply line are formed on the buffer layer 12 and covered with the first planarization film 18.
- the second planarization film 20 is formed of an inorganic material or an organic material and covers the data line 19.
- the organic EL element array 130 includes a plurality of organic EL units 131 arranged in a plurality of rows and columns, and a lattice shape so as to surround each organic EL unit 131 when the organic EL element array 130 is viewed in plan view. And a partition wall portion 32 formed on the surface.
- Each organic EL portion 131 includes a pixel electrode 31a disposed on the second planarizing film 20, an organic light emitting layer 131b stacked on the pixel electrode 31a, an upper surface of each organic light emitting layer 131b, and an upper portion of the partition wall portion 32. And a region on the organic light emitting layer 131b in one common electrode 31c covering the same.
- These organic EL portions 131 are top emission type light emitting elements that emit white light from the common electrode 31c side.
- Each organic light emitting layer 131b can be formed by laminating a blue organic light emitting layer emitting blue light on the pixel electrode 31a.
- the partition wall 32 can be formed, for example, by patterning the resin layer after forming the resin layer, or by curing the resin material after applying the resin material to a predetermined shape by an ink jet method or a printing method.
- the passivation layer 40 is formed of, for example, a transparent organic material and covers the common electrode 31c.
- the wavelength conversion member 150 includes a substrate 51 formed using a transparent inorganic material or a transparent organic material, and a red color filter 52R, a green color filter 52G, and a blue color filter 52B regularly arranged on the substrate 51.
- the red color filter 52R, the green color filter 52G, and the blue color filter 52B constitute a color filter in the organic EL element 200. That is, the color filter of the organic EL element 200 includes a red color filter 52R, a green color filter 52G, and a blue color filter 52B.
- the substrate 51 is made of glass, quartz, or transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).
- Each of the red color filter 52R, the green color filter 52G, and the blue color filter 52B is formed of a resin material colored in red, green, or blue according to a known method. For example, a stripe pattern, a mosaic pattern, It is arranged under a desired pattern such as a Bayer pattern.
- the wavelength conversion member 150 includes a red wavelength conversion layer 53R formed on the red color filter 52R when viewed from the substrate 51, a green wavelength conversion layer 53G formed on the green color filter 52G, and a blue color filter 52B. And a blue diffusion layer 151 formed on the substrate.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G of the wavelength conversion member 150 are cured films formed using the curable resin composition of the third embodiment to be described later, and are each configured to contain quantum dots.
- the blue diffusion layer 151 can be formed, for example, by dispersing light scattering particles in a resin serving as a base material.
- the red wavelength conversion layer 53R of the wavelength conversion member 150 When the red wavelength conversion layer 53R of the wavelength conversion member 150 is irradiated with excitation light, specifically, excitation light (blue light) from the organic EL unit 131, the wavelength is converted to red fluorescence.
- the green wavelength conversion layer 53G When the green wavelength conversion layer 53G is irradiated with excitation light (blue light), the green wavelength conversion layer 53G converts the wavelength and emits green fluorescence.
- the blue diffusion layer 151 can diffuse and emit the blue light when receiving the blue light from the organic EL unit 131.
- each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151 of the wavelength conversion member 150 is preferably about 100 nm to 100 ⁇ m, and more preferably 1 ⁇ m to 100 ⁇ m.
- the thickness of the red wavelength conversion layer 53R and the green wavelength conversion layer 53G is less than 100 nm, the excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, so that the luminance of the display element cannot be sufficiently secured. Problems arise.
- the blue diffusion layer 151 preferably has a thickness in the above range so that the blue light from the organic EL element 131 can be efficiently diffused and emitted.
- Each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151 is substantially the same size as one organic EL unit 131 in plan view, or from one organic EL unit 131. Also, one wavelength conversion layer 53R, 53G or blue diffusion layer 151 is located above one organic EL unit 131. That is, the organic EL unit 131 and the wavelength conversion layers 53R and 53G having the same size as each other are arranged to face each other and convert the wavelength of blue light from the organic EL unit 131.
- the organic EL unit 131 and the blue diffusion layer 151 having the same size are disposed so as to diffuse the blue light from the organic EL unit 131.
- the blue diffusion layer 151 is preferably configured by dispersing transparent particles serving as light scattering particles in a resin component.
- the resin used for the blue diffusion layer 151 a conventionally known resin can be used, and is not particularly limited, but a resin having light transmittance is preferable. And in the curable resin composition of 3rd Embodiment mentioned later, it replaces with a quantum dot and it is preferable to add and disperse
- the transparent particles contained in the blue diffusion layer 151 are not particularly limited as long as they can scatter and transmit light from the organic EL part 131.
- the average particle diameter is 25 ⁇ m, and the standard deviation of the particle size distribution is 1 ⁇ m.
- Polystyrene particles or the like can be used.
- the content of the transparent particles in the blue diffusion layer 151 can be appropriately changed and is not particularly limited.
- the organic EL unit 131 corresponds to the corresponding red color.
- the wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151 do not substantially protrude outward.
- the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151 corresponding to each of the color filters 52R, 52G, and 52B are viewed in plan from the color filter side, the red wavelength conversion layer 53R, The green wavelength conversion layer 53G and the blue diffusion layer 151 do not substantially protrude outward from the color filters 52R, 52G, and 52B.
- the color filter is provided on the anti-organic EL element side of each of the wavelength conversion layers 53 ⁇ / b> R and 53 ⁇ / b> G and the blue diffusion layer 151 disposed to face the organic EL unit 131. That is, the color filter is provided above the wavelength conversion unit, and is disposed on the side opposite to the side on which the light source unit including the organic EL unit 131 is disposed with the wavelength conversion unit interposed therebetween.
- the wavelength conversion member 150 has a black matrix 54 formed on the substrate 51 with a light-shielding inorganic material or organic material.
- the black matrix 54 surrounds the color filters 52R, 52G, and 52B in plan view, and also surrounds the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151.
- the black matrix 54 can be formed by patterning according to a known method using a known light-shielding material. Note that the black matrix 54 is not an essential component in the wavelength conversion member 150, and the wavelength conversion member 150 may be configured without the black matrix 54.
- the wavelength conversion member 150 is bonded onto the passivation layer 40 after the wavelength conversion member 150 is formed alone.
- the color filters 52R, 52G, and 52B and the black matrix 54 are sequentially formed on the passivation layer 40, the color filters 52R and 52G are formed.
- 52B and the black matrix 54 can be formed by bonding the substrate 51 on the upper surface.
- the blue light from the organic EL element array 130 is used as excitation light, and the excitation light is converted into red light and green light by the red wavelength conversion layer 53R and the green wavelength conversion layer 53G of the wavelength conversion member 150, respectively. Can be converted to light. Then, the blue light from the organic EL element array 130 can be diffused and emitted by the blue diffusion layer 151.
- the organic EL element 200 converts the red light, the green light, and the blue light emitted from each of the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue diffusion layer 151 of the wavelength conversion member 150 into each color filter. High color purity can be achieved by transmitting 52R, 52G, and 52B.
- the organic EL element 200 when the blue light from the organic EL part 131 of the organic EL element array 130 passes through the red wavelength conversion layer 53R or the green wavelength conversion layer 53G and is emitted without wavelength conversion,
- the color filters 52R and 52G of the wavelength conversion member 150 the wavelength characteristics can be adjusted to assist the red wavelength conversion layer 53R or the green wavelength conversion layer 53G. Then, it is possible to reduce the blue light from the organic EL element array 130 that is transmitted without being wavelength-converted by the red wavelength conversion layer 53R or the green wavelength conversion layer 53G and emitted outside the element.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G are formed of the curable resin composition of the third embodiment of the present invention described later. For this reason, the red wavelength conversion layer 53R and the green wavelength conversion layer 53G exhibit excellent fluorescence characteristics, specifically wavelength conversion efficiency. Further, since it is difficult for a residue to occur when the red wavelength conversion layer 53R and the green wavelength conversion layer 53G are formed, color mixing between pixels due to the occurrence of the residues of the wavelength conversion layers 53R and 53G at an undesired portion is also difficult to occur. . As a result of these, the organic EL element 200 can be used for the configuration of an organic EL device that can easily increase the luminance and display an image with high luminance and high image quality.
- Embodiment 3 FIG. ⁇ Curable resin composition>
- the curable resin composition of the third embodiment of the present invention includes [A] the same or different polymer molecules, (a1) a structural unit containing an acidic group and (a2) an organic group having 4 to 20 carbon atoms.
- a polymer having a structural unit hereinafter also referred to as [A] polymer or simply [A] component
- [B] quantum dots hereinafter also simply referred to as [B] component
- It is a curable resin composition.
- the structural unit (a2) containing the organic group having 4 to 20 carbon atoms of the [A] polymer described above is an organic group having 4 to 20 carbon atoms other than the structural unit containing (a1) an acidic group.
- the constituent unit is preferably included.
- the curable resin composition of the third embodiment of the present invention contains a [A] polymer and is a resin composition suitable for simple formation of a film or layer by coating or the like.
- the curable resin composition of 3rd Embodiment of this invention contains the quantum dot of a [B] component with [A] component, [B] increasing the content of a quantum dot [B]. A good dispersion state of the quantum dots can be realized.
- quantum dots when quantum dots are used together with a resin component, a solvent, or the like to form a composition, they tend to aggregate in the composition, and it is difficult to realize a good dispersion state. In a quantum dot, aggregation will impair its fluorescent properties. Therefore, a composition containing quantum dots usually cannot contain a large amount of quantum dots.
- the [A] component that is a resin component is selected so as to realize a good dispersion state while containing a large amount of [B] quantum dots. Contained.
- the curable resin composition of the third embodiment of the present invention can form a resin composition in which a good dispersion state of [B] quantum dots is realized while containing a large amount of [B] quantum dots. it can.
- the curable resin composition of 3rd Embodiment of this invention forms a layer and a film
- the curable resin composition of the third embodiment of the present invention can have radiation sensitivity. Therefore, the curable resin composition according to the third embodiment of the present invention preferably contains a [C] polymerizable initiator (hereinafter also simply referred to as “C” component), and [D] polymerization. It is preferable to contain a polymerizable unsaturated compound (hereinafter also simply referred to as [D] component). And the curable resin composition of 3rd Embodiment of this invention can be patterned using the photolithographic method etc. based on the radiation sensitivity.
- C polymerizable initiator
- [D] component polymerizable unsaturated compound
- radiation irradiated upon exposure includes visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.
- a so-called resist composition is applied to the surface of a substrate to be processed or processed to form a resist film, and a predetermined resist pattern is exposed by irradiation with light or an electron beam.
- the curable resin composition according to the third embodiment of the present invention can be patterned when necessary to form a cured film patterned into a desired shape. Therefore, the curable resin composition of the third embodiment of the present invention includes a red wavelength conversion layer, a green wavelength, which is a wavelength conversion portion of the wavelength conversion member of the organic EL element of the first embodiment and the second embodiment of the present invention. A conversion layer and a blue wavelength conversion layer can be formed. Each wavelength conversion layer which the wavelength conversion member of the organic EL element of 1st Embodiment of this invention and 2nd Embodiment has is comprised by including [B] quantum dot in resin.
- the curable resin composition of the third embodiment of the present invention contains [A] component and [B] quantum dots.
- the curable resin composition of Embodiment 3 of this invention can form the resin composition in which the favorable dispersion state of [B] quantum dots was implement
- the curable resin composition according to the third embodiment of the present invention uses [B] quantum dots and has an excellent fluorescence emission (wavelength conversion) function (hereinafter referred to as a “wavelength conversion” function).
- the wavelength conversion portion can be formed by forming a wavelength conversion layer having simply fluorescence or fluorescence characteristics.
- the curable resin composition of the third embodiment of the present invention can have radiation sensitivity. Therefore, as described above, the curable resin composition of the third embodiment of the present invention preferably further includes [C] a polymerizable initiator, and further includes [D] a polymerizable unsaturated compound. It is preferable to contain.
- the curable resin composition of 3rd Embodiment of this invention contains an [E] stabilizer (henceforth only [E] component) with [A] component, [B] quantum dot, etc. And a cured film having stable fluorescence characteristics can be formed, and each wavelength conversion layer can be formed.
- curable resin composition of 3rd Embodiment of this invention can contain the other arbitrary component mentioned later, unless the effect of this invention is impaired.
- the curable resin composition of 3rd Embodiment of this invention contains a [A] polymer.
- the polymer has (a1) a structural unit containing an acidic group (hereinafter also simply referred to as the structural unit (a1)) and (a2) 4 carbon atoms in the same or different polymer molecules.
- To 20 hereinafter also simply referred to as a structural unit (a2)
- a structural unit (a2) may have other structural units as necessary.
- the structural unit (a2) of the polymer [A] is preferably a structural unit containing an organic group having 4 to 20 carbon atoms other than the structural unit (a1).
- the mode of the [A] polymer is not particularly limited, (I) When both the structural unit (a1) and the structural unit (a2) are contained in the same polymer molecule, and [A] one polymer molecule is present in the polymer; (Ii) having a structural unit (a1) in one polymer molecule, and having both the structural unit (a2) in a different polymer molecule, and [A] two kinds of structural units in the polymer When polymer molecules are present; (Iii) having both the structural unit (a1) and the structural unit (a2) in one polymer molecule, and having the structural unit (a1) in a polymer molecule different from the structural unit (a1).
- polymer molecule has the structural unit (a2), and [A] three polymer molecules exist in the polymer; (Iv) In addition to the polymer molecules specified in (i) to (iii), there may be mentioned a case where [A] the polymer further contains one or more polymer molecules.
- Examples of the acidic group contained in the structural unit (a1) include a carboxyl group, a phenolic hydroxyl group, and a sulfo group, and a carboxyl group is preferable.
- Examples of the organic group contained in the structural unit (a1) include an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 20 or less carbon atoms, And one or more hydrogen atoms of these aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups are a hydroxyl group, a carboxyl group, a halogen, a nitrile group, an alkoxyl group having 1 to 12 carbon atoms, a mercapto group, And groups substituted with a sulfo group.
- Examples of the aliphatic hydrocarbon group include straight chain such as n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group and n-octadecyl group. And branched alkyl groups such as an alkyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group and 3-hexyl group.
- examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl, a cyclooctyl, a bornyl group, a norbornyl group, an adamantyl group, and the like.
- examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
- an aliphatic hydrocarbon group having 4 to 20 carbon atoms and one or more hydrogen atoms of the aliphatic hydrocarbon group may be a hydroxyl group, a carboxyl group, a halogen, or a nitrile.
- the polymer can be produced by radical copolymerization of a monomer that provides the structural unit (a1), a monomer that provides the structural unit (a2), and a monomer that provides the other structural unit.
- a monomer that provides the structural unit (a1) a monomer that provides the structural unit (a2)
- a monomer that provides the other structural unit a monomer that provides the other structural unit.
- the [A] polymer containing both the structural unit (a1) and the structural unit (a2) in the same polymer molecule at least the monomer that gives the structural unit (a1) and the structural unit (a2) What is necessary is just to copolymerize using the mixture containing the monomer to give.
- the [A] polymer having the structural unit (a1) in one polymer molecule and the structural unit (a2) in a different polymer molecule is produced, at least the structural unit (a1) is included.
- a polymer solution having a structural unit (a1) is obtained by radical polymerization of a polymerizable solution containing a monomer to be given, and a polymerizable solution containing at least a monomer giving a structural unit (a2) is separately radically polymerized.
- the polymer molecule having the structural unit (a2) is obtained, and finally both are mixed to form the [A] polymer.
- the content of the structural unit (a1) in the polymer is such that when the structural unit (a1) and the structural unit (a2) are included in one polymer molecule, [A] all the structural units included in the polymer
- the monomer charge ratio is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
- the structural unit in the one polymer molecule having the structural unit (a1) is preferably 40% by mass to 99% by mass and more preferably 50% by mass to 98% by mass or less as a monomer charge ratio with respect to all the structural units contained in the polymer molecule.
- the content of the structural unit (a2) in the [A] polymer is such that when the structural unit (a1) and the structural unit (a2) are contained in one polymer molecule, 10 mass% or more and 60 mass% or less are preferable by monomer preparation ratio with respect to a structural unit, 15 mass% or more and 55 mass% or less are more preferable, and 20 mass% or more and 50 mass% or less are especially preferable.
- the structural unit in the one polymer molecule having the structural unit (a2) is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass or less, based on the monomer charge ratio with respect to all the structural units contained in the polymer molecule. More preferably, 25 mass% or more and 60 mass% or less are especially preferable.
- the polymer described above is contained in the curable resin composition of the third embodiment of the present invention and dissolved or dispersed.
- the curable resin composition of 3rd Embodiment of this invention contains the quantum dot of the [B] component mentioned later with a [A] component, and increases [B] quantum dot while increasing the content of a [B] quantum dot. A good dispersion state can be realized.
- membrane containing a [B] quantum dot can be formed using simple formation methods, such as application
- the polymer is desirably contained in an amount of 5% by mass or more, more preferably 10% by mass or more, based on the total mass of the curable resin composition. [A] When the polymer is less than 5% by mass in the total mass of the curable resin composition, it is impossible to sufficiently secure the thickness of the coating film obtained from the curable resin composition.
- Quantum dots which are essential components of the curable resin composition of the third embodiment of the present invention, are preferably semiconductor quantum dots configured using a semiconductor material.
- the [B] quantum dot is preferably a quantum dot made of a safe material that does not contain Cd and Pb as constituents, and is composed of, for example, In (indium) or Si (silicon). .
- quantum dots are at least two or more selected from the group of elements represented by Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements.
- a quantum dot made of a compound containing an element is preferable.
- elements such as Pb and Cd which are of great concern for human safety, are excluded, and Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (Barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), C (Carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen), S A quantum dot made of a compound containing at least two elements selected from the group consisting of (sulfur), Se (selenium), Te (tellurium) and Po (polonium) is preferable.
- the [B] quantum dot is preferably composed of a compound (a) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a compound (b) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm.
- the quantum dot is composed of the compound (a) and / or the compound (b) having such fluorescence emission characteristics, so that the quantum dot is fluorescent in the wavelength region of 500 nm to 600 nm and / or in the wavelength region of 600 nm to 700 nm. Can have a maximum.
- the curable resin composition according to the third embodiment of the present invention containing [B] quantum dots can form each wavelength conversion layer in a CCM organic EL element that emits visible light. .
- the above-described first embodiment and second embodiment of the present invention are included by including [B] quantum dots having desired fluorescence emission characteristics.
- Curing resin composition for forming red wavelength conversion layer 53R which is a wavelength conversion part of wavelength conversion members 50 and 150 of organic EL elements 100 and 200 of embodiment, and hardening for forming green wavelength conversion layer 53G It can be used as a curable resin composition or a curable resin composition for forming the blue wavelength conversion layer 53B.
- the [B] quantum dot contained in the curable resin composition of the third embodiment of the present invention is a quantum dot made of a compound containing In as a constituent component.
- [B] quantum dots may include Si or Si compounds.
- Si is particularly preferable among Si or Si compounds.
- the curable resin composition of the third embodiment of the present invention can form a cured film having safer and more excellent fluorescence characteristics. Furthermore, each wavelength conversion which is a wavelength conversion part of the wavelength conversion members 50 and 150 of the organic EL elements 100 and 200 of the first embodiment and the second embodiment of the present invention, which is safe and has superior fluorescence characteristics. Layers 53R, 53G, and 53B can be formed.
- Quantum dots contained in the curable resin composition of the third embodiment of the present invention are selected from a homogeneous structure type composed of one compound and a core-shell structure type composed of two or more compounds. It is preferable that the quantum dots have at least one structure type.
- the core-shell structure type [B] quantum dots are formed by forming a core structure with one kind of compound and covering the periphery of the core structure with another compound. For example, by covering the core semiconductor with a semiconductor having a larger energy band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the quantum dots is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of [B] quantum dots are improved.
- Quantum dots contained in the curable resin composition of the third embodiment of the present invention are InP / ZnS, CuInS 2 / ZnS, which are core-shell structured quantum dots, in consideration of the component configuration and structure, and It is preferably at least one selected from the group consisting of (ZnS / AgInS 2 ) solid solution / ZnS, and AgInS 2 which is a homogeneous structure type quantum dot and Zn-doped AgInS 2 .
- [B] quantum dots contained in the curable resin composition of the third embodiment of the present invention are InP / ZnS compound, CuInS 2 / ZnS compound, AgInS 2 compound, (ZnS / AgInS 2 ) solid solution / It is preferably at least one selected from the group consisting of ZnS compounds, Zn-doped AgInS 2 compounds and Si compounds.
- the curable resin composition according to the third embodiment of the present invention containing the [B] quantum dots exemplified above can form a cured film that is safe and has excellent fluorescence characteristics.
- each wavelength conversion layer which is a wavelength conversion part of the wavelength conversion member of the organic EL element of 1st Embodiment and 2nd Embodiment of this invention provided with the outstanding fluorescence characteristic can be formed.
- the [B] quantum dots contained in the curable resin composition of the third embodiment of the present invention preferably have an average particle size of 0.5 nm to 20 nm, and preferably 1.0 nm to 10 nm. More preferred.
- the average particle size is less than 0.5 nm, it is difficult to prepare [B] quantum dots, and even if it can be prepared, the fluorescence characteristics of [B] quantum dots may become unstable.
- the average particle diameter of the quantum dots exceeds 20 nm, the quantum confinement effect due to the size of the quantum dots may not be obtained, and the desired fluorescence characteristics cannot be obtained, which is not desirable.
- the shape of the quantum dots is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disk shape, or other shapes.
- Information such as the particle size, shape, and dispersion state of the quantum dots can be obtained by a transmission electron microscope (TEM).
- a known method of thermally decomposing an organometallic compound in a coordinating organic solvent may be used. it can.
- core-shell type quantum dots form a homogeneous core structure by reaction, then add a precursor to form a shell on the core surface in the reaction system, and stop the reaction after shell formation. It can be obtained by separating from a solvent.
- a commercially available product can also be used.
- the content of [B] quantum dots in the curable resin composition of the third embodiment of the present invention is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned [A] component. More preferably, it is 0.2 to 50 parts by mass.
