Resin molded product and manufacturing method thereof, and wavelength conversion member and illumination member
12187011 ยท 2025-01-07
Assignee
Inventors
Cpc classification
H01L2924/00012
ELECTRICITY
H01L2924/00014
ELECTRICITY
H01L2924/00014
ELECTRICITY
H01L2924/00012
ELECTRICITY
B32B27/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
B32B27/00
PERFORMING OPERATIONS; TRANSPORTING
C09K11/02
CHEMISTRY; METALLURGY
Abstract
A resin molded product is provided and capable of increasing a degree of freedom of a shape compared to prior arts, further provided with increased durability against environmental changes and improved reliability, a manufacturing method thereof, and a wavelength conversion member and an illumination member. The resin molded product is implemented by molding resin in which quantum dots are dispersed. The resin preferably contains a dispersant composed of metal soap. For example, a wavelength conversion bar (fluorescent bar) interposed between a light-emitting device such as an LED and a light-guiding board is molded using quantum-dot-containing resin.
Claims
1. A method for manufacturing a resin molded product, for a backlight of a display, the resin molded product obtained by molding a resin composition in which quantum dots are dispersed, the method comprising: stirring resin and metal soap to form a resin mixture, wherein the metal soap is contained in the resin in a range of 1 ppm to 40,000 ppm with respect to the resin; obtaining a quantum dot liquid by dispersing the quantum dots in a solvent; obtaining a resin composition in a solid state by kneading the quantum dot liquid in the resin mixture, wherein a weight ratio of the metal soap to the quantum dots is within a range from 1/10:1 to 10:1; and forming a sheet-like shaped resin molded product by extrusion molding the resin composition in the solid state.
2. The method according to claim 1, wherein calcium stearate is used for the metal soap.
3. The method according to claim 1, wherein organosilane or hexane is used for the solvent.
4. The method according to claim 1, wherein a scattering agent is mixed into the quantum dot liquid.
5. The method according to claim 1, wherein the resin includes polypropylene.
6. The method according to claim 1, further comprising: mixing an elastomer with the resin mixture.
7. The method according to claim 4, wherein the scattering agent includes minute particles, the minute particles comprising one of SiO.sub.2, BN, or AlN.
8. The method according to claim 1, wherein the quantum dots contain at least one of ZnCuInS, CdS, CdSe, ZnS, ZnSe, InP, or CdTe.
9. The method according to claim 1, wherein each quantum dot possesses a core-shell structure comprising a core and a shell, the shell of the core-shell structure comprises a first shell that covers a surface of the core, and a second shell that covers a surface of the first shell, thereby forming a multi-shell configuration, and a bandgap of the second shell is greater than a bandgap of the first shell.
10. The method according to claim 1, wherein in the obtaining of the resin composition, the metal soap wraps the quantum dots in the resin to improve dispersibility of the quantum dots.
11. A method, for a backlight of a display, the resin molded product obtained by molding a resin composition in which quantum dots are dispersed, the method comprising: stirring resin and metal soap to form a resin mixture, wherein the metal soap is contained in the resin in a range of 1 ppm to 40,000 ppm with respect to the resin; obtaining a quantum dot liquid by dispersing the quantum dots in a solvent; improving dispersibility of the quantum dots in the resin mixture by kneading the resin mixture and the quantum dot liquid to obtain a resin composition in a solid state, wherein a weight ratio of the metal soap to the quantum dots in the resin composition is within a range from 1/10:1 to 10:1; and forming a sheet-like shaped resin molded product by extrusion molding the resin composition in the solid state.
12. The method according to claim 11, wherein in the improving of the dispersibility of the quantum dots, the metal soap wraps the quantum dots in the resin to improve the dispersibility of the quantum dots.
13. The method according to claim 11, wherein the metal soap is calcium stearate.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(34) Hereinafter, embodiments of the present invention will be described in detail. A resin molded product according to the present embodiment is configured by molding resin on which many quantum dots are dispersed.
(35) The quantum dots of the present embodiment can each include a core of semiconductor particles and a shell that coats the perimeter of the core. For example, CdSe is used for the core, but the material thereof is not particularly limited. For example, a core material containing at least Zn and Cd, a core material containing Zn, Cd, Se and S, or a composite of some of ZnCuInS, CdS, CdSe, ZnS, ZnSe, InP and CdTe can be used.