- [B] By setting the content of quantum dots in the above range, a cured film having excellent fluorescence characteristics is formed, and as a result, each wavelength that is a wavelength conversion part of a wavelength conversion member having excellent fluorescence characteristics A conversion layer can be formed.
- the content of the quantum dots is less than 0.1 parts by mass with respect to 100 parts by mass of the [A] component, the desired fluorescent properties cannot be obtained in the cured film to be formed.
- the wavelength conversion layer of the wavelength conversion member having the characteristics cannot be formed.
- the stability of the cured film formed will be impaired and in the organic EL element, each stable wavelength conversion layer cannot be formed.
- the curable resin composition of the third embodiment of the present invention can further contain a [C] polymerization initiator.
- the [C] polymerization initiator of this embodiment is preferably one that generates an active species that can initiate polymerization of a compound having a polymerizable group in response to radiation. Therefore, the [C] polymerization initiator of this embodiment is preferably a radiation-sensitive polymerization initiator, that is, a radiation-sensitive polymerization initiator.
- the curable resin composition of 3rd Embodiment of this invention can improve radiation sensitivity and can improve patternability by containing a [C] polymerization initiator. And the curable resin composition of 3rd Embodiment of this invention can form the cured film patterned using well-known patterning methods, such as the photolithographic method, The wavelength conversion member of an organic EL element It is possible to easily form each wavelength conversion layer that is the wavelength conversion part.
- [C] The polymerization initiator is used together with the [D] polymerizable unsaturated compound described later, and is preferably contained in the curable resin composition of the third embodiment of the present invention. Thereby, the curable resin composition of the third embodiment of the present invention can further improve the cross-linking reactivity, the strength of each wavelength conversion layer of the wavelength conversion member formed from this curable resin composition, and Adhesion with the substrate can be further enhanced.
- examples of the [C] polymerization initiator include oxime ester compounds, acetophenone compounds, biimidazole compounds, and the like. In addition, you may use [C] polymerization initiator individually or in combination of 2 or more types.
- oxime ester compound examples include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2-octane.
- acetophenone compound examples include ⁇ -aminoketone compounds.
- Examples of the ⁇ -aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.
- the acetophenone compound is preferably an ⁇ -aminoketone compound, such as 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is more preferred.
- biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole and the like.
- a commercially available product may be used as the polymerization initiator.
- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure (registered trademark) 907)
- 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379)
- 1,2-octanedione-1- [4- ( Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01)
- ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure (registered trademark) OXE02) (manufactured by BASF Japan Ltd.).
- the [C] polymerization initiator is preferably a polymerization initiator having no nitrogen atom in the molecule.
- the curable resin composition of the third embodiment of the present invention can easily form a wavelength conversion layer of an organic EL device having better fluorescence characteristics. Can be formed.
- Such a polymerization initiator having no nitrogen atom in the molecule include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651), 1- Hydroxycyclohexyl phenyl ketone (Irgacure® 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure® 1173), 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure® 2959), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] phenyl ⁇ -2-methyl-propan-1-one (Irgacure® 127), phenylglyoxyl Acid methyl ester (Darocur® MBF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine
- the content of the polymerization initiator is preferably 0.1 part by mass to 40 parts by mass, and more preferably 0.5 part by mass to 20 parts by mass with respect to 100 parts by mass of the component [A].
- the curable resin composition of the third embodiment of the present invention exhibits good patternability even in the case of a low exposure amount, and has a sufficient surface.
- a cured film having hardness and adhesion can be formed to provide a wavelength conversion layer of the organic EL element.
- the curable resin composition of the third embodiment of the present invention may further contain a [D] polymerizable unsaturated compound.
- the [D] polymerizable unsaturated compound contained in the curable resin composition of the third embodiment of the present invention is a compound having a polymerizable unsaturated structure. Crosslinking reactivity can be improved because the curable resin composition of 3rd Embodiment of this invention contains a [D] polymerizable unsaturated compound.
- each wavelength conversion layer which is a wavelength conversion part of the wavelength conversion member of the organic EL element of 1st Embodiment and 2nd Embodiment of this invention formed from this curable resin composition, intensity
- the [D] polymerizable unsaturated compound is preferably used together with the above-described [C] polymerization initiator and contained in the curable resin composition of the third embodiment of the present invention.
- Such a [D] polymerizable unsaturated compound is a monofunctional, bifunctional, or trifunctional (meth) acrylic acid ester from the viewpoint of good polymerizability and improved strength of the resulting cured film. Is preferred.
- Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxy Propyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ⁇ -carboxypolycaprolactone monoacrylate.
- bifunctional (meth) acrylic acid ester examples include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol.
- Examples include dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate.
- Examples of commercially available products include Aronix (registered trademark) M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) HDDA, HX-220, R-604. (Nippon Kayaku Co., Ltd.); Biscoat 260, 312, and 335HP (Osaka Organic Chemical Co., Ltd.); Light acrylate (registered trademark) 1,9-NDA (Kyoeisha Chemical Co., Ltd.) and the like.
- tri- or more functional (meth) acrylic acid ester examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and ditrimethylolpropane.
- tri (2-acryloyloxyethyl) phosphate tri (2-methacryloyloxyethyl) phosphate
- succinic acid-modified pentaerythritol triacrylate succinic acid-modified dipentaerythritol pentaacrylate
- Examples of commercially available products include Aronix (registered trademark) M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, and TO-1450. (Above, manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120, DPEA-12 (above, Nippon Kayaku Co., Ltd.) ); Biscoat (registered trademark) 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier (Registered Trademark) R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (Registered Trademark) DPHA-40H (Nippon Kayaku Co., Ltd.),
- the polymerizable unsaturated compound described above may be used alone or in combination of two or more.
- the proportion of the [D] polymerizable unsaturated compound used in the curable resin composition of the third embodiment of the present invention is preferably 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the component [A]. More preferred is 200 to 200 parts by weight.
- the curable resin composition of the third embodiment of the present invention can further contain an [E] stabilizer.
- the curable resin composition of the third embodiment of the present invention is obtained by using an [E] stabilizer in addition to the essential components such as the [A] component and the [B] component.
- the light conversion efficiency can be improved.
- a stabilizer [E] preferable as a component of the curable resin composition of the third embodiment of the present invention includes a phosphite antioxidant.
- the phosphite antioxidant comprises a compound having a phosphite structure.
- examples of the [E] stabilizer include a phosphine compound, a phenol compound, a compound having a hindered phenol structure, a compound having a hindered amine structure, and a compound having a thioether structure.
- phosphite antioxidants include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester.
- Phosphorous acid bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol-di-phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and the like.
- ADK STAB registered trademark
- PEP-36 Examples of commercially available products include ADK STAB (registered trademark) PEP-36, PEP-4C, PEP-8, PEP-8F, PEP-8W, PEP-11C, PEP-24G, and HP-10.
- ADK STAB registered trademark
- P Examples of commercially available products include ADK STAB (registered trademark) PEP-36, PEP-4C, PEP-8, PEP-8F, PEP-8W, PEP-11C, PEP-24G, and HP-10.
- 2112, 260 ADK STAB (registered trademark) P, ADK STAB (registered trademark) QL, 522A, 329K, 1178, 1500
- ADK STAB (registered trademark) C, 135A, 3010 Examples of commercially available products include ADK STAB (registered trademark) ) TPP (above, manufactured by Adeka), Irgafos (registered trademark) 38, Irgafos (registered
- Examples of the phosphine compound include triphenylphosphine, cyclohexyldiphenylphosphine, ethyldiphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and tris (2,5-dimethyl). Phenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, and the like. Examples of commercially available products include TPP, DPCP, TOTP, TMTP, TPTP (all of which are manufactured by Hokuko Chemical Co., Ltd.). Of these, aromatic phosphite antioxidants or phosphine compounds represented by the following formula are particularly preferred.
- R A represents a single bond or an oxygen atom.
- R B represents an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, or a naphthyl group.
- R C represents a hydrocarbon group having 1 to 30 carbon atoms. n represents an integer of 1 to 3, and m represents an integer of 0 to 5.
- R B in the above formula methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group, naphthyl group and the like.
- R C in the above formula methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, Eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl
- Examples of the above-mentioned phenol compound include 4-methoxyphenol, 4-ethoxyphenol, and the like.
- Examples of the compound having a hindered phenol structure described above include 2,6-di-tert-butyl-4-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl).
- Examples of commercially available compounds having the above hindered phenol structure include ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, and AO-70. , AO-80, AO-330 (manufactured by Adeka), sumilizer (registered trademark) GM, GS, MDP-S, BBM-S, WX-R, GA-80 (and above) Manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD (Registered trademark) 295 (above, manufactured by BASF Japan), Yoshinox (registered trademark) BHT, BB, 2246G, 425, 250, 930, the SS, the TT, the 917, the 314 (or, API Corporation Co., Ltd.
- Examples of commercially available compounds having a hindered amine structure include ADK STAB (registered trademark) LA-52, LA57, LA-62, LA-67, LA-63P, LA-68LD, LA-77, LA-82, LA-87 (manufactured by Adeka), sumilizer (registered trademark) 9A (manufactured by Sumitomo Chemical), CHIMASSORB (registered trademark) 119FL, 2020FDL, 944FDL, TINUVIN (registered trademark) 622LD 144, 765, and 770DF (manufactured by BASF Japan Ltd.).
- Adekastab registered trademark
- AO-412S manufactured by Adeka
- sumilizer registered trademark
- TPL-R manufactured by Adeka
- TPM manufactured by TPM
- TPS TP-D
- MB above, manufactured by Sumitomo Chemical Co., Ltd.
- IRGANOX registered trademark
- PS800FD PS802FD
- DLTP DLTP
- DSTP DSTP
- DMTP DMTP
- DTTP aboveve, manufactured by API Corporation
- [E] stabilizers may be used alone or in admixture of two or more.
- the content of [E] stabilizer in the curable resin composition of the third embodiment of the present invention is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of [A] component. Is 0.2 to 5 parts by mass.
- the organic EL device of the first embodiment and the second embodiment of the present invention obtained from the curable resin composition of the third embodiment of the present invention is used. In each wavelength conversion layer that is a wavelength conversion unit, the light conversion efficiency can be further improved.
- the curable resin composition of the third embodiment of the present invention contains the [A] component and [B] quantum dots as essential components, and contains other optional components as long as the effects of the present invention are not impaired. be able to.
- other optional components include a solvent, a curing accelerator, and a thermal acid generator.
- the curing accelerator is a compound that functions to accelerate the curing of the film formed by the curable resin composition of the present embodiment.
- the thermal acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when the resin is cured by applying heat.
- the curable resin composition of the third embodiment of the present invention is a range that does not impair the effects of the present invention, such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver.
- a surfactant such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium
- the curable resin composition of the third embodiment of the present invention is prepared by uniformly mixing the [A] polymer and [B] quantum dots.
- the optional [C] component, [D] component, and [E] component are included, the [C] component and [D] as necessary together with the [A] component and [B] component It is prepared by mixing the components and [E] component uniformly.
- an organic solvent can be used to prepare a curable resin composition in a dispersion state.
- the organic solvent for example, by adjusting the viscosity of the curable resin composition of the third embodiment of the present invention, it is possible to improve applicability to a substrate, etc., and improve operability and moldability. For example.
- organic solvent examples include those that dissolve or disperse other components and that do not react with other components.
- organic solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propio.
- examples include nates, hydrocarbons, ketones, and esters.
- Examples of alcohols include benzyl alcohol and diacetone alcohol;
- Examples of ethers include tetrahydrofuran, dialkyl ethers such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
- Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
- Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
- Examples of propylene glycol monoalkyl ethers include propylene
- a hydrocarbon solvent is preferred from the viewpoint of the dispersibility of the quantum dots.
- the hydrocarbon include an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent.
- the aromatic hydrocarbon solvent include toluene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cymene, tetralin, biphenyl, mesitylene and the like.
- Aliphatic hydrocarbon solvents include hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, pinane, decalin, isooctane, isododecane, cyclohexene, cyclopentane, dipentene, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M (manufactured by Kokura Kosan), turpentine oil, decahydronaphthalene, limonene, ⁇ -pinene, ⁇ -pinene, benzine, Kyowasol C-800, shell sol , Isosol, ligroin (manufactured by Gordo Kogyo Co., Ltd.), and the like.
- ethers such as dialkyl ethers, diethylene glycol alkyl ethers, ethylene glycol from the viewpoint of excellent solubility, non-reactivity with each component, and ease of film formation.
- Alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Tyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate
- High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate can be used in combination.
- the content of the organic solvent in the curable resin composition of the third embodiment of the present invention can be appropriately determined in consideration of viscosity and the like. That is, the solid content concentration of the curable resin composition of the present embodiment (components other than the solvent component in the curable resin composition solution) can be arbitrarily set according to the purpose of use, desired film thickness, and the like. However, it is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 15% by mass to 35% by mass.
- each wavelength conversion layer which is a wavelength conversion part of the organic EL element of a form.
- Embodiment 4 FIG. ⁇ Method for forming wavelength conversion section>
- the wavelength conversion unit obtained by the wavelength conversion unit forming method of the fourth embodiment of the present invention includes, for example, the organic EL element 100 of the first embodiment of the present invention shown in FIGS. 1 and 2 and the second of the present invention. It is a wavelength conversion part of the wavelength conversion members 50 and 150 of the organic EL element 200 of the embodiment, and specifically, the wavelength conversion layers 53R, 53G, and 53B.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G included in the wavelength conversion member 150 of the organic EL element 200 according to the second embodiment of the present invention shown in FIG. Can be formed.
- the curable resin composition of the third embodiment of the present invention described above is applied onto a base material, patterned as necessary, and then exposed. Curing is performed to form a patterned cured film. And the obtained cured film can be made into the wavelength conversion part which the wavelength conversion member of the organic EL element of 1st Embodiment of this invention and 2nd Embodiment has, More specifically, each wavelength conversion layer It can be.
- the substrate as shown in FIGS. 1 and 2, a substrate having red color filters 52R, green color filters 52G, and blue color filters 52B regularly arranged on the substrate 51 is used. be able to.
- the following steps (1) to (step) are performed so that the wavelength converter having a desired shape and arrangement is formed on the base material. It is preferable to include (4) in the following order.
- the coating film formation process which forms the coating film of the curable resin composition of 3rd Embodiment of this invention on a base material.
- a radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
- FIGS. 3 to 6 are diagrams for explaining an example of the method of forming the wavelength conversion unit according to the fourth embodiment of the present invention.
- FIG. 3 is a cross-sectional view of a base material for explaining an example of a coating film forming step in the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention.
- FIG. 4 is a cross-sectional view schematically illustrating an example of a radiation irradiation step in the method for forming a wavelength conversion unit according to the fourth embodiment of the present invention.
- FIG. 5 is a cross-sectional view of a substrate for explaining an example of a developing process in the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention.
- FIG. 6 is a cross-sectional view of a cured film and a substrate for explaining an example of a curing process in the method for forming a wavelength conversion portion of the fourth embodiment of the present invention.
- the base material 2 in FIGS. 3 to 6 has the red color filter 52R, the green color filter 52G, and the blue color filter 52B regularly arranged on the substrate 51 as described above. 3 to 6, the red color filter 52R, the green color filter 52G, and the blue color filter 52B are not shown and are shown as the base material 2 for convenience.
- step (1) coating film forming step
- step (4) curing step
- Step (1) In the coating film forming step, which is the step (1) of the method for forming the wavelength conversion portion of the fourth embodiment of the present invention, as illustrated in FIG. 3, the curable resin composition of the third embodiment of the present invention A coating film 1 is formed on the substrate 2.
- the curable resin composition described above contains selected and selected quantum dots that convert excitation light into red light. Yes.
- the curable resin composition described above contains selected and contained quantum dots that convert excitation light into green light, thereby forming the blue wavelength conversion layer 53B. In this case, a quantum dot that converts excitation light into blue light is selected and contained in the curable resin composition described above.
- the red wavelength conversion layer, the green wavelength conversion layer, and the blue wavelength conversion layer of the wavelength conversion member of the organic EL element are to be formed, different emission characteristics are obtained.
- three types of curable resin compositions of the third embodiment are prepared.
- the method for forming the wavelength conversion section of the fourth embodiment of the present invention including the above-described steps (1) to (4) is repeated, so that the red wavelength conversion layer and the green wavelength conversion layer are formed on one substrate.
- the blue wavelength conversion layer can be formed sequentially.
- each wavelength conversion layer can be formed on one base material, a wavelength conversion part can be comprised, and the wavelength conversion member of an organic EL element can be obtained.
- the base material 2 on which the coating film 1 is formed regularly arranges the red color filter 52R, the green color filter 52G, and the blue color filter 52B on the substrate 51 of FIG. Have.
- the substrate 51 glass, quartz, silicon, or resin (for example, polyimide, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyester, cyclic olefin ring-opening polymer and hydrogen thereof)
- a substrate made of an additive or the like can be used.
- these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.
- the base material 2 after applying the curable resin composition of 3rd Embodiment of this invention to one surface, it prebakes and components, such as the organic solvent contained in the curable resin composition, evaporate. Then, the coating film 1 is formed.
- Examples of the coating method of the curable resin composition of the third embodiment of the present invention in this step include a spray method, a roll coating method, and a spin coating method (sometimes referred to as a spin coating method or a spinner method).
- An appropriate method such as a slit coating method (slit die coating method), a bar coating method, or an ink jet coating method can be employed.
- the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.
- the pre-baking conditions described above vary depending on the type of each component constituting the curable resin composition, the blending ratio, etc., but it is preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is heated by a hot plate, oven, or the like. Although it varies depending on the apparatus, it is about 1 to 15 minutes.
- Step (2) Next, in the radiation irradiation step, which is the step (2) of the method for forming the wavelength conversion part of the fourth embodiment of the present invention, as illustrated in FIG. 4, the step was formed on the substrate 2 in the step (1).
- Radiation 4 is applied to at least a part of the coating film 1.
- the photomask 3 having a pattern corresponding to formation of a desired shape.
- a part of the irradiated radiation 4 passes through the photomask, and a part of the radiation 4 a is irradiated onto the coating film 1.
- Examples of the radiation 4 used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.
- the dose of radiation 4 (exposure amount), the intensity at the wavelength 365nm radiation 4 as a value measured by a luminometer (OAI model 356, Optical Associates Ltd. Inc.), be 10J / m 2 ⁇ 10000J / m 2 can be preferably 100J / m 2 ⁇ 5000J / m 2, 200J / m 2 ⁇ 3000J / m 2 is more preferable.
- Step (3) Next, in the development step, which is the step (3) of the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention, as illustrated in FIG. Then, unnecessary portions are removed, and the coating film 1a patterned into a predetermined shape is obtained.
- Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, and tetramethylammonium hydroxide and tetraethylammonium hydroxide.
- An aqueous solution of an alkaline compound such as a quaternary ammonium salt, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene Can be used.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above.
- the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent.
- the developing method may be any of a liquid piling method, a dipping method, a shower method, a spray method, and the like.
- the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Following the development treatment, for example, washing with running water is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen to obtain the coating film 1a patterned into a predetermined shape.
- Step (4) Next, in the curing step, which is the step (4) of the method for forming the wavelength conversion portion of the fourth embodiment of the present invention, the patterned coating film 1a illustrated in FIG. 5 is exposed by exposure using an exposure apparatus. Curing (also called post exposure). Thereby, the cured film 5 formed on the base material 2 is obtained as illustrated in FIG. The cured film 5 is patterned by the above process so as to have a desired shape.
- the cured film 5 is formed using the curable resin composition of the third embodiment of the present invention described above. Irradiate part of the film. Specifically, the coating film formed in step (1) and patterned in step (2) and step (3) is irradiated with predetermined radiation. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
- Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like.
- Examples of the far ultraviolet light include KrF excimer laser light.
- Examples of X-rays include synchrotron radiation.
- Examples of the charged particle beam include an electron beam.
- ultraviolet rays are preferably used, and among these ultraviolet rays, radiation containing at least one of g-line, h-line and i-line is more preferable.
- the exposure dose of radiation is preferably 0.1 J / m 2 to 30000 J / m 2 .
- the cured film formed by the above steps (1) to (4) includes [B] quantum dots in the resin component, and has a fluorescence emission (wavelength conversion) function based on [B] quantum dots. . Therefore, the formed cured film includes the red wavelength conversion layer 53R, the green wavelength conversion layer 53G, and the blue color that the wavelength conversion member 50 of the organic EL element 100 according to the first embodiment of the present invention illustrated in FIGS. 1 and 2 has.
- the red wavelength conversion layer 53R and the green wavelength conversion layer 53G included in the wavelength conversion layer 53B and the wavelength conversion member 150 of the organic EL element 200 of the second embodiment can be configured.
- the wavelength included in the wavelength conversion members 50 and 150 of the organic EL elements 100 and 200 of the first embodiment and the second embodiment of the present invention is different from the excitation light.
- the wavelength conversion layers 53R, 53G, and 53B can be formed as a wavelength conversion unit that emits the fluorescence.
- the cured film formed by the steps (1) to (4) has a total light transmittance (thickness of 0.1 mm) in the resin constituting the cured film so that the light use efficiency can be increased.
- JIS K7105 is preferably 75% to 95%, more preferably 78% to 95%, still more preferably 80% to 95%. If the total light transmittance is in such a range, the obtained cured film can form the wavelength conversion layers 53R, 53G, and 53B with excellent light utilization efficiency, and can constitute a wavelength conversion unit.
- Synthesis example 1 [Synthesis of Polymer (A-1)] A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heating to 80 ° C., at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of 2-methacryloyloxyethyl succinic acid, 10 parts by mass of benzyl methacrylate, 60 parts by mass of 2-ethylhexyl methacrylate and 2,2 ′ A mixed solution of 6 parts by mass of azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature.
- azobis 2,4-dimethylvaleronitrile
- the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-1).
- Quantum dot A InP / ZnS core-shell quantum dot
- quantum dot A InP / ZnS core-shell type quantum dot used in the following examples can be synthesized by a generally known method.
- quantum dots A InP / ZnS core-shell quantum dots can be synthesized by referring to the method described in the technical document “Journal of American Chemical Society. 2007, 129, 15432-15433”.
- Example 1 [Preparation of Curable Resin Composition ( ⁇ -I)] After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-1) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and 1,2-octanedione-1 -[4- (Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF Japan Ltd.) 10 parts by mass and 70 parts by mass of 1,9-nonanediol diacrylate were mixed and cured. A resin composition ( ⁇ -I) was prepared.
- Example 2 [Formation of cured film using curable resin composition ( ⁇ -I)]
- the curable resin composition ( ⁇ -I) prepared in Example 1 was applied onto an alkali-free glass substrate with a spinner and then pre-baked on an 80 ° C. hot plate for 2 minutes to form a coating film.
- the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed. As a result, the patternability of the cured film formed by patterning using the curable resin composition ( ⁇ -I) was good.
- Example 3 Evaluation of fluorescence characteristics
- the cured film obtained by the formation method of Example 2 was further examined for fluorescence quantum yield at 25 ° C. using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics).
- the fluorescence quantum yield was 38%, and the fluorescence characteristics were judged to be good. Therefore, the cured film by the forming method of Example 2 contains quantum dots.
- the cured film by the formation method of Example 2 is applied to an organic EL element, and a red wavelength conversion layer can be formed as a wavelength conversion part of the wavelength conversion member, thereby increasing the brightness of the organic EL element. Can be realized.
- the cured film formed using the curable resin composition of the present invention has excellent fluorescence characteristics and is easy to pattern. Therefore, it can utilize also in the field
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Abstract
Description
本発明は、有機EL素子、硬化性樹脂組成物、波長変換部の形成方法および有機EL装置に関する。 The present invention relates to an organic EL element, a curable resin composition, a method for forming a wavelength conversion unit, and an organic EL device.
電子を3次元的に閉じ込めることができる極小さな粒(ドット)は量子ドットと称され、近年注目を集めている。1粒の量子ドットの大きさは、直径数ナノメートル(nm)から数10ナノメートル(nm)である。 The extremely small particles (dots) that can confine electrons three-dimensionally are called quantum dots and have attracted attention in recent years. The size of one quantum dot is several nanometers (nm) to several tens of nanometers (nm) in diameter.
量子ドットは、そのサイズを変えるとエネルギーバンドギャップも変わって、励起状態から基底状態に遷移するときに生じる蛍光の色(波長)が変わるため、波長変換材料としての有機EL素子への適用、特に、有機EL素子を用いた有機EL表示装置への適用が検討されている(特許文献1~特許文献3を参照のこと。)。
When quantum dots change their size, the energy band gap also changes, and the color (wavelength) of fluorescence generated when transitioning from the excited state to the ground state changes. Therefore, application to organic EL elements as wavelength conversion materials, especially Application to an organic EL display device using an organic EL element has been studied (see
波長変換材料として量子ドットを含む波長変換(色変換)部を、例えば、有機EL素子に適用する場合、優れた輝度特性の実現が求められる。そのため、例えば、層状または膜状に形成された波長変換部において量子ドットの含有量を多くすることが望まれる。しかしながら、量子ドットを含む波長変換部の場合、パターニング性が低下することが問題となる。 When a wavelength conversion (color conversion) part including quantum dots as a wavelength conversion material is applied to, for example, an organic EL element, it is required to realize excellent luminance characteristics. Therefore, for example, it is desired to increase the content of quantum dots in the wavelength conversion section formed in a layered or film shape. However, in the case of a wavelength conversion unit including quantum dots, there is a problem that patterning properties are deteriorated.
例えば、有機EL素子を用いて表示装置を構成する場合、表示の画素サイズに応じたサイズの波長変換部を形成するか、または所望サイズのストライプ状に波長変換部をパターニングすることが求められる。 For example, when a display device is configured using an organic EL element, it is required to form a wavelength conversion unit having a size corresponding to a display pixel size or pattern the wavelength conversion unit in a stripe shape having a desired size.
しかしながら、量子ドットの含有量を高めた場合、パターニングを行って波長変換部を形成するときに、不所望の箇所に残渣が生じ易くなる。そして、不所望の箇所に波長変換部の残渣が生じると、有機EL素子を用いて表示装置を構成する場合、その駆動時に残渣中の量子ドットからも蛍光が生じて画素間で混色が起こり、表示特性が低下する。 However, when the content of the quantum dots is increased, when patterning is performed to form the wavelength conversion part, a residue is likely to occur at an undesired location. And when the residue of a wavelength conversion part arises in an undesired part, when comprising a display device using an organic EL element, fluorescence will arise also from the quantum dot in a residue at the time of the drive, and color mixing will occur between pixels, Display characteristics deteriorate.
本発明は、上記の問題に鑑みてなされたものである。すなわち、本発明の目的は、量子ドットを含む波長変換部を有してそのパターニング性の低下を抑え、輝度を高め易い有機EL素子を提供することにある。 The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an organic EL element that has a wavelength conversion unit including quantum dots, suppresses a decrease in patterning property, and easily increases luminance.
また、本発明の他の目的は、量子ドットを含み、優れた蛍光特性とパターニング性を示す硬化膜を形成して有機EL素子の波長変換部を提供する硬化性樹脂組成物を提供することにある。 Another object of the present invention is to provide a curable resin composition that includes a quantum dot and provides a wavelength conversion part of an organic EL device by forming a cured film that exhibits excellent fluorescence characteristics and patterning properties. is there.
また、本発明のさらに他の目的は、蛍光特性に優れた波長変換部を有機EL素子の所望箇所に形成する波長変換部の形成方法を提供することにある。 Still another object of the present invention is to provide a method for forming a wavelength conversion part that forms a wavelength conversion part having excellent fluorescence characteristics at a desired location of an organic EL element.
また、本発明のさらに他の目的は、高輝度で画質に優れた画像表示を行い易い有機EL装置を提供することにある。 Still another object of the present invention is to provide an organic EL device that can easily display an image with high luminance and excellent image quality.
本発明の他の目的および利点は、以下の記載から明らかとなるであろう。 Other objects and advantages of the present invention will become apparent from the following description.
本発明の第1の態様は、発光部と波長変換部とを有する有機EL素子であって、
前記波長変換部が、
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)上記(a1)以外の炭素数4~20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物を用いて形成されたものであることを特徴とする有機EL素子に関する。
A first aspect of the present invention is an organic EL element having a light emitting part and a wavelength converting part,
The wavelength converter is
[A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms other than (a1) in the same or different polymer molecules, and [B] The present invention relates to an organic EL device characterized by being formed using a curable resin composition containing quantum dots.
本発明の第1の態様において、[B]量子ドットが、2族元素、11族元素、12族元素、13族元素、14族元素、15族元素および16族元素よりなる群から選ばれる少なくとも2種の元素を含む化合物からなることが好ましい。
In the first aspect of the present invention, the [B] quantum dot is at least selected from the group consisting of a
本発明の第1の態様において、[B]量子ドットが、Inを構成成分として含む化合物からなることが好ましい。 In the first aspect of the present invention, it is preferable that the [B] quantum dot is made of a compound containing In as a constituent component.
本発明の第1の態様において、[B]量子ドットが、InP/ZnS化合物、CuInS2/ZnS化合物、AgInS2化合物、(ZnS/AgInS2)固溶体/ZnS化合物、ZnドープAgInS2化合物およびSi化合物よりなる群から選ばれる少なくとも1種であることが好ましい。 In the first aspect of the present invention, the [B] quantum dot comprises an InP / ZnS compound, a CuInS 2 / ZnS compound, an AgInS 2 compound, a (ZnS / AgInS 2 ) solid solution / ZnS compound, a Zn-doped AgInS 2 compound, and an Si compound. It is preferably at least one selected from the group consisting of:
本発明の第1の態様において、さらに、カラーフィルタを有することが好ましい。 In the first aspect of the present invention, it is preferable to further include a color filter.
本発明の第2の態様は、
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)炭素数4~20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物であって、
本発明の第1の態様の有機EL素子の前記波長変換部の形成に用いられることを特徴とする硬化性樹脂組成物に関する。
The second aspect of the present invention is:
[A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms in the same or different polymer molecules, and [B] a quantum dot A curable resin composition containing,
The present invention relates to a curable resin composition that is used for forming the wavelength conversion part of the organic EL device according to the first aspect of the present invention.
本発明の第2の態様において、[B]量子ドットが、2族元素、11族元素、12族元素、13族元素、14族元素、15族元素および16族元素よりなる群から選ばれる少なくとも2種の元素を含む化合物からなることが好ましい。
In the second aspect of the present invention, the [B] quantum dot is at least selected from the group consisting of a
本発明の第2の態様において、[B]量子ドットが、Inを構成成分として含む化合物からなることが好ましい。 In the second aspect of the present invention, it is preferable that the [B] quantum dot is made of a compound containing In as a constituent component.
本発明の第2の態様において、[B]量子ドットが、InP/ZnS化合物、CuInS2/ZnS化合物、AgInS2化合物、(ZnS/AgInS2)固溶体/ZnS化合物、ZnドープAgInS2化合物およびSi化合物よりなる群から選ばれる少なくとも1種であることが好ましい。 In the second aspect of the present invention, the [B] quantum dot comprises an InP / ZnS compound, a CuInS 2 / ZnS compound, an AgInS 2 compound, a (ZnS / AgInS 2 ) solid solution / ZnS compound, a Zn-doped AgInS 2 compound, and an Si compound. It is preferably at least one selected from the group consisting of:
本発明の第3の態様は、少なくとも青色の光を含んで発する光源部と波長変換部とを有する有機EL素子の該波長変換部を形成する波長変換部の形成方法であって、
(1)本発明の第2の態様の硬化性樹脂組成物の塗膜を基材上に形成する工程、
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する工程、
(3)工程(2)で放射線を照射された塗膜を現像する工程、および
(4)工程(3)で現像された塗膜を露光する工程
を有することを特徴とする波長変換部の形成方法に関する。
A third aspect of the present invention is a method of forming a wavelength conversion unit that forms the wavelength conversion unit of an organic EL element having a light source unit that emits light containing at least blue light and a wavelength conversion unit,
(1) The process of forming the coating film of the curable resin composition of the 2nd aspect of this invention on a base material,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) The step of developing the coating film irradiated with radiation in the step (2), and (4) The step of exposing the coating film developed in the step (3). Regarding the method.
本発明の第4の態様は、本発明の第1の態様の有機EL素子を含んで構成され、画像表示に用いられることを特徴とする有機EL装置に関する。 The fourth aspect of the present invention relates to an organic EL device comprising the organic EL element of the first aspect of the present invention and used for image display.
本発明の第1の態様によれば、量子ドットを含む波長変換部を有してそのパターニング性の低下を抑え、輝度を高め易い有機EL素子が提供される。 According to the first aspect of the present invention, there is provided an organic EL element that has a wavelength conversion unit including quantum dots and suppresses a decrease in patterning property and easily increases luminance.
また、本発明の第2の態様によれば、量子ドットを含み、優れた蛍光特性とパターニング性を示す硬化膜を形成して有機EL素子の波長変換部を提供する硬化性樹脂組成物が提供される。 In addition, according to the second aspect of the present invention, there is provided a curable resin composition that provides a wavelength conversion part of an organic EL element by forming a cured film that includes quantum dots and exhibits excellent fluorescence characteristics and patterning properties. Is done.
また、本発明の第3の態様によれば、蛍光特性に優れた波長変換部を有機EL素子の所望箇所に形成する波長変換部の形成方法が提供される。 Also, according to the third aspect of the present invention, there is provided a method for forming a wavelength conversion unit that forms a wavelength conversion unit with excellent fluorescence characteristics at a desired location of an organic EL element.
さらに、本発明の第4の態様によれば、高輝度で画質に優れた画像表示を行い易い有機EL装置が提供される。 Furthermore, according to the fourth aspect of the present invention, there is provided an organic EL device that can easily display an image with high luminance and excellent image quality.
実施の形態1.
<有機EL素子(1)>
図1は、本発明の第1実施形態の有機EL素子を概略的に示す断面図である。
<Organic EL element (1)>
FIG. 1 is a cross-sectional view schematically showing an organic EL element according to the first embodiment of the present invention.
図1に示す有機EL素子100は、画素回路が形成された基板である回路基板10と、回路基板10上に形成された第2平坦化膜20と、第2平坦化膜20上に複数行複数列に亘って配置された複数の有機EL部31からなる有機EL素子アレイ30と、有機EL素子アレイ30上に形成されたパッシベーション層40と、パッシベーション層40上に配置された波長変換部材50とを備えるアクティブマトリクス駆動方式の画像表示素子である。
An
そして、有機EL素子100において、有機EL素子アレイ30の有機EL部31は、後述するように白色光を発光することができる。有機EL素子アレイ30は、本発明の第1実施形態の有機EL素子100において発光部であり、少なくとも青色の光を含んで発する光源部を構成する。
And in the
また、有機EL素子100において、波長変換部材50は、発光部であって光源となる有機EL素子アレイ30の有機EL部31に対向配置されて有機EL部31からの光の波長を変換する波長変換部として、赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bを有する。波長変換部材50の赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bはそれぞれ、量子ドットを含有して構成される。
Moreover, in the
すなわち、有機EL素子100においては、波長変換部材50の赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bがそれぞれ量子ドットを含有し、それぞれが波長変換部となる。そして、赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bは、有機EL部31に対向配置されて、有機EL部31からの光を赤色光、緑色光または青色光に変換することができる。したがって、有機EL素子100は、波長変換部材50から出射される赤色光、緑色光および青色光の光量を制御することによりカラー画像を形成し、カラー表示を行うことが可能である。
That is, in the
以下、有機EL素子100の各構成要素を具体的に説明する。
Hereinafter, each component of the
回路基板10は、ガラスまたは樹脂等からなる基板11上に例えばスピンオングラス(SOG)からなるバッファ層12を介して形成された複数の画素回路を有する。個々の画素回路には、有機EL素子アレイ30を構成する複数の有機EL部31の各々毎に1つのスイッチング回路が形成されており、これらのスイッチング回路は、平面視上、複数行複数列に亘って行列状に配置されている。各スイッチング回路は、1つの選択用薄膜トランジスタ(以下、薄膜トランジスタを「TFT」と略記する。)と、1つの駆動用TFTと、1対のキャパシタ(保持容量)電極とを含む。図1においては、計4つの選択用TFT15と計4対のキャパシタ電極それぞれにおける一方のキャパシタ電極16とが表れており、駆動用TFTおよび計4対のキャパシタ電極それぞれにおける他方のキャパシタ電極は表れていない。
The
各選択用TFT15におけるソース13sおよびドレイン13dは、バッファ層12上に形成されたシリコン層13に形成され、これらの選択用TFT15におけるゲート14は、シリコン層13上にゲート絶縁膜(図示せず。)を介して形成される。また、1つの行を構成する各選択用TFT15のソース13sは、コンタクトプラグ17aによってデータライン19に接続され、これらの選択用TFT15それぞれのドレイン13dは、コンタクトプラグ17bによってデータライン19に接続されるとともに、対応する駆動用TFTのゲートと、対応する1対のキャパシタ電極における一方のキャパシタ電極16とに接続される。そして、これらの選択用TFT15それぞれのゲート14は、コンタクトプラグによって1つの選択ライン(いずれも図示せず。)に接続される。
The
一方、1つの列を構成する各駆動用TFTのソースは1つの電源ラインに接続され、これらの駆動用TFTそれぞれのドレインは、対応する有機EL部31の画素電極31aと、対応する1対のキャパシタ電極における他方のキャパシタ電極とに接続される。尚、各選択用TFT15および各駆動用TFTは、例えば、無機材料によって形成された第1平坦化膜18で覆われる。データライン19は、第1平坦化膜18上に形成される。選択ラインおよび電源ラインは、例えば、バッファ層12上に形成されて第1平坦化膜18により覆われる。
On the other hand, the source of each driving TFT constituting one column is connected to one power supply line, and the drain of each of these driving TFTs is connected to the
第2平坦化膜20は、無機材料または有機材料によって形成されて、データライン19を覆う。
The
有機EL素子アレイ30は、複数行複数列に亘って配置された複数の有機EL部31と、当該有機EL素子アレイ30を平面視したときに個々の有機EL部31を取り囲むようにして格子状に形成された隔壁部32とを有する。各有機EL部31は、第2平坦化膜20上に配置された画素電極31aと、画素電極31a上に積層された有機発光層31bと、各有機発光層31bの上面および隔壁部32の上部を覆う1つの共通電極31cにおける有機発光層31b上の領域とによって構成される。これらの有機EL部31は、共通電極31cの側から白色光を出射するトップエミッション型の発光素子である。
The organic
個々の有機発光層31bは、例えば、赤色光を出射する赤色有機発光層、緑色光を出射する緑色有機発光層、および青色光を出射する青色有機発光層を順不同で、かつ上下方向に隣り合う有機発光層同士の間に電荷発生層を介在させた状態で画素電極31a上に順次積層することによって形成可能である。あるいは、黄色光を出射する黄色有機発光層と青色有機発光層とを順不同で、かつ黄色有機発光層と青色有機発光層との間に電荷発生層を介在させた状態で画素電極31a上に順次積層することによって形成可能である。有機発光層31bは、上記の積層による各色有機発光層からの光を組み合わせて、白色光を発することができる。
The individual organic
また、有機EL素子アレイ30の隔壁部32は、例えば、樹脂層を形成した後に当該樹脂層をパターニングすることによって、あるいは樹脂材料をインクジェット法や印刷法で所定形状に塗工した後に硬化させることによって形成可能である。
The
パッシベーション層40は、例えば、透明有機材料によって形成されて、共通電極31cを覆う。
The
波長変換部材50は、透明無機材料または透明有機材料を用いて形成された基板51と、基板51上に規則的に配置された赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bとを有する。赤色カラーフィルタ52R、緑色カラーフィルタ52Gおよび青色カラーフィルタ52Bは、有機EL素子100において、カラーフィルタを構成する。すなわち、有機EL素子100の有するカラーフィルタは、赤色カラーフィルタ52R、緑色カラーフィルタ52Gおよび青色カラーフィルタ52Bを含んで構成される。
The
基板51は、例えば、ガラス、石英、または、透明樹脂(例えば、透明ポリイミド、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリエステルフィルム、環状オレフィン系樹脂フィルム等)等からなる。そして、赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bの各々は、公知の方法に従い、赤色、緑色、または青色に着色した樹脂材料によって形成されて、例えば、ストライプパターン、モザイクパターン、ベイヤーパターン等の所望パターンの下に配置される。
The
また、波長変換部材50は、基板51から見て赤色カラーフィルタ52R上に形成された赤色波長変換層53Rと、緑色カラーフィルタ52G上に形成された緑色波長変換層53Gと、青色カラーフィルタ52B上に形成された青色波長変換層53Bとを有する。
Further, the
赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bは、後述する本発明の第3実施形態の硬化性樹脂組成物を用いて形成された硬化膜であり、それぞれ量子ドットを含有して構成される。そして、赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bは、それぞれが、有機EL部31からの白色光に含まれる、例えば、青色光等の所定波長範囲の光を、赤色光、緑色光、または青色光に変換する波長変換部となる。尚、以下、赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bを、総称して、波長変換層53R,53G,53Bと言うことがある。
The red
そして、例えば、赤色波長変換層53Rは励起光、具体的には有機EL部31からの励起光の照射を受けたときに赤色の蛍光を発する。すなわち、赤色波長変換層53Rは有機EL部31からの光を赤色光に変換する。また、緑色波長変換層53Gは励起光の照射を受けたときに緑色の蛍光を発する。すなわち、緑色波長変換層53Gは有機EL部31からの光を緑色光に変換する。そして、青色波長変換層53Bは励起光の照射を受けたときに青色の蛍光を発する。すなわち、青色波長変換層53Bは有機EL部31からの光を青色光に変換する。
For example, the red
波長変換部材50の赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53Bの厚さはそれぞれ、100nm~100μm程度が好ましく、1μm~100μmがより好ましい。その厚さが100nm未満であると、励起光を十分吸収することができず、光変換効率が低下するために、表示素子の輝度が十分に確保できないといった問題が生じる。さらに、励起光の吸収を高め、表示素子の輝度を十分に確保するためには、厚さとして、1μm以上とすることが好ましい。
The thicknesses of the red
そして、これら赤色波長変換層53R、緑色波長変換層53G、および青色波長変換層53Bの各々は、平面視上、1つの有機EL部31と実質的に同じ大きさ、または1つの有機EL部31よりも若干大きな大きさを有し、1つの有機EL部31の上方に1つの波長変換層53R,53G,53Bが位置する。
Each of the red
すなわち、有機EL部31とそれと同様の大きさの波長変換層53R,53G,53Bのそれぞれとは、互いに対向配置され、有機EL部31からの光を赤色光、緑色光または青色光に変換する。そして、波長変換層53R,53G,53Bの側から、波長変換層53R,53G,53Bのそれぞれに対応する有機EL部31を平面視したとき、当該有機EL部31は、対応する波長変換層53R,53G,53Bの外方へは実質的に突出しない。同様に、カラーフィルタ側から、各カラーフィルタ52R,52G,52Bのそれぞれに対応する各波長変換層53R,53G,53Bを平面視したとき、当該波長変換層53R,53G,53Bは、各カラーフィルタ52R,52G,52Bの外方へは実質的に突出しない。そして、カラーフィルタは、有機EL部31と対向配置された波長変換層53R,53G,53Bの反有機EL素子側に設けられている。すなわち、カラーフィルタは、波長変換部の上部に設けられ、波長変換部を挟んで、有機EL部31を含む光源部が配置された側とは反対となる側に配置されている。
That is, the
さらに、波長変換部材50は、遮光性を有する無機材料または有機材料によって基板51上に形成されたブラックマトリクス54を有する。当該ブラックマトリクス54は、平面視上、各カラーフィルタ52R,52G,52Bを取り囲むとともに、波長変換層53R,53G,53Bのそれぞれを取り囲む。ブラックマトリクス54は、公知の遮光性の材料を用い、公知の方法に従ってパターニングして形成することができる。尚、ブラックマトリクス54は、波長変換部材50において、必須の構成要素ではなく、波長変換部材50は、ブラックマトリクス54を設けない構成とすることも可能である。
Further, the
この波長変換部材50は、例えば、当該波長変換部材50を単独で作成した後にパッシベーション層40上に貼り合わされる。あるいは、パッシベーション層40上に波長変換層53R,53G,53Bのそれぞれ、各カラーフィルタ52R,52G,52B、およびブラックマトリクス54を順次形成した後に、各カラーフィルタ52R,52G,52Bおよびブラックマトリクス54それぞれの上面上に基板51を貼り合わせることによって形成することができる。
The
そして、有機EL素子100では、有機EL素子アレイ30からの白色光を励起光とし、波長変換部材50の赤色波長変換層53R、緑色波長変換層53G、および青色波長変換層53Bのそれぞれによって、その励起光を赤色光、緑色光、および青色光に変換することができる。また、有機EL素子100は、波長変換部材50の赤色波長変換層53R、緑色波長変換層53G、および青色波長変換層53Bの各々から出射された赤色光、緑色光、および青色光を、各カラーフィルタ52R,52G,52Bを透過させることによって高色純度化することができる。
In the
さらに、有機EL素子100においては、有機EL素子アレイ30の有機EL部31からの光が赤色波長変換層53R、緑色波長変換層53G、または青色波長変換層53Bを透過し、波長変換されずに出射された場合に、波長変換部材50の各カラーフィルタ52R,52G,52Bを用いることにより、赤色波長変換層53R、緑色波長変換層53G、または青色波長変換層53Bを補助するように波長特性の調整を行うことができる。そして、有機EL素子100において、望まれない色の光が素子外に出射されるのを低減することができる。
Furthermore, in the
上述した各構成要素を備えた有機EL素子100では、後述する本発明の第3実施形態の硬化性樹脂組成物によって、量子ドットを含有する波長変換層53R,53G,53Bのそれぞれが形成されている。このため、波長変換層53R,53G,53Bはそれぞれ、量子ドットの含有により、優れた蛍光特性、具体的には波長変換効率を示す。また、波長変換層53R,53G,53Bそれぞれの形成時には残渣が生じ難いため、不所望の箇所に波長変換層53R,53G,53Bの残渣が生じたことに起因する画素間での混色も起こり難い。これらの結果として、有機EL素子100は輝度を高め易く、高輝度で高画質の画像表示を行うことができる有機EL装置の構成に用いることができる。
In the
実施の形態2.