(36) The shell protects the core as a fluorescence section. Quantum efficiency improves by removing surface defects or dangling bond of the core. As an example, a bandgap of the shell is greater than a bandgap of the core, but the bandgap is not limited to this.
(37) The shell may have a so-called multi-shell structure including a first shell (shell I) that coats the surface of the core and a second shell (shell II) that coats the surface of the first shell. In this case, for example, the bandgap of the second shell is greater than the bandgap of the first shell, but the bandgap is not limited to this.
(38) The quantum dots according to the present embodiment may be composed of only cores without any shells being formed. That is, the quantum dots may not be provided with any coating structure with shells as long as the quantum dots are provided with at least cores. For example, when the cores are coated with shells, a region having a coating structure may be small or a coating portion may be too thin to analyze or check the coating structure. Therefore, it is possible to determine quantum dots by an analysis regardless of the presence/absence of the shells.
(39) In the present embodiment, metal soap is preferably included as a dispersant to appropriately disperse many quantum dots in the resin of the resin molded product. Thus, it is possible to effectively enhance the dispersibility in the resin of quantum dots in the resin molded product.
(40) The metal soap is made of minute particles, exhibits excellent dispersibility with respect to quantum dots which are inorganic substances and adds sufficient smoothness to resin.
(41) Fatty acid such as stearic acid, oleic acid, ricinoleic acid, octylic acid, lauric acid or metal such as lithium, magnesium, calcium, barium, zinc is used for the metal soap. Among them, the metal soap is preferably calcium stearate.
(42) In the present embodiment, the metal soap contained in resin preferably falls within a range of 1 ppm to 40,000 ppm by weight with respect to the resin. This makes it possible to increase dispersibility or smoothness and also prevents turbidity or surface irregularity or the like on the resin surface. The weight ratio of the metal soap to the quantum dots contained is 1/10 (1:10) to 10 (10:1). The quantum dots are suitably on the order of 10 ppm to 4,000 ppm by weight with respect to the resin. Therefore, the metal soap is suitably 1 ppm to 40,000 ppm by weight with respect to the resin.
(43) Thus, the Applicant has discovered that when the metal soap (especially, calcium stearate) is introduced, the metal soap wraps the quantum dots and thereby improves dispersibility.
(44) Furthermore, in the present embodiment, the resin preferably contains elastomer. For example, when polypropylene (PP) is selected as resin, transparency can be improved by mixing elastomer. In this case, elastomer highly compatible with polypropylene resin is preferable.
(45) In the present embodiment, the resin preferably contains a scattering agent. Addition of the scattering agent can improve a light emission characteristic. Minute particles such as silica (SiO.sub.2), BN, AlN can be presented as the scattering agent.
(46) The resin molded product according to the present embodiment may be configured so as to include a resin layer in which quantum dots are contained in the resin and a coating layer that coats the surface of the resin. Glass coating, epoxy coating, diamond-like carbon (DLC) or the like can be presented as the coating layer. This makes it possible to improve durability with respect to water content in the atmosphere and thereby provide high reliability.
(47) Although the resin constituting the resin molded product is not particularly limited, it is possible to use polypropylene, polyethylene, polystyrene, AS resin, ABS resin, methacryl resin, polyvinyl chloride, polyacetal, polyamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyethersulphone, polyphenylene sulfide, polyamide imide, polymethylpentene, liquid crystal polymer, epoxy resin, phenol resin, urea resin, melamine resin, epoxy resin, diallyl phthalate resin, unsaturated polyester resin, polyimide, polyurethane, silicone resin, or a mixture of some of these substances.
(48) The resin molded product according to the present embodiment may include quantum dots fluorescent pigments other than quantum dots and fluorescent substances as fluorescent dye. Examples of such materials include, a red light emission quantum dot that emits red light when irradiated with blue light and a green light emission fluorescent substance that emits green light or a red light emission quantum dot that emits green light and a red light emission fluorescent substance that emits red light. White light can be obtained by irradiating such a resin molded product with blue light. Examples of the fluorescent substance include YAG (yttrium aluminum garnet) base, TAG (terbium aluminum garnet) base, sialon base, BOS (barium orthosilicate) base, but the material is not particularly limited.
(49) A dispersion state of quantum dots of the present embodiment refers to a dispersion state in which quantum dots are singly dispersed in resin, a dispersion state in which a plurality of quantum dots form an aggregate and such aggregates are dispersed in resin or single quantum dots and an aggregate of quantum dots are dispersed respectively in resin.
(50) Not more than several hundreds of aggregates are contained in resin within a square of 500 nm. To be more specific, on the order of 3 to 300 aggregates are preferably contained. Regarding the scale of each aggregate, the length in the longitudinal direction is 100 nm or less and preferably 70 nm or less. Furthermore, the aggregate is preferably composed of not more than several hundreds of aggregated quantum dots. To be more specific, the aggregate is preferably composed of on the order of 1 to 300 quantum dots. In this way, according to the present embodiment, quantum dots form each aggregate and these aggregates are appropriately dispersed in resin.
(51) The following applications can be provided using the resin molded product according to the present embodiment.
(52) In
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(54) The light-guiding board 4 itself may be molded using the quantum-dot-containing resin of the present embodiment. In this case, it does not matter whether or not the wavelength conversion sheet 5 is present. Both the light-guiding board 4 and the wavelength conversion sheet 5 may also include quantum dots that emit green light and quantum dots that emit red light. Furthermore, the light-guiding board 4 may also include quantum dots that emit green light and the wavelength conversion sheet may include quantum dots that emit red light. Conversely, the light-guiding board 4 may include quantum dots that emit red light and the wavelength conversion sheet 5 may include quantum dots that emit green light.
(55) Note that the fluorescence member using the resin molded product of the present embodiment can conduct wavelength conversion, and therefore, it can be said to be a wavelength conversion member, and both are not clearly distinguishable.
(56) In
(57) As a mode of the illumination device, the structure shown in
(58) Furthermore, a structure may also be adopted in which the space between the light-emitting device of the illumination device and the illumination surface (light emission surface) is filled with quantum-dot-containing resin. That is, it is possible to create an illumination of a free shape.
(59)
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(61) In
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(63) The light diffusion apparatus 17 shown in
(64) In
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(66) The light source apparatus 19 in
(67) The light source apparatus 19 has a structure in which the reflector 23 is arranged around each light source 22, light returning to the light source apparatus 19 side is reflected by the reflector 23, allowing the entire surface of the light source apparatus 19 to emit uniform light toward the display section.
(68) In the light source apparatus 20 shown in
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(70) Note that although not shown in
(71) Although the sheet member 65 is formed as a single sheet, a plurality of sheet members 65 may be connected together so as to have a predetermined size. The configuration in which the plurality of sheet members 65 connected together through tiling will be referred to as a composite sheet member hereinafter.
(72) In
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(74) As shown in
(75) The container 71 is provided with a storage space 73 that can accommodate and store the molded body 72 including a wavelength conversion substance. The container 71 is preferably a transparent member. The term transparent refers to what is generally recognized as being transparent or what has a visible light transmittance of approximately 50% or more.
(76) The longitudinal and lateral sizes of the container 71 are on the order of several mm to several tens of mm, and the longitudinal and lateral sizes of the storage space 73 are on the order of several hundreds of m to several mm.
(77) As shown in
(78) As shown in
(79) The container 71 shown in
(80) As shown in
(81) The molded body 72 containing the wavelength conversion substance can be inserted into the storage space 73 by means such as pressure fitting or adhesion. When the molded body 72 is press-fitted, by molding the molded body 72 containing the wavelength conversion substance in completely the same size as the storage space 73 or in a size slightly greater than the storage space and inserting the molded body 72 containing the wavelength conversion substance into the storage space 73 while adding a pressure, it is possible to prevent a gap from being produced not only in the molded body 72 containing the wavelength conversion substance but also between the molded body 72 containing the wavelength conversion substance and the container 71.
(82) Furthermore, when the molded body 72 containing the wavelength conversion substance is adhered and fixed to the storage space 73, the molded body 72 containing the wavelength conversion substance is molded so as to be smaller than the storage space 73, and with an adhesion layer applied to the side face of the molded body 72 containing the wavelength conversion substance, the molded body 72 containing the wavelength conversion substance is inserted into the storage space 73. In this case, the cross-sectional area of the molded body 72 may be slightly smaller than the cross-sectional area of the storage space 73. In this way, the molded body 72 containing the wavelength conversion substance and the container 71 come into close contact with each other via the adhesion layer, making it possible to prevent a gap from being formed between the molded body 72 containing the wavelength conversion substance and the container 71. For the adhesion layer, the same resin as the molded body 72 or resin having a common basic structure can be used. Alternatively, a transparent adhesive member may also be used as the adhesion layer.