<有機EL素子(2)>
図2は、本発明の第2実施形態の有機EL素子を概略的に示す断面図である。
<Organic EL element (2)>
FIG. 2 is a cross-sectional view schematically showing an organic EL element according to the second embodiment of the present invention.
図2に示す第2実施形態の有機EL素子200は、青色光を励起光として用い、波長変換部材150が赤色波長変換層53R、緑色波長変換層53Gおよび青色拡散層151を含むこと以外、第1実施形態の有機EL素子100と同様の構造を有する。したがって、図2に示す第2実施形態の有機EL素子200においては、図1の有機EL素子100と共通する構成要素について同じ符号を付し、その説明を行うようにする。
The
図2に示す有機EL素子200は、画素回路が形成された回路基板10と、回路基板10上に形成された第2平坦化膜20と、第2平坦化膜20上に複数行複数列に亘って配置された複数の有機EL部131からなる有機EL素子アレイ130と、有機EL素子アレイ130上に形成されたパッシベーション層40と、パッシベーション層40上に配置された波長変換部材150とを備えるアクティブマトリクス駆動方式の画像表示素子である。
An
そして、有機EL素子200において、有機EL素子アレイ130の有機EL部131は、後述するように青色光を発光することができる。すなわち、有機EL素子アレイ130は、本発明の第2実施形態の有機EL素子200において発光部であり、青色の光を含んで発する光源部を構成する。
In the
また、有機EL素子200において、波長変換部材150は、発光部であって光源となる有機EL素子アレイ130の有機EL部131に対向配置されて有機EL部131からの光の波長を変換する波長変換部として、赤色波長変換層53Rおよび緑色波長変換層53Gを有する。そして、さらに、波長変換部材150は、有機EL部131に対向配置されて有機EL部131からの光を拡散させて出射する光拡散層として青色拡散層151を有する。
In the
波長変換部材150の赤色波長変換層53Rおよび緑色波長変換層53Gはそれぞれ、量子ドットを含有して構成される。すなわち、有機EL素子200においては、波長変換部材150の赤色波長変換層53Rおよび緑色波長変換層53Gがそれぞれ量子ドットを含有し、それぞれが波長変換部となる。そして、赤色波長変換層53Rおよび緑色波長変換層53Gは、有機EL部131に対向配置されて、有機EL部131からの青色光を赤色光または緑色光に変換することができる。
The red
また、波長変換部材150の青色拡散層151は、有機EL部131からの青色光を波長変換することなく、同じ波長(色)特性のまま拡散させて出射させることができる。
したがって、有機EL素子200は、波長変換部材150から出射される赤色光、緑色光および青色光の光量を制御することにより、カラー画像を形成し、カラー表示を行うことが可能である。
Further, the
Therefore, the
以下、有機EL素子200の各構成要素を具体的に説明する。
Hereinafter, each component of the
回路基板10は、ガラスまたは樹脂等からなる基板11上に例えばスピンオングラス(SOG)からなるバッファ層12を介して形成された複数の画素回路を有する。個々の画素回路には、有機EL素子アレイ130を構成する複数の有機EL部131の各々毎に1つのスイッチング回路が形成されており、これらのスイッチング回路は、平面視上、複数行複数列に亘って行列状に配置されている。各スイッチング回路は、1つの選択用薄膜トランジスタ(以下、薄膜トランジスタを「TFT」と略記する。)と、1つの駆動用TFTと、1対のキャパシタ(保持容量)電極とを含む。図2においては、計4つの選択用TFT15と計4対のキャパシタ電極それぞれにおける一方のキャパシタ電極16とが表れており、駆動用TFTおよび計4対のキャパシタ電極それぞれにおける他方のキャパシタ電極は表れていない。
The
各選択用TFT15におけるソース13sおよびドレイン13dは、バッファ層12上に形成されたシリコン層13に形成され、これらの選択用TFT15におけるゲート14は、シリコン層13上にゲート絶縁膜(図示せず。)を介して形成される。また、1つの行を構成する各選択用TFT15のソース13sは、コンタクトプラグ17aによってデータライン19に接続され、これらの選択用TFT15それぞれのドレイン13dは、コンタクトプラグ17bによってデータライン19に接続されるとともに、対応する駆動用TFTのゲートと、対応する1対のキャパシタ電極における一方のキャパシタ電極16とに接続される。そして、これらの選択用TFT15それぞれのゲート14は、コンタクトプラグによって1つの選択ライン(いずれも図示せず。)に接続される。
The
一方、1つの列を構成する各駆動用TFTのソースは1つの電源ラインに接続され、これらの駆動用TFTそれぞれのドレインは、対応する有機EL部131の画素電極31aと、対応する1対のキャパシタ電極における他方のキャパシタ電極とに接続される。尚、各選択用TFT15および各駆動用TFTは、例えば、無機材料によって形成された第1平坦化膜18で覆われる。データライン19は、第1平坦化膜18上に形成される。選択ラインおよび電源ラインは、例えば、バッファ層12上に形成されて第1平坦化膜18により覆われる。
On the other hand, the source of each driving TFT constituting one column is connected to one power supply line, and the drain of each of these driving TFTs is connected to the
第2平坦化膜20は、無機材料または有機材料によって形成されて、データライン19を覆う。
The
有機EL素子アレイ130は、複数行複数列に亘って配置された複数の有機EL部131と、当該有機EL素子アレイ130を平面視したときに個々の有機EL部131を取り囲むようにして格子状に形成された隔壁部32とを有する。各有機EL部131は、第2平坦化膜20上に配置された画素電極31aと、画素電極31a上に積層された有機発光層131bと、各有機発光層131bの上面および隔壁部32の上部を覆う1つの共通電極31cにおける有機発光層131b上の領域とによって構成される。これらの有機EL部131は、共通電極31cの側から白色光を出射するトップエミッション型の発光素子である。
The organic
個々の有機発光層131bは、青色光を出射する青色有機発光層を画素電極31a上に積層することによって形成可能である。また、隔壁部32は、例えば、樹脂層を形成した後に当該樹脂層をパターニングすることによって、あるいは樹脂材料をインクジェット法や印刷法で所定形状に塗工した後に硬化させることによって形成可能である。
Each organic
パッシベーション層40は、例えば、透明有機材料によって形成されて、共通電極31cを覆う。
The
波長変換部材150は、透明無機材料または透明有機材料を用いて形成された基板51と、基板51上に規則的に配置された赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bとを有する。赤色カラーフィルタ52R、緑色カラーフィルタ52Gおよび青色カラーフィルタ52Bは、有機EL素子200において、カラーフィルタを構成する。すなわち、有機EL素子200のカラーフィルタは、赤色カラーフィルタ52R、緑色カラーフィルタ52Gおよび青色カラーフィルタ52Bからなる。
The
基板51は、ガラス、石英、または、透明樹脂(例えば、透明ポリイミド、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリエステルフィルム、環状オレフィン系樹脂フィルム等)等からなる。そして、赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bの各々は、公知の方法に従い、赤色、緑色、または青色に着色した樹脂材料によって形成されて、例えば、ストライプパターン、モザイクパターン、ベイヤーパターン等の所望パターンの下に配置される。
The
また、波長変換部材150は、基板51から見て赤色カラーフィルタ52R上に形成された赤色波長変換層53Rと、緑色カラーフィルタ52G上に形成された緑色波長変換層53Gと、青色カラーフィルタ52B上に形成された青色拡散層151とを有する。
Further, the
波長変換部材150の赤色波長変換層53Rおよび緑色波長変換層53Gは、後述する第3実施形態の硬化性樹脂組成物を用いて形成された硬化膜であり、それぞれ量子ドットを含有して構成される。青色拡散層151は、例えば、母材となる樹脂中に光散乱粒子を分散することによって形成することができる。
The red
そして、波長変換部材150の赤色波長変換層53Rは、励起光、具体的には有機EL部131からの励起光(青色光)の照射を受けたときに、その波長を変換して赤色の蛍光を発し、緑色波長変換層53Gは励起光(青色光)の照射を受けたときに、その波長を変換して緑色の蛍光を発する。そして、青色拡散層151は、有機EL部131からの青色光の照射を受けたときに、その青色光を拡散させて出射させることができる。
When the red
波長変換部材150の赤色波長変換層53R、緑色波長変換層53Gおよび青色拡散層151の厚さはそれぞれ、100nm~100μm程度が好ましく、1μm~100μmがより好ましい。赤色波長変換層53Rおよび緑色波長変換層53Gの厚さが100nm未満であると、励起光を十分吸収することができず、光変換効率が低下するために表示素子の輝度が十分に確保できないといった問題が生じる。さらに、励起光の吸収を高め、表示素子の輝度を十分に確保するためには、赤色波長変換層53Rおよび緑色波長変換層53Gの厚さとして、1μm以上とすることが好ましい。そして、青色拡散層151は、有機EL素子131からの青色光を効率良く拡散させて出射させることができるように、上記範囲の厚さを有することが好ましい。
The thickness of each of the red
そして、これら赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151の各々は、平面視上、1つの有機EL部131と実質的に同じ大きさ、または1つの有機EL部131よりも若干大きな大きさを有し、1つの有機EL部131の上方に1つの波長変換層53R,53Gまたは青色拡散層151が位置する。すなわち、有機EL部131とそれと同様の大きさの波長変換層53R,53Gのぞれぞれとは、互いに対向配置され、有機EL部131からの青色光の波長を変換する。
Each of the red
また、有機EL部131とそれと同様の大きさの青色拡散層151とが対向配置され、有機EL部131からの青色光を拡散させる。
青色拡散層151は、上述したように、成分である樹脂中に光散乱粒子となる透明粒子が分散されて構成されることが好ましい。
In addition, the
As described above, the
青色拡散層151に使用される樹脂としては、従来公知のものを使用することができ、特に限定されるものではないが、光透過性を有するものが好ましい。そして、後述する第3実施形態の硬化性樹脂組成物において、量子ドットに代えて、光散乱粒子となる透明粒子を用いて添加し、分散させて使用することが好ましい。そして、その透明粒子を含有する硬化性樹脂組成物を用い、後述する本発明の第4実施形態の波長変換部の形成方法と同様の方法に従い、青色拡散層151を形成することが好ましい。
As the resin used for the
青色拡散層151に含有される透明粒子としては、有機EL部131からの光を散乱、透過させることができるものであれば特に限定されず、例えば、平均粒径25μm、粒度分布の標準偏差1μmのポリスチレン粒子等を使用することができる。また、青色拡散層151中の透明粒子の含有量は、適宜変更可能であり、特に限定されない。
The transparent particles contained in the
有機EL素子200において、赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151の側から各々に対応する有機EL部131を平面視したとき、当該有機EL部131は、対応する赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151の外方へは実質的に突出しない。同様に、カラーフィルタ側から、各カラーフィルタ52R,52G,52Bのそれぞれに対応する赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151を平面視したとき、赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151は、当該各カラーフィルタ52R,52G,52Bの外方へは実質的に突出しない。そして、カラーフィルタは、有機EL部131と対向配置された波長変換層53R,53Gおよび青色拡散層151のそれぞれの反有機EL素子側に設けられている。すなわち、カラーフィルタは、波長変換部の上部に設けられ、波長変換部を挟んで、有機EL部131を含む光源部が配置された側とは反対となる側に配置されている。
In the
さらに、波長変換部材150は、遮光性を有する無機材料または有機材料によって基板51上に形成されたブラックマトリクス54を有する。当該ブラックマトリクス54は、平面視上、各カラーフィルタ52R,52G,52Bを取り囲むとともに、赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151を取り囲む。ブラックマトリクス54は、公知の遮光性の材料を用い、公知の方法に従ってパターニングして形成することができる。尚、ブラックマトリクス54は、波長変換部材150において、必須の構成要素ではなく、波長変換部材150は、ブラックマトリクス54を設けない構成とすることも可能である。
Furthermore, the
この波長変換部材150は、例えば、当該波長変換部材150を単独で作成した後にパッシベーション層40上に貼り合わされる。あるいは、パッシベーション層40上に、赤色波長変換層53R、緑色波長変換層53G、青色拡散層151、各カラーフィルタ52R,52G,52B、およびブラックマトリクス54を順次形成した後に、各カラーフィルタ52R,52G,52Bおよびブラックマトリクス54それぞれの上面上に基板51を貼り合わせることによって形成することができる。
For example, the
そして、有機EL素子200では、有機EL素子アレイ130からの青色光を励起光とし、波長変換部材150の赤色波長変換層53Rおよび緑色波長変換層53Gの各々によって、その励起光を赤色光および緑色光に変換することができる。そして、青色拡散層151によって、有機EL素子アレイ130からの青色光を拡散させて出射させることができる。
In the
また、有機EL素子200は、波長変換部材150の赤色波長変換層53R、緑色波長変換層53G、および青色拡散層151の各々から出射された赤色光、緑色光、および青色光を、各カラーフィルタ52R,52G,52Bを透過させることによって高色純度化することができる。
In addition, the
さらに、有機EL素子200においては、有機EL素子アレイ130の有機EL部131からの青色光が赤色波長変換層53Rまたは緑色波長変換層53Gを透過し、波長変換されずに出射された場合に、波長変換部材150の各カラーフィルタ52R,52Gを用いることにより、赤色波長変換層53Rまたは緑色波長変換層53Gを補助するように波長特性の調整を行うことができる。そして、有機EL素子アレイ130からの青色光が赤色波長変換層53Rまたは緑色波長変換層53Gで波長変換されずに透過し、素子外に出射されるのを低減することができる。
Furthermore, in the
上述した各構成要素を備えた有機EL素子200では、後述する本発明の第3実施形態の硬化性樹脂組成物によって赤色波長変換層53Rおよび緑色波長変換層53Gが形成されている。このため、赤色波長変換層53Rおよび緑色波長変換層53Gは、優れた蛍光特性、具体的には波長変換効率を示す。また、赤色波長変換層53Rおよび緑色波長変換層53Gの形成時には残渣が生じ難いため、不所望の箇所に波長変換層53R,53Gの残渣が生じたことに起因する画素間での混色も起こり難い。これらの結果として、有機EL素子200は輝度を高め易く、高輝度で高画質の画像表示を行うことができる有機EL装置の構成に用いることができる。
In the
実施の形態3.
<硬化性樹脂組成物>
本発明の第3実施形態の硬化性樹脂組成物は、[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)炭素数4~20の有機基を含む構成単位とを有する重合体(以下、[A]重合体または単に[A]成分とも言う。)、並びに、[B]量子ドット(以下、単に[B]成分とも言う。)を含有してなる硬化性の樹脂組成物である。
<Curable resin composition>
The curable resin composition of the third embodiment of the present invention includes [A] the same or different polymer molecules, (a1) a structural unit containing an acidic group and (a2) an organic group having 4 to 20 carbon atoms. A polymer having a structural unit (hereinafter also referred to as [A] polymer or simply [A] component), and [B] quantum dots (hereinafter also simply referred to as [B] component). It is a curable resin composition.
そして、上述した[A]重合体の(a2)炭素数4~20の有機基を含む構成単位は、上述した(a1)酸性基を含む構成単位以外の、炭素数4~20の有機基を含む構成単位であることが好ましい。 The structural unit (a2) containing the organic group having 4 to 20 carbon atoms of the [A] polymer described above is an organic group having 4 to 20 carbon atoms other than the structural unit containing (a1) an acidic group. The constituent unit is preferably included.
本発明の第3実施形態の硬化性樹脂組成物は、[A]重合体を含有し、塗布等による膜や層の簡便な形成に好適な樹脂組成物となる。 The curable resin composition of the third embodiment of the present invention contains a [A] polymer and is a resin composition suitable for simple formation of a film or layer by coating or the like.
そして、本発明の第3実施形態の硬化性樹脂組成物は、[A]成分とともに[B]成分の量子ドットを含有することで、[B]量子ドットの含有量を多くしながら[B]量子ドットの良好な分散状態を実現することができる。 And the curable resin composition of 3rd Embodiment of this invention contains the quantum dot of a [B] component with [A] component, [B] increasing the content of a quantum dot [B]. A good dispersion state of the quantum dots can be realized.
一般に量子ドットは、樹脂成分や溶剤等とともに用いられて組成物を構成する場合、組成物中で凝集する傾向があって、良好な分散状態の実現が難しい。量子ドットにおいて、凝集は、その蛍光特性を損なわせることになる。したがって、量子ドットを含有する組成物では、通常、量子ドットを多い量で含有することができない。 Generally, when quantum dots are used together with a resin component, a solvent, or the like to form a composition, they tend to aggregate in the composition, and it is difficult to realize a good dispersion state. In a quantum dot, aggregation will impair its fluorescent properties. Therefore, a composition containing quantum dots usually cannot contain a large amount of quantum dots.
そのため、本発明の第3実施形態の硬化性樹脂組成物では、[B]量子ドットを多く含有しながら、その良好な分散状態を実現するように、樹脂成分である[A]成分が選択されて含有されている。 Therefore, in the curable resin composition of the third embodiment of the present invention, the [A] component that is a resin component is selected so as to realize a good dispersion state while containing a large amount of [B] quantum dots. Contained.
その結果、本発明の第3実施形態の硬化性樹脂組成物は、[B]量子ドットを多く含有しながら[B]量子ドットの良好な分散状態が実現された樹脂組成物を形成することができる。そして、本発明の第3実施形態の硬化性樹脂組成物は、塗布等の簡便な形成方法を利用して、[B]量子ドットを多く含有するとともに、それらが分散された層や膜を形成することができる。 As a result, the curable resin composition of the third embodiment of the present invention can form a resin composition in which a good dispersion state of [B] quantum dots is realized while containing a large amount of [B] quantum dots. it can. And the curable resin composition of 3rd Embodiment of this invention forms a layer and a film | membrane in which they contained [B] many quantum dots using simple formation methods, such as application | coating, and they were disperse | distributed. can do.
また、本発明の第3実施形態の硬化性樹脂組成物は感放射線性を有することができる。そのために、本発明の第3実施形態の硬化性樹脂組成物は、[C]重合性開始剤(以下、単に[C]成分とも言う。)を含有することが好ましく、さらに、[D]重合性不飽和化合物(以下、単に[D]成分とも言う。)を含有することが好ましい。そして、本発明の第3実施形態の硬化性樹脂組成物は、その感放射線性に基づき、例えば、フォトリソグラフィ法等を利用したパターニングが可能である。 Also, the curable resin composition of the third embodiment of the present invention can have radiation sensitivity. Therefore, the curable resin composition according to the third embodiment of the present invention preferably contains a [C] polymerizable initiator (hereinafter also simply referred to as “C” component), and [D] polymerization. It is preferable to contain a polymerizable unsaturated compound (hereinafter also simply referred to as [D] component). And the curable resin composition of 3rd Embodiment of this invention can be patterned using the photolithographic method etc. based on the radiation sensitivity.
尚、本発明において、露光に際して照射される「放射線」には、可視光線、紫外線、遠紫外線、X線および荷電粒子線等が含まれる。 In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.
また、フォトリソグラフィ法には、加工や処理を受ける基材の表面に、所謂レジスト組成物を塗布してレジスト膜を形成する工程、光や電子線を照射して所定のレジストパターンを露光することによりレジストパターン潜像を形成する露光工程、必要に応じ加熱処理する工程、次いでこれを現像して所望の微細パターンを形成する現像工程、および、この微細パターンをマスクとして基板に対してエッチング等の加工を行う工程等が含まれる。 In the photolithography method, a so-called resist composition is applied to the surface of a substrate to be processed or processed to form a resist film, and a predetermined resist pattern is exposed by irradiation with light or an electron beam. An exposure process for forming a latent resist pattern image, a heat treatment process as necessary, a development process for developing the resist pattern to form a desired fine pattern, and etching the substrate using the fine pattern as a mask. The process etc. which process are included.
そして、本発明の第3実施形態の硬化性樹脂組成物は、必要な場合にパターニングが施されて、所望形状にパターニングされた硬化膜を形成することができる。したがって、本発明の第3実施形態の硬化性樹脂組成物は、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材の波長変換部である赤色波長変換層、緑色波長変換層、および青色波長変換層を形成することができる。本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材が有する各波長変換層は、樹脂中に[B]量子ドットが含まれて構成される。 The curable resin composition according to the third embodiment of the present invention can be patterned when necessary to form a cured film patterned into a desired shape. Therefore, the curable resin composition of the third embodiment of the present invention includes a red wavelength conversion layer, a green wavelength, which is a wavelength conversion portion of the wavelength conversion member of the organic EL element of the first embodiment and the second embodiment of the present invention. A conversion layer and a blue wavelength conversion layer can be formed. Each wavelength conversion layer which the wavelength conversion member of the organic EL element of 1st Embodiment of this invention and 2nd Embodiment has is comprised by including [B] quantum dot in resin.
以下、本発明の第3実施形態の硬化性樹脂組成物について説明する。 Hereinafter, the curable resin composition of the third embodiment of the present invention will be described.
本発明の第3実施形態の硬化性樹脂組成物は、[A]成分および[B]量子ドットを含有する。そして、本発明の実施形態3の硬化性樹脂組成物は、[B]量子ドットを含有するとともに、[B]量子ドットの良好な分散状態が実現された樹脂組成物を形成することができる。
The curable resin composition of the third embodiment of the present invention contains [A] component and [B] quantum dots. And the curable resin composition of
本発明の第3実施形態の硬化性樹脂組成物は、上述したように、塗布等の方法を利用することにより、[B]量子ドットを含有して優れた蛍光発光(波長変換)機能(以下、単に、蛍光性または蛍光特性等とも言う。)を備えた波長変換層を形成し、波長変換部を構成することができる。 As described above, the curable resin composition according to the third embodiment of the present invention uses [B] quantum dots and has an excellent fluorescence emission (wavelength conversion) function (hereinafter referred to as a “wavelength conversion” function). The wavelength conversion portion can be formed by forming a wavelength conversion layer having simply fluorescence or fluorescence characteristics.
また、本発明の第3実施形態の硬化性樹脂組成物は感放射線性を有することができる。そのため、上述したように、本発明の第3実施形態の硬化性樹脂組成物は、さらに、[C]重合性開始剤を含有することが好ましく、またさらに、[D]重合性不飽和化合物を含有することが好ましい。 Also, the curable resin composition of the third embodiment of the present invention can have radiation sensitivity. Therefore, as described above, the curable resin composition of the third embodiment of the present invention preferably further includes [C] a polymerizable initiator, and further includes [D] a polymerizable unsaturated compound. It is preferable to contain.
また、本発明の第3実施形態の硬化性樹脂組成物は、[A]成分および[B]量子ドット等とともに、[E]安定剤(以下、単に[E]成分とも言う。)を含有することができ、安定した蛍光特性を備えた硬化膜を形成することができ、各波長変換層を形成することができる。 Moreover, the curable resin composition of 3rd Embodiment of this invention contains an [E] stabilizer (henceforth only [E] component) with [A] component, [B] quantum dot, etc. And a cured film having stable fluorescence characteristics can be formed, and each wavelength conversion layer can be formed.
そして、本発明の第3実施形態の硬化性樹脂組成物は、本発明の効果を損なわない限り、後述するその他の任意成分を含有することができる。 And the curable resin composition of 3rd Embodiment of this invention can contain the other arbitrary component mentioned later, unless the effect of this invention is impaired.
以下で、本発明の第3実施形態の硬化性樹脂組成物の各含有成分についてより詳しく説明する。 Hereinafter, each component contained in the curable resin composition of the third embodiment of the present invention will be described in more detail.
〔[A]重合体〕
本発明の第3実施形態の硬化性樹脂組成物は、[A]重合体を含有する。
[[A] polymer]
The curable resin composition of 3rd Embodiment of this invention contains a [A] polymer.
[A]重合体は、上述したように、同一または異なる重合体分子中に、(a1)酸性基を含む構成単位(以下、単に構成単位(a1)とも言う。)と(a2)炭素数4~20の有機基を含む構成単位(以下、単に構成単位(a2)とも言う。)とを有しており、必要に応じてその他の構成単位を有していてもよい。 [A] As described above, the polymer has (a1) a structural unit containing an acidic group (hereinafter also simply referred to as the structural unit (a1)) and (a2) 4 carbon atoms in the same or different polymer molecules. To 20 (hereinafter also simply referred to as a structural unit (a2)), and may have other structural units as necessary.
そして、上述したように、[A]重合体の構成単位(a2)は、上述の構成単位(a1)以外の、炭素数4~20の有機基を含む構成単位であることが好ましい。 As described above, the structural unit (a2) of the polymer [A] is preferably a structural unit containing an organic group having 4 to 20 carbon atoms other than the structural unit (a1).
すなわち、[A]重合体の態様としては特に限定されず、
(i)同一の重合体分子中に構成単位(a1)および構成単位(a2)の両方を有しており、[A]重合体中に1種の重合体分子が存在する場合;
(ii)一の重合体分子中に構成単位(a1)を有し、それとは異なる重合体分子中に構成単位(a2)の両方を有しており、[A]重合体中に2種の重合体分子が存在する場合;
(iii)一の重合体分子中に構成単位(a1)および構成単位(a2)の両方を有し、それとは異なる重合体分子中に構成単位(a1)を有し、これらとはさらに異なる重合体分子中に構成単位(a2)を有しており、[A]重合体中に3種の重合体分子が存在する場合;
(iv)(i)~(iii)に規定の重合体分子に加え、[A]重合体中にさらに別の1種または2種以上の重合体分子を含む場合等が挙げられる。
That is, the mode of the [A] polymer is not particularly limited,
(I) When both the structural unit (a1) and the structural unit (a2) are contained in the same polymer molecule, and [A] one polymer molecule is present in the polymer;
(Ii) having a structural unit (a1) in one polymer molecule, and having both the structural unit (a2) in a different polymer molecule, and [A] two kinds of structural units in the polymer When polymer molecules are present;
(Iii) having both the structural unit (a1) and the structural unit (a2) in one polymer molecule, and having the structural unit (a1) in a polymer molecule different from the structural unit (a1). When the polymer molecule has the structural unit (a2), and [A] three polymer molecules exist in the polymer;
(Iv) In addition to the polymer molecules specified in (i) to (iii), there may be mentioned a case where [A] the polymer further contains one or more polymer molecules.
構成単位(a1)に含まれる酸性基としては、カルボキシル基、フェノール性水酸基、スルホ基を挙げることができ、カルボキシル基が好ましい。 Examples of the acidic group contained in the structural unit (a1) include a carboxyl group, a phenolic hydroxyl group, and a sulfo group, and a carboxyl group is preferable.
構成単位(a1)に含まれる有機基としては、炭素数4~20の脂肪族炭化水素基、炭素数4~20の脂環式炭化水素基、炭素数が20以下の芳香族炭化水素基、並びにこれらの脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基の1つ以上の水素原子が、水酸基、カルボキシル基、ハロゲン、ニトリル基、炭素数1~12のアルコキシル基、メルカプト基、スルホ基で置換された基を挙げることができる。 Examples of the organic group contained in the structural unit (a1) include an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 20 or less carbon atoms, And one or more hydrogen atoms of these aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups are a hydroxyl group, a carboxyl group, a halogen, a nitrile group, an alkoxyl group having 1 to 12 carbon atoms, a mercapto group, And groups substituted with a sulfo group.
上記の脂肪族炭化水素基としては、例えば、n-ブチル基、n-ペンチル基、n-ヘキシル基、n-オクチル基、n-ドデシル基、n-テトラデシル基、n-オクタデシル基等の直鎖状アルキル基、i-ブチル基、t-ブチル基、ネオペンチル基、2-ヘキシル基、3-ヘキシル基等の分岐状アルキル基が挙げられる。 Examples of the aliphatic hydrocarbon group include straight chain such as n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group and n-octadecyl group. And branched alkyl groups such as an alkyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group and 3-hexyl group.
また、上記の脂環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル、シクロオクチル、ボルニル基、ノルボルニル基、アダマンチル基等が挙げられる。 In addition, examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl, a cyclooctyl, a bornyl group, a norbornyl group, an adamantyl group, and the like.
また、上記の芳香族炭化水素基としては、例えば、フェニル基、ナフチル基等が挙げられる。 Moreover, examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
そして、構成単位(a1)に含まれる有機基としては、炭素数4~20の脂肪族炭化水素基およびその脂肪族炭化水素基の1つ以上の水素原子が、水酸基、カルボキシル基、ハロゲン、ニトリル基、炭素数1~12のアルコキシル基、メルカプト基、スルホ基で置換された基が好ましい。 As the organic group contained in the structural unit (a1), an aliphatic hydrocarbon group having 4 to 20 carbon atoms and one or more hydrogen atoms of the aliphatic hydrocarbon group may be a hydroxyl group, a carboxyl group, a halogen, or a nitrile. And a group substituted with an alkoxyl group having 1 to 12 carbon atoms, a mercapto group, or a sulfo group.
[A]重合体は、構成単位(a1)を与える単量体、構成単位(a2)を与える単量体、その他の構成単位を与える単量体のラジカル共重合により製造できる。同一の重合体分子に構成単位(a1)および構成単位(a2)の両方を含む[A]重合体を製造する場合は、少なくとも構成単位(a1)を与える単量体と構成単位(a2)を与える単量体とを含む混合物を用いて共重合させればよい。一方、一の重合体分子に構成単位(a1)を有し、かつそれとは異なる重合体分子に構成単位(a2)を有する[A]重合体を製造する場合は、少なくとも構成単位(a1)を与える単量体を含む重合性溶液をラジカル重合させて構成単位(a1)を有する重合体分子を得ておき、別途少なくとも構成単位(a2)を与える単量体を含む重合性溶液をラジカル重合させて構成単位(a2)を有する重合体分子を得て、最後に両者を混合して[A]重合体とすればよい。 [A] The polymer can be produced by radical copolymerization of a monomer that provides the structural unit (a1), a monomer that provides the structural unit (a2), and a monomer that provides the other structural unit. In the case of producing the [A] polymer containing both the structural unit (a1) and the structural unit (a2) in the same polymer molecule, at least the monomer that gives the structural unit (a1) and the structural unit (a2) What is necessary is just to copolymerize using the mixture containing the monomer to give. On the other hand, when the [A] polymer having the structural unit (a1) in one polymer molecule and the structural unit (a2) in a different polymer molecule is produced, at least the structural unit (a1) is included. A polymer solution having a structural unit (a1) is obtained by radical polymerization of a polymerizable solution containing a monomer to be given, and a polymerizable solution containing at least a monomer giving a structural unit (a2) is separately radically polymerized. The polymer molecule having the structural unit (a2) is obtained, and finally both are mixed to form the [A] polymer.
[A]重合体における構成単位(a1)の含有量としては、一の重合体分子に構成単位(a1)と構成単位(a2)とを含む場合、[A]重合体に含まれる全構成単位に対して、単量体仕込み比で、5質量%~70質量%が好ましく、10質量%~60質量%がより好ましく、20質量%~50質量%が特に好ましい。 [A] The content of the structural unit (a1) in the polymer is such that when the structural unit (a1) and the structural unit (a2) are included in one polymer molecule, [A] all the structural units included in the polymer On the other hand, the monomer charge ratio is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
一方、一の重合体分子に構成単位(a1)を有し、かつ別の一の重合体分子に構成単位(a2)を有する場合、構成単位(a1)を有する一の重合体分子における構成単位(a1)の含有量としては、その重合体分子に含まれる全構造単位に対して、単量体仕込み比で、40質量%~99質量%が好ましく、50質量%~98質量%以下がより好ましく、55質量%~95質量%が特に好ましい。 On the other hand, when one polymer molecule has the structural unit (a1) and another polymer molecule has the structural unit (a2), the structural unit in the one polymer molecule having the structural unit (a1) The content of (a1) is preferably 40% by mass to 99% by mass and more preferably 50% by mass to 98% by mass or less as a monomer charge ratio with respect to all the structural units contained in the polymer molecule. Preferably, 55% by mass to 95% by mass is particularly preferable.
また、[A]重合体における構成単位(a2)の含有量としては、一の重合体分子に構成単位(a1)と構成単位(a2)とを含む場合、[A]重合体に含まれる全構成単位に対して、単量体仕込み比で、10質量%以上60質量%以下が好ましく、15質量%以上55質量%以下がより好ましく、20質量%以上50質量%以下が特に好ましい。 The content of the structural unit (a2) in the [A] polymer is such that when the structural unit (a1) and the structural unit (a2) are contained in one polymer molecule, 10 mass% or more and 60 mass% or less are preferable by monomer preparation ratio with respect to a structural unit, 15 mass% or more and 55 mass% or less are more preferable, and 20 mass% or more and 50 mass% or less are especially preferable.
一方、一の重合体分子に構成単位(a1)を有し、かつ別の一の重合体分子に構成単位(a2)を有する場合、構成単位(a2)を有する一の重合体分子における構成単位(a2)の含有量としては、その重合体分子に含まれる全構成単位に対して、単量体仕込み比で、10質量%以上80質量%以下が好ましく、20質量%以上70質量%以下がより好ましく、25質量%以上60質量%以下が特に好ましい。 On the other hand, when one polymer molecule has the structural unit (a1) and another polymer molecule has the structural unit (a2), the structural unit in the one polymer molecule having the structural unit (a2) The content of (a2) is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass or less, based on the monomer charge ratio with respect to all the structural units contained in the polymer molecule. More preferably, 25 mass% or more and 60 mass% or less are especially preferable.
以上で説明した[A]重合体は、本発明の第3実施形態の硬化性樹脂組成物に含有されて、溶解または分散される。本発明の第3実施形態の硬化性樹脂組成物は、[A]成分とともに後述する[B]成分の量子ドットを含有し、[B]量子ドットの含有量を多くしながら[B]量子ドットの良好な分散状態を実現することができる。そして、塗布等の簡便な形成方法を利用して、[B]量子ドットを含む層や膜を得るための樹脂組成物を形成することができる。 [A] The polymer described above is contained in the curable resin composition of the third embodiment of the present invention and dissolved or dispersed. The curable resin composition of 3rd Embodiment of this invention contains the quantum dot of the [B] component mentioned later with a [A] component, and increases [B] quantum dot while increasing the content of a [B] quantum dot. A good dispersion state can be realized. And the resin composition for obtaining the layer and film | membrane containing a [B] quantum dot can be formed using simple formation methods, such as application | coating.
[A]重合体は硬化性樹脂組成物の全質量中5質量%以上含むことが望ましく、10質量%以上含むことがより好ましい。[A]重合体が硬化性樹脂組成物の全質量中5質量%より少ない場合は、硬化性樹脂組成物から得られる塗膜の厚さを十分に確保できなくなる。 [A] The polymer is desirably contained in an amount of 5% by mass or more, more preferably 10% by mass or more, based on the total mass of the curable resin composition. [A] When the polymer is less than 5% by mass in the total mass of the curable resin composition, it is impossible to sufficiently secure the thickness of the coating film obtained from the curable resin composition.
〔[B]量子ドット〕
本発明の第3実施形態の硬化性樹脂組成物の必須の成分である[B]量子ドットは、半導体材料を用いて構成された半導体量子ドットであることが好ましい。そして、[B]量子ドットは、CdやPbを構成成分とせず、例えば、In(インジウム)やSi(珪素)等を構成成分として構成された、安全な材料からなる量子ドットであることが好ましい。
[[B] quantum dots]
[B] Quantum dots, which are essential components of the curable resin composition of the third embodiment of the present invention, are preferably semiconductor quantum dots configured using a semiconductor material. The [B] quantum dot is preferably a quantum dot made of a safe material that does not contain Cd and Pb as constituents, and is composed of, for example, In (indium) or Si (silicon). .
したがって、[B]量子ドットは、2族元素、11族元素、12族元素、13族元素、14族元素、15族元素および16族元素で示される元素の群から選ばれる少なくとも2種以上の元素を含む化合物からなる、量子ドットであることが好ましい。
Accordingly, [B] quantum dots are at least two or more selected from the group of elements represented by
そして、より具体的には、人に対する安全性について懸念の大きい、例えば、PbおよびCd等の元素が除外され、Be(ベリリウム)、Mg(マグネシウム)、Ca(カルシウム)、Sr(ストロンチウム)、Ba(バリウム)、Cu(銅)、Ag(銀)、金(Au)、亜鉛(Zn)、B(ホウ素)、Al(アルミニウム)、Ga(ガリウム)、In(インジウム)、Tl(タリウム)、C(炭素)、Si(珪素)、Ge(ゲルマニウム)、Sn(錫)、N(窒素)、P(リン)、As(ヒ素)、Sb(アンチモン)、Bi(ビスマス)、O(酸素)、S(硫黄)、Se(セレン)、Te(テルル)およびPo(ポロニウム)よりなる群から選ばれる少なくとも2種以上の元素を含む化合物からなる、量子ドットであることが好ましい。 More specifically, elements such as Pb and Cd, which are of great concern for human safety, are excluded, and Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (Barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), C (Carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen), S A quantum dot made of a compound containing at least two elements selected from the group consisting of (sulfur), Se (selenium), Te (tellurium) and Po (polonium) is preferable.
このとき、[B]量子ドットが500nm~600nmの波長領域に蛍光極大を有する化合物(a)および/または600nm~700nmの波長領域に蛍光極大を有する化合物(b)からなることが好ましい。 At this time, the [B] quantum dot is preferably composed of a compound (a) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a compound (b) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm.
[B]量子ドットは、このような蛍光発光特性を有する化合物(a)および/または化合物(b)からなることで、500nm~600nmの波長領域、および/または、600nm~700nmの波長領域に蛍光極大を有することができる。その結果、[B]量子ドットを含有する本発明の第3実施形態の硬化性樹脂組成物は、可視域の光を出射するCCM方式の有機EL素子における各波長変換層を形成することができる。 [B] The quantum dot is composed of the compound (a) and / or the compound (b) having such fluorescence emission characteristics, so that the quantum dot is fluorescent in the wavelength region of 500 nm to 600 nm and / or in the wavelength region of 600 nm to 700 nm. Can have a maximum. As a result, the curable resin composition according to the third embodiment of the present invention containing [B] quantum dots can form each wavelength conversion layer in a CCM organic EL element that emits visible light. .
すなわち、本発明の第3実施形態の硬化性樹脂組成物では、所望とする蛍光発光特性を有する[B]量子ドットを含有させることで、例えば、上述した本発明の第1実施形態および第2実施形態の有機EL素子100,200の波長変換部材50,150の波長変換部である赤色波長変換層53Rを形成するための硬化性樹脂組成物や、緑色波長変換層53Gを形成するための硬化性樹脂組成物や、青色波長変換層53Bを形成するための硬化性樹脂組成物として使用することができる。
That is, in the curable resin composition of the third embodiment of the present invention, for example, the above-described first embodiment and second embodiment of the present invention are included by including [B] quantum dots having desired fluorescence emission characteristics. Curing resin composition for forming red
そしてさらに、本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットが、Inを構成成分として含む化合物からなる量子ドットであることがより好ましい。またほかに、[B]量子ドットとしては、SiまたはSi化合物を挙げることができる。 Furthermore, it is more preferable that the [B] quantum dot contained in the curable resin composition of the third embodiment of the present invention is a quantum dot made of a compound containing In as a constituent component. In addition, [B] quantum dots may include Si or Si compounds.
[B]量子ドットとして、SiまたはSi化合物のうち、Siが特に好ましい。 [B] As the quantum dots, Si is particularly preferable among Si or Si compounds.
[B]量子ドットの成分構成を上述のようにすることで、本発明の第3実施形態の硬化性樹脂組成物は、安全で、より優れた蛍光特性を有する硬化膜を形成することができ、さらには、安全で、より優れた蛍光特性を有する、本発明の第1実施形態および第2実施形態の有機EL素子100,200の波長変換部材50,150の波長変換部である各波長変換層53R、53G、53Bを形成することができる。
[B] By making the component constitution of the quantum dots as described above, the curable resin composition of the third embodiment of the present invention can form a cured film having safer and more excellent fluorescence characteristics. Furthermore, each wavelength conversion which is a wavelength conversion part of the
また、本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットは、1種の化合物からなる均質構造型、および、2種以上の化合物からなるコアシェル構造型から選ばれる少なくとも一方の構造型の量子ドットであることが好ましい。 [B] Quantum dots contained in the curable resin composition of the third embodiment of the present invention are selected from a homogeneous structure type composed of one compound and a core-shell structure type composed of two or more compounds. It is preferable that the quantum dots have at least one structure type.
コアシェル構造型の[B]量子ドットは、1つの種類の化合物でコア構造を形成し、別の化合物でコア構造の周囲を被覆して構成される。例えば、エネルギーバンドギャップのより大きい半導体でコアの半導体を被覆することにより、光励起によって生成された励起子(電子-正孔対)はコア内に閉じ込められる。その結果、量子ドット表面での無輻射遷移の確率が減少し、発光の量子収率および[B]量子ドットの蛍光特性の安定性が向上する。 The core-shell structure type [B] quantum dots are formed by forming a core structure with one kind of compound and covering the periphery of the core structure with another compound. For example, by covering the core semiconductor with a semiconductor having a larger energy band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the quantum dots is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of [B] quantum dots are improved.
本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットは、成分構成と構造を考慮した場合、コアシェル構造型量子ドットであるInP/ZnS、CuInS2/ZnS、および(ZnS/AgInS2)固溶体/ZnS、並びに、均質構造型量子ドットであるAgInS2およびZnドープAgInS2よりなる群から選ばれる少なくとも1種であることが好ましい。 [B] Quantum dots contained in the curable resin composition of the third embodiment of the present invention are InP / ZnS, CuInS 2 / ZnS, which are core-shell structured quantum dots, in consideration of the component configuration and structure, and It is preferably at least one selected from the group consisting of (ZnS / AgInS 2 ) solid solution / ZnS, and AgInS 2 which is a homogeneous structure type quantum dot and Zn-doped AgInS 2 .