(83) Furthermore, a refractive index of the molded body 72 containing the wavelength conversion substance may be preferably smaller than a refractive index of the container 71. Thus, part of light incident on the molded body 72 containing the wavelength conversion substance is totally reflected by the side wall portion of the container 71 facing the storage space 73. This is because an angle of incidence on the medium side which has a smaller refractive index is greater than an angle of incidence on the medium side which has a greater refractive index. This makes it possible to reduce the amount of light leaking from the side of the container 71 toward the outside, thus improving color conversion efficiency and light emission intensity.
(84) A light-emitting device is disposed on the light incident surface 71a side of the wavelength conversion apparatus 70 shown in
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(86) The light-emitting device 75 shown in
(87) An undersurface of the container 79 of the wavelength conversion member 76 shown in
(88) As shown in
(89) As shown in
(90) It is thereby possible to freely mold the quantum-dot-containing resin according to the present embodiment into various shapes and manufacture a resin molded product of a predetermined shape at low cost. In this case, the quantum-dot-containing resin includes metal soap (preferably calcium stearate), it is possible to increase dispersibility of particles of quantum dots and improve durability with respect to environmental changes. Note that an example using quantum dots that emit green light and quantum dots that emit red light when blue light is radiated has been described as an application using the resin molded product according to the present embodiment, but the application is not limited to this. That is, as the resin molded product in the present embodiment, a resin molded product containing quantum dots and fluorescent substances other than the quantum dots can also be used for the applications in
(91) The method for manufacturing a resin molded product according to the present embodiment has a feature of molding a resin composition obtained by dispersing quantum dots in resin. A specific manufacturing method thereof will be described using
(92) In step ST1 in
(93) Next, in step ST2 in
(94) Next, in step ST3 in
(95) Next, in step ST4 in
(96) In step ST6 in
(97) According to the method for manufacturing a resin molded product of the present embodiment described above, it is possible to freely create molded products of various shapes using quantum-dot-containing resin.
(98) The present embodiment mixes the metal soap when generating the PP mixture in ST1 in order to increase dispersibility of quantum dots. The metal soap wraps the quantum dots in the resin. The metal soap is distributed around the quantum dots and the dispersibility of the quantum dots in the resin thereby further improves. For example, instead of mixing the metal soap during injection molding in ST6, the PP mixture into which the metal soap is introduced is extruded and kneaded. Thus, dispersibility of quantum dots with respect to resin in the resin molded product effectively increases.
(99) The order of steps ST1 and ST2 shown in
(100) Furthermore, for example, instead of generating the PP mixture beforehand as shown in ST1, after generating the QD solution in ST2, polypropylene, elastomer and metal soap may be mixed into the QD solution. In this case, the order in which polypropylene, elastomer and metal soap are mixed is not determined.
(101) Furthermore, according to the present embodiment, a scattering agent may be mixed into the QD solution. Minute particles of silica (SiO.sub.2), BN, AlN or the like can be presented as the scattering agent.
EXAMPLES
(102) Hereinafter, examples and comparative examples implemented to clarify the effects of the present invention will be described in detail. Note that the present invention will not be limited by the following examples at all. For example, although examples will be described in the following examples where a resin molded product is molded by injection molding, the resin molded product of the present invention may also be created using methods such as extrusion molding, hollow molding, thermoforming, compression molding, calendar molding, inflation method or casting method.
Materials
(103) The following materials were used to create the following resin molded product. Resin: polypropylene Elastomer: Hybrar (registered trademark) 7311 manufactured by KURARAY CO., LTD Organosilane: cyclohexyl (dimethoxy) methyl silane Quantum dot (QD): red light emission quantum dots and green light emission quantum dots having core/shell structure Dispersant: calcium stearate
Extruder
(104) Small two-axis extruder Name of manufacturer: Kawabe Manufacturing Co., Ltd. Specification screw diameter: 16 mm L/D: 40 Maximum kneading temperature: 400 C.