以上より、本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットは、InP/ZnS化合物、CuInS2/ZnS化合物、AgInS2化合物、(ZnS/AgInS2)固溶体/ZnS化合物、ZnドープAgInS2化合物およびSi化合物の群から選ばれる少なくとも1つであることが好ましい。 From the above, [B] quantum dots contained in the curable resin composition of the third embodiment of the present invention are InP / ZnS compound, CuInS 2 / ZnS compound, AgInS 2 compound, (ZnS / AgInS 2 ) solid solution / It is preferably at least one selected from the group consisting of ZnS compounds, Zn-doped AgInS 2 compounds and Si compounds.
以上で例示した[B]量子ドットにより、それを含有する本発明の第3実施形態の硬化性樹脂組成物は、安全で、優れた蛍光特性を有する硬化膜を形成することができる。そして、優れた蛍光特性を備えた、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材の波長変換部である各波長変換層を形成することができる。 The curable resin composition according to the third embodiment of the present invention containing the [B] quantum dots exemplified above can form a cured film that is safe and has excellent fluorescence characteristics. And each wavelength conversion layer which is a wavelength conversion part of the wavelength conversion member of the organic EL element of 1st Embodiment and 2nd Embodiment of this invention provided with the outstanding fluorescence characteristic can be formed.
また、本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットは、平均粒径が0.5nm~20nmであることが好ましく、1.0nm~10nmであることがより好ましい。平均粒径が0.5nm未満である場合には、[B]量子ドットを調製することが難しく、調製ができたとしても、[B]量子ドットの蛍光特性が不安定になる場合がある。[B]量子ドットの平均粒径が20nmを超える場合には、量子ドットの大きさによる量子閉じ込め効果が得られない場合があって、所望とする蛍光特性が得られず、望ましくない。 The [B] quantum dots contained in the curable resin composition of the third embodiment of the present invention preferably have an average particle size of 0.5 nm to 20 nm, and preferably 1.0 nm to 10 nm. More preferred. When the average particle size is less than 0.5 nm, it is difficult to prepare [B] quantum dots, and even if it can be prepared, the fluorescence characteristics of [B] quantum dots may become unstable. [B] When the average particle diameter of the quantum dots exceeds 20 nm, the quantum confinement effect due to the size of the quantum dots may not be obtained, and the desired fluorescence characteristics cannot be obtained, which is not desirable.
また、[B]量子ドットの形状は特に限定されず、例えば、球状、棒状、円盤状、その他の形状であっても良い。量子ドットの粒径、形状、分散状態等の情報については、透過型電子顕微鏡(TEM)により得ることができる。 [B] The shape of the quantum dots is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disk shape, or other shapes. Information such as the particle size, shape, and dispersion state of the quantum dots can be obtained by a transmission electron microscope (TEM).
本発明の第3実施形態の硬化性樹脂組成物に含有される[B]量子ドットを得る方法としては、配位性有機溶媒中で有機金属化合物を熱分解する公知の方法を利用することができる。また、コアシェル構造型の量子ドットは、反応により均質なコア構造を形成した後、反応系内に、コア表面にシェルを形成するための前駆体を添加し、シェル形成の後、反応を停止し、溶媒から分離することで得ることができる。尚、市販されているものを利用することも可能である。 As a method for obtaining [B] quantum dots contained in the curable resin composition of the third embodiment of the present invention, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent may be used. it can. In addition, core-shell type quantum dots form a homogeneous core structure by reaction, then add a precursor to form a shell on the core surface in the reaction system, and stop the reaction after shell formation. It can be obtained by separating from a solvent. A commercially available product can also be used.
本発明の第3実施形態の硬化性樹脂組成物における[B]量子ドットの含有量としては、上述した[A]成分100質量部に対して、好ましくは、0.1質量部~100質量部、より好ましくは0.2質量部~50質量部である。[B]量子ドットの含有量を上述の範囲とすることで、優れた蛍光特性を有する硬化膜を形成し、その結果、優れた蛍光特性を備えた波長変換部材の波長変換部である各波長変換層を形成することができる。[B]量子ドットの含有量が、[A]成分100質量部に対して、0.1質量部より少ないと、形成される硬化膜において所望とする蛍光特性を得ることができず、所望とする特性の波長変換部材の波長変換層を形成することができない。また、[A]成分100質量部に対して、100質量部より多いと、形成される硬化膜の安定性が損なわれ、有機EL素子において、安定な各波長変換層を形成することができない。 The content of [B] quantum dots in the curable resin composition of the third embodiment of the present invention is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned [A] component. More preferably, it is 0.2 to 50 parts by mass. [B] By setting the content of quantum dots in the above range, a cured film having excellent fluorescence characteristics is formed, and as a result, each wavelength that is a wavelength conversion part of a wavelength conversion member having excellent fluorescence characteristics A conversion layer can be formed. [B] If the content of the quantum dots is less than 0.1 parts by mass with respect to 100 parts by mass of the [A] component, the desired fluorescent properties cannot be obtained in the cured film to be formed. Therefore, the wavelength conversion layer of the wavelength conversion member having the characteristics cannot be formed. Moreover, when there are more than 100 mass parts with respect to 100 mass parts of [A] component, the stability of the cured film formed will be impaired and in the organic EL element, each stable wavelength conversion layer cannot be formed.
〔[C]重合開始剤〕
本発明の第3実施形態の硬化性樹脂組成物は、さらに[C]重合開始剤を含有することができる。本実施形態の[C]重合開始剤は、放射線に感応して重合性基を有する化合物の重合を開始しうる活性種を生じるものが好ましい。したがって、本実施形態の[C]重合開始剤は、感放射線性の重合開始剤、すなわち、感放射線性重合開始剤が好ましい。
[[C] polymerization initiator]
The curable resin composition of the third embodiment of the present invention can further contain a [C] polymerization initiator. The [C] polymerization initiator of this embodiment is preferably one that generates an active species that can initiate polymerization of a compound having a polymerizable group in response to radiation. Therefore, the [C] polymerization initiator of this embodiment is preferably a radiation-sensitive polymerization initiator, that is, a radiation-sensitive polymerization initiator.
本発明の第3実施形態の硬化性樹脂組成物は、[C]重合開始剤を含有することで、感放射線性を高め、パターニング性を向上させることができる。そして、本発明の第3実施形態の硬化性樹脂組成物は、フォトリソグラフィ法等の公知のパターニング方法を利用して、パターニングされた硬化膜を形成することができ、有機EL素子の波長変換部材の波長変換部である各波長変換層を簡便に形成することができる。また、[C]重合開始剤は、後述する[D]重合性不飽和化合物とともに用いられ、本発明の第3実施形態の硬化性樹脂組成物に含有されることが好ましい。それによって、本発明の第3実施形態の硬化性樹脂組成物は、架橋反応性をより向上させることができ、この硬化性樹脂組成物から形成される波長変換部材の各波長変換層の強度および基材との密着性をさらに高めことができる。 The curable resin composition of 3rd Embodiment of this invention can improve radiation sensitivity and can improve patternability by containing a [C] polymerization initiator. And the curable resin composition of 3rd Embodiment of this invention can form the cured film patterned using well-known patterning methods, such as the photolithographic method, The wavelength conversion member of an organic EL element It is possible to easily form each wavelength conversion layer that is the wavelength conversion part. [C] The polymerization initiator is used together with the [D] polymerizable unsaturated compound described later, and is preferably contained in the curable resin composition of the third embodiment of the present invention. Thereby, the curable resin composition of the third embodiment of the present invention can further improve the cross-linking reactivity, the strength of each wavelength conversion layer of the wavelength conversion member formed from this curable resin composition, and Adhesion with the substrate can be further enhanced.
本発明の第3実施形態の硬化性樹脂組成物において、[C]重合開始剤としては、例えば、オキシムエステル化合物、アセトフェノン化合物、ビイミダゾール化合物等が挙げられる。尚、[C]重合開始剤は、単独でまたは2種以上を組み合わせて用いてもよい。 In the curable resin composition of the third embodiment of the present invention, examples of the [C] polymerization initiator include oxime ester compounds, acetophenone compounds, biimidazole compounds, and the like. In addition, you may use [C] polymerization initiator individually or in combination of 2 or more types.
上記オキシムエステル化合物としては、例えば、エタノン-1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、1-〔9-エチル-6-ベンゾイル-9H-カルバゾール-3-イル〕-オクタン-1-オンオキシム-O-アセテート、1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、1-〔9-n-ブチル-6-(2-エチルベンゾイル)-9H-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、エタノン-1-[9-エチル-6-(2-メチル-4-テトラヒドロフラニルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロピラニルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-5-テトラヒドロフラニルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロフラニルメトキシベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-{2-メチル-4-(2,2-ジメチル-1,3-ジオキソラニル)メトキシベンゾイル}-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)等のO-アシルオキシム化合物等が挙げられる。 Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2-octane. Dione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2- Ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-the) Lahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1 -(O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-cal 3-yl]-1-(O-acetyl oxime) O- acyloxime compounds such like.
上述した中で、オキシムエステル化合物としては、エタノン-1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロフラニルメトキシベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-{2-メチル-4-(2,2-ジメチル-1,3-ジオキソラニル)メトキシベンゾイル}-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)が好ましい。 Among the oxime ester compounds described above, etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2 -Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}- 9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.
上記アセトフェノン化合物としては、例えば、α-アミノケトン化合物挙げられる。 Examples of the acetophenone compound include α-aminoketone compounds.
上記α-アミノケトン化合物としては、例えば、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン等が挙げられる。 Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.
上記アセトフェノン化合物としては、α-アミノケトン化合物が好ましく、2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オンがより好ましい。 The acetophenone compound is preferably an α-aminoketone compound, such as 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is more preferred.
上記ビイミダゾール化合物としては、例えば、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラキス(4-エトキシカルボニルフェニル)-1,2’-ビイミダゾール、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4-ジクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4,6-トリクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール等が挙げられる。これらの中では、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4-ジクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4,6-トリクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾールが好ましく、2,2’-ビス(2,4-ジクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾールがより好ましい。 Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole and the like. Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′- Tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is more preferred .
[C]重合開始剤としては、市販品を使用してもよく、例えば、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(イルガキュア(登録商標)907)、2-(4-メチルベンジル)-2-(ジメチルアミノ)-1-(4-モルフォリノフェニル)-ブタン-1-オン(イルガキュア379)、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)](イルガキュア(登録商標)OXE01)、エタノン-1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)(イルガキュア(登録商標)OXE02)(以上、BASFジャパン社製)等が挙げられる。 [C] A commercially available product may be used as the polymerization initiator. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure (registered trademark) 907) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379), 1,2-octanedione-1- [4- ( Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure (registered trademark) OXE02) (manufactured by BASF Japan Ltd.).
さらに、[C]重合開始剤は、分子中に窒素原子を有さない重合開始剤であることが好ましい。このような構造を備えた[C]重合開始剤とすることで、本発明の第3実施形態の硬化性樹脂組成物は、蛍光特性のより優れた、有機EL素子の波長変換層を簡便に形成することができる。 Furthermore, the [C] polymerization initiator is preferably a polymerization initiator having no nitrogen atom in the molecule. By using the [C] polymerization initiator having such a structure, the curable resin composition of the third embodiment of the present invention can easily form a wavelength conversion layer of an organic EL device having better fluorescence characteristics. Can be formed.
このような分子中に窒素原子を有さない重合開始剤の具体例としては、例えば、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(イルガキュア(登録商標)651)、1-ヒドロキシシクロヘキシルフェニルケトン(イルガキュア(登録商標)184)、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(イルガキュア(登録商標)1173)、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(イルガキュア(登録商標)2959)、2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン(イルガキュア(登録商標)127)、フェニルグリオキシリックアシッドメチルエステル(Darocur(登録商標)MBF)、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(LUCIRIN(登録商標)TPO)、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(イルガキュア(登録商標)819)等が挙げられる。 Specific examples of such a polymerization initiator having no nitrogen atom in the molecule include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651), 1- Hydroxycyclohexyl phenyl ketone (Irgacure® 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure® 1173), 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure® 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] phenyl} -2-methyl-propan-1-one (Irgacure® 127), phenylglyoxyl Acid methyl ester (Darocur® MBF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN® TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine And oxide (Irgacure (registered trademark) 819).
[C]重合開始剤の含有量としては、[A]成分100質量部に対して、0.1質量部~40質量部が好ましく、0.5質量部~20質量部がより好ましい。[C]重合開始剤の含有量を上記範囲とすることで、本発明の第3実施形態の硬化性樹脂組成物は、低露光量の場合でも良好なパターニング性を示し、また、十分な表面硬度および密着性を有する硬化膜を形成して、有機EL素子の波長変換層を提供することができる。 [C] The content of the polymerization initiator is preferably 0.1 part by mass to 40 parts by mass, and more preferably 0.5 part by mass to 20 parts by mass with respect to 100 parts by mass of the component [A]. [C] By setting the content of the polymerization initiator in the above range, the curable resin composition of the third embodiment of the present invention exhibits good patternability even in the case of a low exposure amount, and has a sufficient surface. A cured film having hardness and adhesion can be formed to provide a wavelength conversion layer of the organic EL element.
〔[D]重合性不飽和化合物〕
本発明の第3実施形態の硬化性樹脂組成物は、さらに[D]重合性不飽和化合物を含有することができる。本発明の第3実施形態の硬化性樹脂組成物に含有される[D]重合性不飽和化合物は、重合性の不飽和構造を有する化合物である。本発明の第3実施形態の硬化性樹脂組成物が[D]重合性不飽和化合物を含有することで架橋反応性を高めることができる。そして、この硬化性樹脂組成物から形成される、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材の波長変換部である各波長変換層において、強度および基材との密着性を向上させることができる。その場合、[D]重合性不飽和化合物は、上述した[C]重合開始剤とともに用いられ、本発明の第3実施形態の硬化性樹脂組成物に含有されることが好ましい。
[[D] polymerizable unsaturated compound]
The curable resin composition of the third embodiment of the present invention may further contain a [D] polymerizable unsaturated compound. The [D] polymerizable unsaturated compound contained in the curable resin composition of the third embodiment of the present invention is a compound having a polymerizable unsaturated structure. Crosslinking reactivity can be improved because the curable resin composition of 3rd Embodiment of this invention contains a [D] polymerizable unsaturated compound. And in each wavelength conversion layer which is a wavelength conversion part of the wavelength conversion member of the organic EL element of 1st Embodiment and 2nd Embodiment of this invention formed from this curable resin composition, intensity | strength and a base material and It is possible to improve the adhesion. In that case, the [D] polymerizable unsaturated compound is preferably used together with the above-described [C] polymerization initiator and contained in the curable resin composition of the third embodiment of the present invention.
このような[D]重合性不飽和化合物としては、重合性が良好であり、得られる硬化膜の強度が向上するという観点から、単官能、2官能または3官能以上の(メタ)アクリル酸エステルが好ましい。 Such a [D] polymerizable unsaturated compound is a monofunctional, bifunctional, or trifunctional (meth) acrylic acid ester from the viewpoint of good polymerizability and improved strength of the resulting cured film. Is preferred.
上述した単官能(メタ)アクリル酸エステルとしては、例えば、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、ジエチレングリコールモノエチルエーテルアクリレート、ジエチレングリコールモノエチルエーテルメタクリレート、(2-アクリロイルオキシエチル)(2-ヒドロキシプロピル)フタレート、(2-メタクリロイルオキシエチル)(2-ヒドロキシプロピル)フタレート、ω-カルボキシポリカプロラクトンモノアクリレート等が挙げられる。市販品としては、例えば、アロニックスM-101、同M-111、同M-114、同M-5300(以上、東亞合成社製);KAYARAD TC-110S、同TC-120S(以上、日本化薬社製);ビスコート158、同2311(以上、大阪有機化学工業社製)等が挙げられる。 Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxy Propyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω-carboxypolycaprolactone monoacrylate. Commercially available products include, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, Nippon Kayaku) Biscoat 158, 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.
2官能(メタ)アクリル酸エステルとしては、例えば、エチレングリコールジアクリレート、プロピレングリコールジアクリレート、プロピレングリコールジメタクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジメタクリレート、1,6-ヘキサンジオールジアクリレート、1,6-ヘキサンジオールジメタクリレート、1,9-ノナンジオールジアクリレート、1,9-ノナンジオールジメタクリレート等が挙げられる。市販品としては、例えば、アロニックス(登録商標)M-210、同M-240、同M-6200(以上、東亞合成社製);KAYARAD(登録商標)HDDA、同HX-220、同R-604(以上、日本化薬社);ビスコート260、同312、同335HP(以上、大阪有機化学工業社製);ライトアクリレート(登録商標)1,9-NDA(共栄社化学社製)等が挙げられる。 Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol. Examples include dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate. Examples of commercially available products include Aronix (registered trademark) M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) HDDA, HX-220, R-604. (Nippon Kayaku Co., Ltd.); Biscoat 260, 312, and 335HP (Osaka Organic Chemical Co., Ltd.); Light acrylate (registered trademark) 1,9-NDA (Kyoeisha Chemical Co., Ltd.) and the like.
3官能以上の(メタ)アクリル酸エステルとしては、例えば、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ジトリメチロールプロパンテトラアクリレート、ジトリメチロールプロパンテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物、ジペンタエリスリトールヘキサメタクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサアクリレート、トリ(2-アクリロイルオキシエチル)フォスフェート、トリ(2-メタクリロイルオキシエチル)フォスフェート、コハク酸変性ペンタエリスリトールトリアクリレート、コハク酸変性ジペンタエリスリトールペンタアクリレートの他、直鎖アルキレン基および脂環式構造を有し、かつ2個以上のイソシアネート基を有する化合物と、分子内に1個以上の水酸基とを有し、かつ3個、4個または5個の(メタ)アクリロイルオキシ基を有する化合物と反応させて得られる多官能ウレタンアクリレート系化合物等が挙げられる。市販品としては、例えば、アロニックス(登録商標)M-309、同M-400、同M-405、同M-450、同M-7100、同M-8030、同M-8060、同TO-1450(以上、東亞合成社製);KAYARAD(登録商標)TMPTA、同DPHA、同DPCA-20、同DPCA-30、同DPCA-60、同DPCA-120、同DPEA-12(以上、日本化薬社);ビスコート(登録商標)295、同300、同360、同GPT、同3PA、同400(以上、大阪有機化学工業社製);多官能ウレタンアクリレート系化合物を含有する市販品としては、ニューフロンティア(登録商標)R-1150(第一工業製薬社製)、KAYARAD(登録商標)DPHA-40H(日本化薬社製)等が挙げられる。 Examples of the tri- or more functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and ditrimethylolpropane. Tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide In addition to id-modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, A compound having a chain alkylene group and an alicyclic structure and having two or more isocyanate groups, one or more hydroxyl groups in the molecule, and 3, 4, or 5 (meth) Examples thereof include polyfunctional urethane acrylate compounds obtained by reacting with a compound having an acryloyloxy group. Examples of commercially available products include Aronix (registered trademark) M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, and TO-1450. (Above, manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120, DPEA-12 (above, Nippon Kayaku Co., Ltd.) ); Biscoat (registered trademark) 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier (Registered Trademark) R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (Registered Trademark) DPHA-40H (Nippon Kayaku Co., Ltd.), and the like.
これらの[D]重合性不飽和化合物のうち、ω-カルボキシポリカプロラクトンモノアクリレート、1,9-ノナンジオールジメタクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ジトリメチロールプロパンテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートや、ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの混合物、エチレンオキサイド変性ジペンタエリスリトールヘキサアクリレート、コハク酸変性ペンタエリスリトールトリアクリレート、コハク酸変性ジペンタエリスリトールペンタアクリレート、多官能ウレタンアクリレート系化合物を含有する市販品等が好ましい。 Among these [D] polymerizable unsaturated compounds, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra Acrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol Triacrylate, succinic acid modified dipentaerythritol Pentaacrylate, including commercial products containing multifunctional urethane acrylate compounds are preferable.
上述した[D]重合性不飽和化合物は、単独で使用してもよいし2種以上を混合して使用してもよい。本発明の第3実施形態の硬化性樹脂組成物における[D]重合性不飽和化合物の使用割合としては、[A]成分100質量部に対して、30質量部~250質量部が好ましく、50質量部~200質量部がより好ましい。[D]重合性不飽和化合物の使用量が30質量部~250質量部の場合、本発明の第3実施形態の硬化性樹脂組成物の感度および得られる硬化膜の耐熱性がより良好となり、ひいては、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部である各波長変換層において、耐熱性がより良好となる。 [D] The polymerizable unsaturated compound described above may be used alone or in combination of two or more. The proportion of the [D] polymerizable unsaturated compound used in the curable resin composition of the third embodiment of the present invention is preferably 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the component [A]. More preferred is 200 to 200 parts by weight. [D] When the amount of the polymerizable unsaturated compound used is 30 parts by mass to 250 parts by mass, the sensitivity of the curable resin composition of the third embodiment of the present invention and the heat resistance of the resulting cured film become better, As a result, in each wavelength conversion layer which is a wavelength conversion part of the organic EL element of 1st Embodiment and 2nd Embodiment of this invention, heat resistance becomes more favorable.
〔[E]安定剤〕
本発明の第3実施形態の硬化性樹脂組成物は、さらに、[E]安定剤を含有することができる。本発明の第3実施形態の硬化性樹脂組成物が、[A]成分や[B]成分等の必須の成分に加え、さらに[E]安定剤を含有することで、それを用いて得られる本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部である各波長変換層において、光変換効率を向上させることできる。
[[E] Stabilizer]
The curable resin composition of the third embodiment of the present invention can further contain an [E] stabilizer. The curable resin composition of the third embodiment of the present invention is obtained by using an [E] stabilizer in addition to the essential components such as the [A] component and the [B] component. In each wavelength conversion layer which is a wavelength conversion part of the organic EL element of the first embodiment and the second embodiment of the present invention, the light conversion efficiency can be improved.
本発明の第3実施形態の硬化性樹脂組成物の成分として好ましい[E]安定剤としては、ホスファイト系酸化防止剤を挙げることができる。ホスファイト系酸化防止剤は、ホスファイト構造を有する化合物からなる。またその他に、[E]安定剤としては、ホスフィン化合物、フェノール化合物、ヒンダードフェノール構造を有する化合物、ヒンダードアミン構造を有する化合物およびチオエーテル構造を有する化合物等を挙げることができる。 [E] A stabilizer [E] preferable as a component of the curable resin composition of the third embodiment of the present invention includes a phosphite antioxidant. The phosphite antioxidant comprises a compound having a phosphite structure. In addition, examples of the [E] stabilizer include a phosphine compound, a phenol compound, a compound having a hindered phenol structure, a compound having a hindered amine structure, and a compound having a thioether structure.
ホスファイト系酸化防止剤としては、例えば、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、ビス[2,4-ビス(1,1-ジメチルエチル)-6-メチルフェニル]エチルエステル亜リン酸、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトール-ジ-ホスファイト、トリスノニルフェニルホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト等を挙げることができる。市販品としては、例えば、アデカスタブ(登録商標)PEP-36、同PEP-4C、同PEP-8、同PEP-8F、同PEP-8W、同PEP-11C、同PEP-24G、同HP-10、同2112、同260、アデカスタブ(登録商標)P、アデカスタブ(登録商標)QL、同522A、同329K、同1178、同1500、アデカスタブ(登録商標)C、同135A、同3010、アデカスタブ(登録商標)TPP、(以上、アデカ社製)、Irgafos(登録商標)38、Irgafos(登録商標)168、Irgafos(登録商標)P-EPQ(以上、いずれもBASFジャパン社製)等を挙げることができる。 Examples of phosphite antioxidants include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester. Phosphorous acid, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol-di-phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and the like. Examples of commercially available products include ADK STAB (registered trademark) PEP-36, PEP-4C, PEP-8, PEP-8F, PEP-8W, PEP-11C, PEP-24G, and HP-10. 2112, 260, ADK STAB (registered trademark) P, ADK STAB (registered trademark) QL, 522A, 329K, 1178, 1500, ADK STAB (registered trademark) C, 135A, 3010, ADK STAB (registered trademark) ) TPP (above, manufactured by Adeka), Irgafos (registered trademark) 38, Irgafos (registered trademark) 168, Irgafos (registered trademark) P-EPQ (all of which are manufactured by BASF Japan) and the like.
ホスフィン化合物としては、例えば、トリフェニルホスフィン、シクロヘキシルジフェニルホスフィン、エチルジフェニルホスフィン、トリ(o-トリル)ホスフィン、トリ(m-トリル)ホスフィン、トリ(p-トリル)ホスフィン、トリス(2,5-ジメチルフェニル)ホスフィン、トリス(3,5-ジメチルフェニル)ホスフィン等を挙げることができる。市販品としては、例えば、TPP、DPCP、TOTP、TMTP、TPTP、(以上、いずれも北興化学社製)等を挙げることができる。
これらのうち、特に下記式で示されるような芳香族を有するホスファイト系酸化防止剤あるいはホスフィン化合物が好ましい。
Examples of the phosphine compound include triphenylphosphine, cyclohexyldiphenylphosphine, ethyldiphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and tris (2,5-dimethyl). Phenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, and the like. Examples of commercially available products include TPP, DPCP, TOTP, TMTP, TPTP (all of which are manufactured by Hokuko Chemical Co., Ltd.).
Of these, aromatic phosphite antioxidants or phosphine compounds represented by the following formula are particularly preferred.
上記式中、RAは、単結合または酸素原子を示す。RBは、炭素数1~12のアルキル基、シクロペンチル基、シクロへキシル基、フェニル基、トリル基、キシリル基、ナフチル基を示す。RCは炭素数1~30の炭化水素基を示す。nは1~3の整数を示し、mは0~5の整数を示す。 In the above formula, R A represents a single bond or an oxygen atom. R B represents an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. R C represents a hydrocarbon group having 1 to 30 carbon atoms. n represents an integer of 1 to 3, and m represents an integer of 0 to 5.
上記式のRBとしては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、シクロペンチル基、シクロへキシル基、フェニル基、トリル基、キシリル基、ナフチル基等を挙げることができる。 As R B in the above formula, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group, naphthyl group and the like.
上記式のRCとしては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、エイコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、トリアコンチル基、フェニル基、トリル基、キシリル基、ナフチル基等の炭素数1~30の直鎖状若しくは分岐状のアルキル基に由来する炭化水素基を挙げることができる。 As R C in the above formula, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, Eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Derived from 30 linear or branched alkyl groups There may be mentioned hydrocarbon groups.
上述したフェノール化合物としては、例えば、4-メトキシフェノール、4-エトキシフェノール等が挙げられる。 Examples of the above-mentioned phenol compound include 4-methoxyphenol, 4-ethoxyphenol, and the like.
上述したヒンダードフェノール構造を有する化合物としては、例えば、2,6-ジ-t-ブチル-4-クレゾール、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、チオジエチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、N,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルプロピオンアミド)]、3,3’,3’’,5’,5’’-ヘキサ-tert-ブチル-a,a’,a’’-(メシチレン-2,4,6-トリイル)トリ-p-クレゾール、4,6-ビス(オクチルチオメチル)-o-クレゾール、4,6-ビス(ドデシルチオメチル)-o-クレゾール、エチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート]、ヘキサメチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、1,3,5-トリス[(4-tert-ブチル-3-ヒドロキシ-2,6-キシリン)メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、2,6-ジ-tert-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミン)フェノール、トリス-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレイト等が挙げられる。 Examples of the compound having a hindered phenol structure described above include 2,6-di-tert-butyl-4-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl). Propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide)], 3,3 ′, 3 ″, 5 ′, 5 ″ -he Tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6 -Bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine- , 4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol, And tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate.
上述のヒンダードフェノール構造を有する化合物の市販品としては、例えば、アデカスタブ(登録商標)AO-20、同AO-30、同AO-40、同AO-50、同AO-60、同AO-70、同AO-80、同AO-330(以上、アデカ社製)、sumilizer(登録商標)GM、同GS、同MDP-S、同BBM-S、同WX-R、同GA-80(以上、住友化学社製)、IRGANOX(登録商標)1010、同1035、同1076、同1098、同1135、同1330、同1726、同1425WL、同1520L、同245、同259、同3114、同565、IRGAMOD(登録商標)295(以上、BASFジャパン社製)、ヨシノックス(登録商標)BHT、同BB、同2246G、同425、同250、同930、同SS、同TT、同917、同314(以上、エーピーアイコーポレーション社製)等が挙げられる。 Examples of commercially available compounds having the above hindered phenol structure include ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, and AO-70. , AO-80, AO-330 (manufactured by Adeka), sumilizer (registered trademark) GM, GS, MDP-S, BBM-S, WX-R, GA-80 (and above) Manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD (Registered trademark) 295 (above, manufactured by BASF Japan), Yoshinox (registered trademark) BHT, BB, 2246G, 425, 250, 930, the SS, the TT, the 917, the 314 (or, API Corporation Co., Ltd.).
ヒンダードアミン構造を有する化合物の市販品としては、例えば、アデカスタブ(登録商標)LA-52、同LA57、同LA-62、同LA-67、同LA-63P、同LA-68LD、同LA-77、同LA-82、同LA-87(以上、アデカ社製)、sumilizer(登録商標)9A(住友化学社製)、CHIMASSORB(登録商標)119FL、同2020FDL、同944FDL、TINUVIN(登録商標)622LD、同144、同765、同770DF(以上、BASFジャパン社製)が挙げられる。 Examples of commercially available compounds having a hindered amine structure include ADK STAB (registered trademark) LA-52, LA57, LA-62, LA-67, LA-63P, LA-68LD, LA-77, LA-82, LA-87 (manufactured by Adeka), sumilizer (registered trademark) 9A (manufactured by Sumitomo Chemical), CHIMASSORB (registered trademark) 119FL, 2020FDL, 944FDL, TINUVIN (registered trademark) 622LD 144, 765, and 770DF (manufactured by BASF Japan Ltd.).
チオエーテル構造を有する化合物の市販品としては、例えば、アデカスタブ(登録商標)AO-412S、同AO-503(以上、アデカ社製)、sumilizer(登録商標)TPL-R、同TPM、同TPS、同TP-D、同MB(以上、住友化学社製)、IRGANOX(登録商標)PS800FD、同PS802FD(以上、BASFジャパン社製)、DLTP、DSTP、DMTP、DTTP(以上、エーピーアイコーポレーション社製)等が挙げられる。 Commercially available compounds having a thioether structure include, for example, Adekastab (registered trademark) AO-412S, AO-503 (manufactured by Adeka), sumilizer (registered trademark) TPL-R, TPM, TPS, TP-D, MB (above, manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) PS800FD, PS802FD (above, manufactured by BASF Japan), DLTP, DSTP, DMTP, DTTP (above, manufactured by API Corporation), etc. Is mentioned.
[E]安定剤は、単独で使用してもよいし2種以上を混合して使用してもよい。本発明の第3実施形態の硬化性樹脂組成物における[E]安定剤の含有量としては、[A]成分100質量部に対して、好ましくは0.1質量部~10質量部、より好ましくは0.2質量部~5質量部である。[E]安定剤の含有量を上記の範囲とすることで、本発明の第3実施形態の硬化性樹脂組成物から得られる本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部である各波長変換層において、光変換効率をより向上させることできる。 [E] stabilizers may be used alone or in admixture of two or more. The content of [E] stabilizer in the curable resin composition of the third embodiment of the present invention is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of [A] component. Is 0.2 to 5 parts by mass. [E] By setting the content of the stabilizer within the above range, the organic EL device of the first embodiment and the second embodiment of the present invention obtained from the curable resin composition of the third embodiment of the present invention is used. In each wavelength conversion layer that is a wavelength conversion unit, the light conversion efficiency can be further improved.
〔その他の任意成分〕
本発明の第3実施形態の硬化性樹脂組成物は、[A]成分および[B]量子ドットを必須の成分として含有するとともに、本発明の効果を損なわない限り、その他の任意成分を含有することができる。その他の任意成分としては、例えば、溶剤、硬化促進剤および熱酸発生剤等を挙げることができる。
[Other optional ingredients]
The curable resin composition of the third embodiment of the present invention contains the [A] component and [B] quantum dots as essential components, and contains other optional components as long as the effects of the present invention are not impaired. be able to. Examples of other optional components include a solvent, a curing accelerator, and a thermal acid generator.
硬化促進剤は、本実施形態の硬化性樹脂組成物により形成される膜の硬化を促進する機能を果たす化合物である。 The curing accelerator is a compound that functions to accelerate the curing of the film formed by the curable resin composition of the present embodiment.
熱酸発生剤は、熱をかけることによって樹脂を硬化させる際の触媒として作用する酸性活性物質を放出することができる化合物である。 The thermal acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when the resin is cured by applying heat.
さらに、本発明の第3実施形態の硬化性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、界面活性剤、保存安定剤、接着助剤、耐熱性向上剤等のその他の任意成分を含有できる。これらの各任意成分は、単独で使用してもよいし、2種以上を混合して使用してもよい。 Furthermore, the curable resin composition of the third embodiment of the present invention is a range that does not impair the effects of the present invention, such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver. Other optional components can be contained. Each of these optional components may be used alone or in combination of two or more.
〔硬化性樹脂組成物の調製方法〕
本発明の第3実施形態の硬化性樹脂組成物は、[A]重合体および[B]量子ドットを均一に混合することによって調製される。また、含有させることが任意の[C]成分や[D]成分や[E]成分を含有させる場合、[A]成分および[B]成分とともに、必要に応じて[C]成分や[D]成分や[E]成分を均一に混合することによって調製される。
[Method for preparing curable resin composition]
The curable resin composition of the third embodiment of the present invention is prepared by uniformly mixing the [A] polymer and [B] quantum dots. In addition, when the optional [C] component, [D] component, and [E] component are included, the [C] component and [D] as necessary together with the [A] component and [B] component It is prepared by mixing the components and [E] component uniformly.
さらに、上述したその他の任意成分を必要に応じて選択し、それらを含有させる場合、[A]成分および[B]成分等とともに、当該その他の任意の成分を均一に混合することによって調製される。 Furthermore, when other optional components described above are selected as necessary, and they are contained, they are prepared by uniformly mixing the other optional components together with the [A] component and the [B] component. .
そして、本発明の第3実施形態の硬化性樹脂組成物を調製するにあたり、分散液状態の硬化性樹脂組成物を調製するため、有機溶剤を用いることができる。 In preparing the curable resin composition of the third embodiment of the present invention, an organic solvent can be used to prepare a curable resin composition in a dispersion state.
有機溶剤の機能としては、本発明の第3実施形態の硬化性樹脂組成物の粘度等を調節して、例えば、基材等への塗布性を向上させることや、操作性や成形性を向上させること等が挙げられる。 As a function of the organic solvent, for example, by adjusting the viscosity of the curable resin composition of the third embodiment of the present invention, it is possible to improve applicability to a substrate, etc., and improve operability and moldability. For example.
本実施形態の硬化性樹脂組成物に使用可能な有機溶剤としては、それ以外の含有成分を溶解または分散させるとともに、それ以外の含有成分と反応しないものを挙げることができる。このような有機溶剤としては、例えば、アルコール類、エーテル類、ジエチレングリコールアルキルエーテル類、エチレングリコールアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテルプロピオネート類、炭化水素類、ケトン類、エステル類等が挙げられる。 Examples of the organic solvent that can be used in the curable resin composition of the present embodiment include those that dissolve or disperse other components and that do not react with other components. Examples of such organic solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propio. Examples include nates, hydrocarbons, ketones, and esters.
これらの有機溶剤としては、
アルコール類として、例えば、ベンジルアルコール、ジアセトンアルコール等;
エーテル類として、例えば、テトラヒドロフランや、ジイソプロピルエーテル、ジn-ブチルエーテル、ジn-ペンチルエーテル、ジイソペンチルエーテル、ジn-ヘキシルエーテル等のジアルキルエーテル等;
ジエチレングリコールアルキルエーテル類として、例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル等;
エチレングリコールアルキルエーテルアセテート類として、例えば、メチルセロソルブアセテート、エチルセロソルブアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等;
プロピレングリコールモノアルキルエーテル類として、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等;
プロピレングリコールモノアルキルエーテルアセテート類として、例えば、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等;
プロピレングリコールモノアルキルエーテルプロピオネート類として、例えば、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、プロピレングリコールモノプロピルエーテルプロピオネート、プロピレングリコールモノブチルエーテルプロピオネート等;
ケトン類として、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン、4-ヒドロキシ-4-メチル-2-ペンタノン等;
エステル類として、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸i-プロピル、酢酸ブチル、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸メチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、3-ヒドロキシプロピオン酸メチル、3-ヒドロキシプロピオン酸エチル、3-ヒドロキシプロピオン酸プロチル、3-ヒドロキシプロピオン酸ブチル、2-ヒドロキシ-3-メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸プロピル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸プロピル、エトキシ酢酸ブチル、プロポキシ酢酸メチル、プロポキシ酢酸エチル、プロポキシ酢酸プロピル、プロポキシ酢酸ブチル、ブトキシ酢酸メチル、ブトキシ酢酸エチル、ブトキシ酢酸プロピル、ブトキシ酢酸ブチル、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-メトキシプロピオン酸ブチル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル等がそれぞれ挙げられる。
As these organic solvents,
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include tetrahydrofuran, dialkyl ethers such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc .;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.
量子ドットの分散性の観点から炭化水素溶剤が好ましい。炭化水素としては、芳香族炭化水素溶剤と脂肪族炭化水素溶剤が挙げられる。芳香族炭化水素溶剤としては、トルエン、エチルベンゼン、アミルベンゼン、イソプロピルベンゼン、キシレン、シクロヘキシルベンゼン、ナフタレン、ジメチルナフタレン、シメン、テトラリン、ビフェニル、メシチレン等が挙げられる。脂肪族炭化水素系溶剤としては、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、p-メンタン、ピナン、デカリン、イソオクタン、イソドデカン、シクロヘキセン、シクロペンタン、ジペンテン、アイソパーE、アイソパーG、アイソパーH、アイソパーL、アイソパーM((株)小倉興産製)、テレピン油、デカヒドロナフタリン、リモネン、α-ピネン、β-ピネン、ベンジン、キョーワゾールC-800、シェルゾール、アイソゾール、リグロイン(ゴードー工業(株)社製)等が挙げられる。 A hydrocarbon solvent is preferred from the viewpoint of the dispersibility of the quantum dots. Examples of the hydrocarbon include an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent include toluene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cymene, tetralin, biphenyl, mesitylene and the like. Aliphatic hydrocarbon solvents include hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, pinane, decalin, isooctane, isododecane, cyclohexene, cyclopentane, dipentene, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M (manufactured by Kokura Kosan), turpentine oil, decahydronaphthalene, limonene, α-pinene, β-pinene, benzine, Kyowasol C-800, shell sol , Isosol, ligroin (manufactured by Gordo Kogyo Co., Ltd.), and the like.
これらの有機溶剤の中でも、溶解性が優れていること、各成分と非反応性であること、並びに塗膜形成の容易性の観点から、ジアルキルエーテル等のエーテル類、ジエチレングリコールアルキルエーテル類、エチレングリコールアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ケトン類およびエステル類が好ましく、特に、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、シクロヘキサノン、酢酸プロピル、酢酸i-プロピル、酢酸ブチル、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸メチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチルが好ましい。これらの有機溶剤は、単独でまたは混合して用いることができる。 Among these organic solvents, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, ethylene glycol from the viewpoint of excellent solubility, non-reactivity with each component, and ease of film formation. Alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Tyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, lactic acid Ethyl, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These organic solvents can be used alone or in combination.
上記した有機溶剤に加え、さらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、1-オクタノール、1-ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ-ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテート、カルビトールアセテート等の高沸点溶媒を併用することもできる。 In addition to the above organic solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1 High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate can be used in combination.
本発明の第3実施形態の硬化性樹脂組成物における有機溶剤の含有量は、粘度等も考慮して適宜決めることができる。すなわち、本実施形態の硬化性樹脂組成物の固形分濃度(硬化性樹脂組成物溶液中に占める溶剤成分以外の成分)は、使用目的や所望の膜厚等に応じて任意に設定することができるが、好ましくは5質量%~50質量%、より好ましくは10質量%~40質量%、さらに好ましくは15質量%~35質量%である。 The content of the organic solvent in the curable resin composition of the third embodiment of the present invention can be appropriately determined in consideration of viscosity and the like. That is, the solid content concentration of the curable resin composition of the present embodiment (components other than the solvent component in the curable resin composition solution) can be arbitrarily set according to the purpose of use, desired film thickness, and the like. However, it is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 15% by mass to 35% by mass.
このようにして調製された本実施形態の硬化性樹脂組成物は、液状である場合、孔径0.5μm程度のミリポアフィルタ等を用いて濾過した後に、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部である各波長変換層の形成に使用することが好ましい。 When the curable resin composition of the present embodiment thus prepared is liquid, it is filtered using a Millipore filter having a pore diameter of about 0.5 μm and then the first and second embodiments of the present invention. It is preferable to use for formation of each wavelength conversion layer which is a wavelength conversion part of the organic EL element of a form.
実施の形態4.
<波長変換部の形成方法>
本発明の第4実施形態の波長変換部の形成方法によって得られる波長変換部は、例えば、図1および図2に示した本発明の第1実施形態の有機EL素子100および本発明の第2実施形態の有機EL素子200の波長変換部材50,150の波長変換部であり、具体的には、各波長変換層53R,53G,53Bとなる。
<Method for forming wavelength conversion section>
The wavelength conversion unit obtained by the wavelength conversion unit forming method of the fourth embodiment of the present invention includes, for example, the
すなわち、図1の本発明の第1実施形態の有機EL素子100の波長変換部材50が有する赤色波長変換層53R、緑色波長変換層53G、および青色波長変換層53Bは、本実施形態の波長変換部の形成方法に従って形成することができる。同様に、図2の本発明の第2実施形態の有機EL素子200の波長変換部材150が有する赤色波長変換層53R、および緑色波長変換層53Gは、本実施形態の波長変換部の形成方法に従って形成することができる。
That is, the red
以下で、本発明の第4実施形態の波長変換部の形成方法について説明する。 Hereinafter, a method of forming the wavelength conversion unit according to the fourth embodiment of the present invention will be described.
本発明の第4実施形態の波長変換部の形成方法では、基材上に、上述した本発明の第3実施形態の硬化性樹脂組成物を塗布し、必要な場合にパターニングをした後、露光による硬化を行って、パターニングされた硬化膜を形成する。そして、得られた硬化膜を、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材が有する波長変換部とすることができ、より具体的には、各波長変換層とすることができる。このとき、基材としては、図1および図2に示したように、基板51上に赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bを規則的に配置して有するものを使用することができる。
In the method for forming a wavelength conversion part of the fourth embodiment of the present invention, the curable resin composition of the third embodiment of the present invention described above is applied onto a base material, patterned as necessary, and then exposed. Curing is performed to form a patterned cured film. And the obtained cured film can be made into the wavelength conversion part which the wavelength conversion member of the organic EL element of 1st Embodiment of this invention and 2nd Embodiment has, More specifically, each wavelength conversion layer It can be. At this time, as the substrate, as shown in FIGS. 1 and 2, a substrate having
そして、本発明の第4実施形態の波長変換部の形成方法では、上述の基材上に所望とする形状と配置の波長変換部が形成されるように、少なくとも下記の工程(1)~工程(4)を下記の順で含むことが好ましい。 In the method for forming a wavelength converter of the fourth embodiment of the present invention, at least the following steps (1) to (step) are performed so that the wavelength converter having a desired shape and arrangement is formed on the base material. It is preferable to include (4) in the following order.
(1)本発明の第3実施形態の硬化性樹脂組成物の塗膜を基材上に形成する塗膜形成工程。
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する放射線照射工程。
(3)工程(2)で放射線を照射された塗膜を現像する現像工程。
(4)工程(3)で現像された塗膜を露光する硬化工程。
(1) The coating film formation process which forms the coating film of the curable resin composition of 3rd Embodiment of this invention on a base material.
(2) A radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
(3) A development step of developing the coating film irradiated with radiation in step (2).
(4) A curing step of exposing the coating film developed in step (3).
そして、図3~図6は、本発明の第4実施形態の波長変換部の形成方法の一例を説明する図である。 FIGS. 3 to 6 are diagrams for explaining an example of the method of forming the wavelength conversion unit according to the fourth embodiment of the present invention.
図3は、本発明の第4実施形態の波長変換部の形成方法における塗膜形成工程の一例を説明する基材の断面図である。 FIG. 3 is a cross-sectional view of a base material for explaining an example of a coating film forming step in the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention.
図4は、本発明の第4実施形態の波長変換部の形成方法における放射線照射工程の一例を模式的に説明する断面図である。 FIG. 4 is a cross-sectional view schematically illustrating an example of a radiation irradiation step in the method for forming a wavelength conversion unit according to the fourth embodiment of the present invention.
図5は、本発明の第4実施形態の波長変換部の形成方法における現像工程の一例を説明する基板の断面図である。 FIG. 5 is a cross-sectional view of a substrate for explaining an example of a developing process in the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention.
図6は、本発明の第4実施形態の波長変換部の形成方法における硬化工程の一例を説明する硬化膜および基板の断面図である。 FIG. 6 is a cross-sectional view of a cured film and a substrate for explaining an example of a curing process in the method for forming a wavelength conversion portion of the fourth embodiment of the present invention.
尚、図3~図6中の基材2は、上述したように、基板51上に赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bを規則的に配置して有するものであるが、図3~図6では、便宜上、赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bの図示を省略し、基材2として示している。
The
以下、上述の工程(1)(塗膜形成工程)~工程(4)(硬化工程)についてそれぞれ説明する。 Hereinafter, each of the above-described step (1) (coating film forming step) to step (4) (curing step) will be described.
[工程(1)]
本発明の第4実施形態の波長変換部の形成方法の工程(1)である、塗膜形成工程では、図3に例示するように、本発明の第3実施形態の硬化性樹脂組成物の塗膜1を基材2上に形成する。
[Step (1)]
In the coating film forming step, which is the step (1) of the method for forming the wavelength conversion portion of the fourth embodiment of the present invention, as illustrated in FIG. 3, the curable resin composition of the third embodiment of the present invention
このとき、上述の工程(1)~工程(4)によって硬化膜を形成し、波長変換部として、図1および図2に示した本発明の第1実施形態の有機EL素子100および本発明の第2実施形態の有機EL素子200の赤色波長変換層53Rを形成しようとする場合、上述した硬化性樹脂組成物には、励起光を赤色の光に変換する量子ドットが選択されて含有されている。また、緑色波長変換層53Gを形成しようとする場合、上述した硬化性樹脂組成物には、励起光を緑色の光に変換する量子ドットが選択されて含有され、青色波長変換層53Bを形成しようとする場合に、上述した硬化性樹脂組成物に、励起光を青色の光に変換する量子ドットが選択されて含有されている。
At this time, a cured film is formed by the above-described steps (1) to (4), and the wavelength conversion section is used as the
すなわち、本発明の第4実施形態の波長変換部の形成方法では、有機EL素子の波長変換部材の赤色波長変換層、緑色波長変換層および青色波長変換層を形成しようとする場合、異なる発光特性の量子ドットを含む、例えば、3種の第3実施形態の硬化性樹脂組成物が準備される。そして、上述した工程(1)~工程(4)を含む本発明の第4実施形態の波長変換部の形成方法が繰り返されて、一つの基材上に、赤色波長変換層および緑色波長変換層、そして必要な場合に、青色波長変換層を順次形成することができる。そして、一つの基材上に各波長変換層を形成して波長変換部を構成し、有機EL素子の波長変換部材を得ることができる。 That is, in the method for forming a wavelength conversion unit according to the fourth embodiment of the present invention, when the red wavelength conversion layer, the green wavelength conversion layer, and the blue wavelength conversion layer of the wavelength conversion member of the organic EL element are to be formed, different emission characteristics are obtained. For example, three types of curable resin compositions of the third embodiment are prepared. Then, the method for forming the wavelength conversion section of the fourth embodiment of the present invention including the above-described steps (1) to (4) is repeated, so that the red wavelength conversion layer and the green wavelength conversion layer are formed on one substrate. And, if necessary, the blue wavelength conversion layer can be formed sequentially. And each wavelength conversion layer can be formed on one base material, a wavelength conversion part can be comprised, and the wavelength conversion member of an organic EL element can be obtained.
工程(1)において、塗膜1を形成する基材2は、上述したように、図1の基板51上に赤色カラーフィルタ52R、緑色カラーフィルタ52G、および青色カラーフィルタ52Bを規則的に配置して有するものである。このとき、基板51として、ガラス、石英、シリコン、または、樹脂(例えば、ポリイミド、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、ポリエステル、環状オレフィンの開環重合体およびその水素添加物等)等からなる基板を用いることができる。また、これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の前処理を施しておくこともできる。
In step (1), as described above, the
基材2において、一方の面に、本発明の第3実施形態の硬化性樹脂組成物が塗布された後、プレベークを行い、その硬化性樹脂組成物に含有される有機溶剤等の成分が蒸発し、塗膜1の形成が行われる。
In the
本工程における本発明の第3実施形態の硬化性樹脂組成物の塗布方法としては、例えば、スプレー法、ロールコート法、回転塗布法(スピンコート法またはスピンナ法と称されることもある。)、スリット塗布法(スリットダイ塗布法)、バー塗布法、インクジェット塗布法等の適宜の方法が採用できる。これらのうち、均一な厚みの膜を形成できる点から、スピンコート法またはスリット塗布法が好ましい。 Examples of the coating method of the curable resin composition of the third embodiment of the present invention in this step include a spray method, a roll coating method, and a spin coating method (sometimes referred to as a spin coating method or a spinner method). An appropriate method such as a slit coating method (slit die coating method), a bar coating method, or an ink jet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.
上述のプレベークの条件は、硬化性樹脂組成物を構成する各成分の種類、配合割合等によって異なるが、70℃~120℃の温度で行うのが好ましく、時間は、ホットプレートやオーブン等の加熱装置によって異なるが、おおよそ1分間~15分間程度である。 The pre-baking conditions described above vary depending on the type of each component constituting the curable resin composition, the blending ratio, etc., but it is preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is heated by a hot plate, oven, or the like. Although it varies depending on the apparatus, it is about 1 to 15 minutes.
[工程(2)]
次いで、本発明の第4実施形態の波長変換部の形成方法の工程(2)である、放射線照射工程では、図4に例示するように、工程(1)で基材2上に形成された塗膜1の少なくとも一部に放射線4を照射する。このとき、塗膜1の一部にのみ、放射線4aを照射するには、例えば、所望の形状の形成に対応するパターンのフォトマスク3を介して行う。このフォトマスク3を用いることにより、照射された放射線4の一部がフォトマスクを透過し、その一部の放射線4aが、塗膜1に照射される。
[Step (2)]
Next, in the radiation irradiation step, which is the step (2) of the method for forming the wavelength conversion part of the fourth embodiment of the present invention, as illustrated in FIG. 4, the step was formed on the
照射に使用される放射線4としては、可視光線、紫外線、遠紫外線等が挙げられる。このうち波長が200nm~550nmの範囲にある放射線が好ましく、365nmの紫外線を含む放射線がより好ましい。
Examples of the
放射線4の照射量(露光量)は、放射線4の波長365nmにおける強度を照度計(OAI model 356、Optical Associates Inc.製)により測定した値として、10J/m2~10000J/m2とすることができ、100J/m2~5000J/m2が好ましく、200J/m2~3000J/m2がより好ましい。
The dose of radiation 4 (exposure amount), the intensity at the
[工程(3)]
次に、本発明の第4実施形態の波長変換部の形成方法の工程(3)である、現像工程では、図5に例示するように、放射線照射後の図4の塗膜1を現像して不要な部分を除去し、所定の形状にパターニングされた塗膜1aを得る。
[Step (3)]
Next, in the development step, which is the step (3) of the method for forming a wavelength conversion portion according to the fourth embodiment of the present invention, as illustrated in FIG. Then, unnecessary portions are removed, and the
現像に使用される現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア等の無機アルカリや、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の4級アンモニウム塩や、コリン、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ-[4.3.0]-5-ノネン等のアルカリ性化合物の水溶液が使用できる。上述のアルカリ性化合物の水溶液には、メタノール、エタノール等の水溶性有機溶媒を適当量添加して使用することもできる。さらに、界面活性剤をそれのみで、または、上述の水溶性有機溶媒の添加とともに、適当量添加して使用することもできる。 Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, and tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkaline compound such as a quaternary ammonium salt, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene Can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent.
現像方法は、液盛り法、ディッピング法、シャワー法、スプレー法等のいずれでもよく、現像時間は、常温で5秒間~300秒間とすることができ、好ましくは常温で10秒間~180秒間程度である。現像処理に続いて、例えば、流水洗浄を30秒間~90秒間行った後、圧縮空気や圧縮窒素で風乾することによって、所定の形状にパターニングされた塗膜1aが得られる。
The developing method may be any of a liquid piling method, a dipping method, a shower method, a spray method, and the like. The developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Following the development treatment, for example, washing with running water is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen to obtain the
[工程(4)]
次に、本発明の第4実施形態の波長変換部の形成方法の工程(4)である、硬化工程では、図5に例示されたパターニングされた塗膜1aを、露光装置を用いた露光によって硬化(ポスト露光ともいう)する。これにより、図6に例示するように、基材2上に形成された硬化膜5が得られる。硬化膜5は、上記の工程によって、所望の形状となるようにパターニングされたものとなる。
[Step (4)]
Next, in the curing step, which is the step (4) of the method for forming the wavelength conversion portion of the fourth embodiment of the present invention, the patterned
本発明の第4実施形態の波長変換部の形成方法において、硬化膜5の形成には、上述した本発明の第3実施形態の硬化性樹脂組成物を用いており、本工程では、その塗膜の一部に放射線を照射する。具体的には、工程(1)で形成され、工程(2)および工程(3)でパターニングされた塗膜に対し、所定の放射線を照射する。このときに用いられる放射線としては、例えば、紫外線、遠紫外線、X線、荷電粒子線等が挙げられる。
In the method for forming a wavelength conversion portion of the fourth embodiment of the present invention, the cured
上述の紫外線としては、例えば、g線(波長436nm)、i線(波長365nm)等が挙げられる。遠紫外線としては、例えば、KrFエキシマレーザー光等が挙げられる。X線としては、例えば、シンクロトロン放射線等が挙げられる。荷電粒子線としては、例えば、電子線等が挙げられる。これらの放射線のうち、紫外線の使用が好ましく、紫外線の中でもg線、h線およびi線のうちの少なくとも一つを含む放射線がより好ましい。放射線の露光量としては、0.1J/m2~30000J/m2が好ましい。 Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser light. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Of these radiations, ultraviolet rays are preferably used, and among these ultraviolet rays, radiation containing at least one of g-line, h-line and i-line is more preferable. The exposure dose of radiation is preferably 0.1 J / m 2 to 30000 J / m 2 .
以上の工程(1)~工程(4)によって形成された硬化膜は、樹脂成分中に[B]量子ドットを含んで構成され、[B]量子ドットに基づく蛍光発光(波長変換)機能を有する。したがって、形成された硬化膜は、図1および図2に示した、本発明の第1実施形態の有機EL素子100の波長変換部材50が有する赤色波長変換層53R、緑色波長変換層53Gおよび青色波長変換層53B、並びに、第2実施形態の有機EL素子200の波長変換部材150が有する赤色波長変換層53Rおよび緑色波長変換層53Gを構成することができる。すなわち、以上の工程(1)~工程(4)により、本発明の第1実施形態および第2実施形態の有機EL素子100,200の波長変換部材50,150に含まれて励起光と異なる波長の蛍光を発光する波長変換部として、各波長変換層53R,53G,53Bを形成することができる。
The cured film formed by the above steps (1) to (4) includes [B] quantum dots in the resin component, and has a fluorescence emission (wavelength conversion) function based on [B] quantum dots. . Therefore, the formed cured film includes the red
そのため、工程(1)~工程(4)によって形成された硬化膜は、光の利用効率を高めることができるように、それを構成する樹脂において、厚さ0.1mmでの全光線透過率(JIS K7105)が、好ましくは75%~95%であり、より好ましくは78%~95%であり、さらに好ましくは80%~95%である。全光線透過率がこのような範囲であれば、得られる硬化膜は優れた光利用効率の各波長変換層53R,53G,53Bを形成することができ、波長変換部を構成することができる。 Therefore, the cured film formed by the steps (1) to (4) has a total light transmittance (thickness of 0.1 mm) in the resin constituting the cured film so that the light use efficiency can be increased. JIS K7105) is preferably 75% to 95%, more preferably 78% to 95%, still more preferably 80% to 95%. If the total light transmittance is in such a range, the obtained cured film can form the wavelength conversion layers 53R, 53G, and 53B with excellent light utilization efficiency, and can constitute a wavelength conversion unit.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
<[A]重合体([A]成分)>
本実施例においては、上述した[A]重合体の例として、重合体(A-1)を用いた。以下に、重合体(A-1)の合成例を示す。
<[A] polymer ([A] component)>
In this example, the polymer (A-1) was used as an example of the above-mentioned [A] polymer. The synthesis example of the polymer (A-1) is shown below.
合成例1
[重合体(A-1)の合成]
冷却管と攪拌機を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート150質量部を仕込んで窒素置換した。80℃に加熱して、同温度で、プロピレングリコールモノメチルエーテルアセテート50質量部、2-メタクリロイロキシエチルコハク酸30質量部、ベンジルメタクリレート10質量部、2-エチルヘキシルメタクリレート60質量部および2,2’-アゾビス(2,4-ジメチルバレロニトリル)6質量部の混合溶液を2時間かけて滴下し、この温度を保持して1時間重合した。その後、反応溶液の温度を90℃に昇温させ、さらに1時間重合することにより、重合体(A-1)を得た。重合体(A-1)は、重合体溶液(固形分濃度=33質量%)の状態で得られ、Mw=11000、Mn=6100、Mw/Mn=1.80であった。これを重合体(A-1)溶液とする。
Synthesis example 1
[Synthesis of Polymer (A-1)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heating to 80 ° C., at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of 2-methacryloyloxyethyl succinic acid, 10 parts by mass of benzyl methacrylate, 60 parts by mass of 2-ethylhexyl methacrylate and 2,2 ′ A mixed solution of 6 parts by mass of azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-1). The polymer (A-1) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11000, Mn = 6100, and Mw / Mn = 1.80. This is referred to as a polymer (A-1) solution.
<[B]量子ドット([B]成分)>
本実施例で用いた量子ドットを次に示す。
量子ドットA:InP/ZnSコアシェル型量子ドット
<[B] Quantum dot ([B] component)>
The quantum dots used in this example are shown below.
Quantum dot A: InP / ZnS core-shell quantum dot
そして、下記実施例で用いた量子ドットA:InP/ZnSコアシェル型量子ドットは、一般的に知られている方法で合成することができる。 And the quantum dot A: InP / ZnS core-shell type quantum dot used in the following examples can be synthesized by a generally known method.
例えば、量子ドットA:InP/ZnSコアシェル型量子ドットに関しては技術文献「Journal of American Chemical Society. 2007, 129, 15432-15433」に記載されている方法を参照して合成することができる。 For example, quantum dots A: InP / ZnS core-shell quantum dots can be synthesized by referring to the method described in the technical document “Journal of American Chemical Society. 2007, 129, 15432-15433”.
以上の[A]重合体([A]成分)および[B]量子ドットを用い、さらに、[C]重合開始剤([C]成分)、[D]重合性不飽和化合物([D]成分)を用いて、実施例の硬化性樹脂組成物を調製した。次いで、それらを用いて実施例の硬化膜を形成し、硬化膜の評価を行った。 Using the above [A] polymer ([A] component) and [B] quantum dots, [C] polymerization initiator ([C] component), [D] polymerizable unsaturated compound ([D] component) ) Was used to prepare the curable resin compositions of the examples. Subsequently, the cured film of the Example was formed using them, and the cured film was evaluated.
実施例1
[硬化性樹脂組成物(β-I)の調製]
重合体(A-1)溶液90質量部にメチルシクロヘキサン40質量部を加えて溶解させた後、量子ドットAを10質量部混合して均一な溶液を作製し、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)](BASFジャパン社製 イルガキュア(登録商標)OXE01)10質量部、1,9-ノナンジオールジアクリレート70質量部を混合し、硬化性樹脂組成物(β-I)を調製した。
Example 1
[Preparation of Curable Resin Composition (β-I)]
After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-1) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and 1,2-octanedione-1 -[4- (Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF Japan Ltd.) 10 parts by mass and 70 parts by mass of 1,9-nonanediol diacrylate were mixed and cured. A resin composition (β-I) was prepared.
実施例2
[硬化性樹脂組成物(β-I)を用いた硬化膜の形成]
無アルカリガラス基板上に、実施例1で調製した硬化性樹脂組成物(β-I)をスピンナにより塗布した後、80℃のホットプレート上で2分間プレベークすることにより塗膜を形成した。
Example 2
[Formation of cured film using curable resin composition (β-I)]
The curable resin composition (β-I) prepared in Example 1 was applied onto an alkali-free glass substrate with a spinner and then pre-baked on an 80 ° C. hot plate for 2 minutes to form a coating film.
次に、所定のパターンを備えたフォトマスクを介し、得られた塗膜に高圧水銀ランプを用いて露光量700J/m2として放射線照射を行いた。次いで、0.04質量%の水酸化カリウム水溶液にて23℃、60秒間現像を行った。
次に、得られたパターンに、高圧水銀ランプを用いて露光量10000J/m2として放射線照射を行い、所定の形状にパターニングされた硬化膜を形成した。
Next, radiation was applied to the obtained coating film through a photomask having a predetermined pattern at an exposure amount of 700 J / m 2 using a high-pressure mercury lamp. Next, development was performed at 23 ° C. for 60 seconds with a 0.04 mass% potassium hydroxide aqueous solution.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m 2 using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.
次に、パターニングされた硬化膜の端部分を光学顕微鏡で観察し、現像残渣がなく、パターンの直線部分が直線状に形成されている場合にパターニング性良好と判断した。
その結果、硬化性樹脂組成物(β-I)を用い、パターニングして形成された硬化膜のパターニング性は良好であった。
Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-I) was good.
実施例3
[蛍光特性の評価]
実施例2の形成方法による硬化膜について、さらに、絶対PL量子収率測定装置(C11347-01、浜松ホトニクス社)を用いて、25℃における蛍光量子収率を調べた。蛍光量子収率は38%であり、蛍光特性は良好と判断した。
したがって、実施例2の形成方法による硬化膜は量子ドットを含有する。そして、実施例2の形成方法による硬化膜は、有機EL素子に適用されて、その波長変換部材の波長変換部として、赤色波長変換層を構成することができ、有機EL素子の高輝度化を実現することができる。
Example 3
[Evaluation of fluorescence characteristics]
The cured film obtained by the formation method of Example 2 was further examined for fluorescence quantum yield at 25 ° C. using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 38%, and the fluorescence characteristics were judged to be good.
Therefore, the cured film by the forming method of Example 2 contains quantum dots. And the cured film by the formation method of Example 2 is applied to an organic EL element, and a red wavelength conversion layer can be formed as a wavelength conversion part of the wavelength conversion member, thereby increasing the brightness of the organic EL element. Can be realized.
本発明の硬化性樹脂組成物を用いて形成された硬化膜は、蛍光特性に優れ、また、パターニングも容易である。したがって、波長変換層または波長変換フィルムとして、表示素子やそれを用いた電子機器の他に、LEDおよび太陽電池の分野でも利用することができる。 The cured film formed using the curable resin composition of the present invention has excellent fluorescence characteristics and is easy to pattern. Therefore, it can utilize also in the field | area of LED and a solar cell other than a display element and an electronic device using the same as a wavelength conversion layer or a wavelength conversion film.
1,1a 塗膜
2 基材
3 フォトマスク
4,4a 放射線
5 硬化膜
10 回路基板
11 基板
12 バッファ層
13 シリコン層
13s ソース
13d ドレイン
14 ゲート
15 選択用TFT
16 キャパシタ電極
17a コンタクトプラグ
18 第1平坦化膜
19 データライン
20 第2平坦化膜
30,130 有機EL素子アレイ
31,131 有機EL部
31a 画素電極
31b,131b 有機発光層
31c 共通電極
32 隔壁部
40 パッシベーション層
50,150 波長変換部材
51 基板
52R 赤色カラーフィルタ
52G 緑色カラーフィルタ
52B 青色カラーフィルタ
53R 赤色波長変換層
53G 緑色波長変換層
53B 青色波長変換層
54 ブラックマトリクス
100,200 有機EL素子
151 青色拡散層
DESCRIPTION OF
16
Claims (8)
前記波長変換部が、
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)上記(a1)以外の炭素数4~20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物を用いて形成されたものであることを特徴とする有機EL素子。 An organic EL element having a light emitting part and a wavelength converting part,
The wavelength converter is
[A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms other than (a1) in the same or different polymer molecules, and [B] An organic EL device formed using a curable resin composition containing quantum dots.
[B]量子ドット
を含有する硬化性樹脂組成物であって、
請求項1~5のいずれか1項に記載の有機EL素子の前記波長変換部の形成に用いられることを特徴とする硬化性樹脂組成物。 [A] a polymer having (a1) a structural unit containing an acidic group and (a2) a structural unit containing an organic group having 4 to 20 carbon atoms in the same or different polymer molecules, and [B] a quantum dot A curable resin composition containing,
6. A curable resin composition, which is used for forming the wavelength conversion part of the organic EL device according to claim 1.
(1)請求項6に記載の硬化性樹脂組成物の塗膜を基材上に形成する工程、
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する工程、
(3)工程(2)で放射線を照射された塗膜を現像する工程、および
(4)工程(3)で現像された塗膜を露光する工程
を有することを特徴とする波長変換部の形成方法。 A method of forming a wavelength conversion unit for forming the wavelength conversion unit of an organic EL element having a light source unit that emits light containing at least blue light and a wavelength conversion unit,
(1) The process of forming the coating film of the curable resin composition of Claim 6 on a base material,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) The step of developing the coating film irradiated with radiation in the step (2), and (4) The step of exposing the coating film developed in the step (3). Method.
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| JP2016564767A JPWO2016098570A1 (en) | 2014-12-15 | 2015-11-30 | Organic EL element, curable resin composition, wavelength conversion part forming method, and organic EL device |
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