Sample 1-1
(105) (1) 1.6 kg of polypropylene (referred to as PP), 0.4 kg of elastomer and approximately 1 g of calcium stearate (referred to as StCa) were entered in a vinyl chuck bag (3450 cm) and well stirred to form a PP mixture. (2) Next, 4 g of quantum dots (referred to as QD) was dispersed into 40 ml of purified and distillated organosilane, added to the PP mixture and well stirred until it became uniform. (3) The mixture obtained in (2) was introduced into a hopper of the extruder, a PP wire was extruded and kneaded at an extrusion temperature of 200 C. to 250 C. (adjusted as appropriate). The PP wire was directly introduced from an outlet nozzle to a water tank and cooled to acquire a wire having a diameter of 1 to 2 mm. This wire was further introduced into a cutter and a pellet having a length of approximately 4 mm was created. The QD concentration of sample 1-1 was 2000 ppm.
Sample 1-2
(106) 0.8 g of QD was dispersed into 40 ml of organosilane, 2.5 ml thereof was added to 500 g of the PP mixture and the rest of operation conducted was similar to that of sample 1-1. The QD concentration in sample 1-2 was 1000 ppm.
Sample 1-3
(107) The same operation as that in sample 1-1 was conducted except using the QD liquid used in sample 1-2 having a QD concentration of 1000 ppm diluted ten times with organosilane. The QD concentration in sample 1-3 was 100 ppm.
Sample 2-1
(108) The mixing condition and the extrusion condition were changed using the same raw materials as those of sample 1-1. To be more specific, PP and elastomer were mixed with the QD liquid. The extrusion temperature was raised to sufficiently evaporate organosilane more than in sample 1 and the extrusion speed was decreased. The QD concentration in sample 2-1 was 2000 ppm.
Sample 2-2
(109) Sample 2-2 was created using a method similar to that of sample 2-1 but calcium stearate was not used. The QD concentration in sample 2-2 was 2000 ppm.
Sample 3
(110) Sample 3 was created using a method similar to that of sample 2-1. However, hexane was used as a solvent to disperse QD. Use of hexane helps QD disperse well, and even when PP was mixed with elastomer, there was less stickness. The QD concentration in sample 3 was 2000 ppm.
Sample 4-1
(111) Sample 4-1 was created using a method similar to that in sample 3. However, the QD concentration was set to 200 ppm.
Sample 4-2
(112) Sample 4-2 was created using a method similar to that in sample 4-1. However, 5 weight % of silica minute particles (SiO.sub.2 minute particles having a particle diameter of 1.0 m) was added as a scattering agent. The QD concentration in sample 4-2 was 200 ppm.
Sample 4-3
(113) Sample 4-3 was created using a method similar to that in sample 4-1. However, 10 weight % of silica minute particles was added as the scattering agent. The QD concentration in sample 4-3 was 200 ppm.
(114) [Durability Test on PP Extrusion Molded Product with Dispersed QD]
(115) A wire-like sample having a length of 5 cm was sandwiched by a sample holder provided with three blue (wavelength: 450 nm) LEDs, the LEDs were turned on under the following conditions and a time variation in light emission intensity from each sample was traced.
Durability Test Conditions
(116) (1) 60 C. 90RH, LED turned ON at 60 mA (2) 60 C. 90RH, LED turned ON at 30 mA (3) 60 C. 90RH, LED not turned ON (4) In room, LED turned ON at 60 mA (5) Under 60 C. atmosphere, LED turned ON at 60 mA
(117) Note that a thermo-hygrostat IW222 manufactured by YAMATO Scientific Co., Ltd. was used for a durability test under 60 C. 90RH. Regarding light emission intensity, each sample was sandwiched by a sample holder provided with three blue (wavelength: 450 nm) LEDs and when the LEDs were caused to emit light with LED excitation light of 450 nm (20 mW3), a total luminous flux was measured using a total luminous flux measuring system manufactured by OTSUKA ELECTRONICS Co., Ltd.
(118) Table 1 below shows experiment results of samples 1-1 and 1-2.
(119) TABLE-US-00001 TABLE 1 GRAPH GREEN PEAK GREEN PEAK GREEN PEAK SAMPLE NAME COMMENT TIME (h) CLASSIFICATION REMARKS WAVELENGTH (nm) INTENSITY AREA RT 60 mA 1000 ppm 0 1000 ppm 60 mA ON 533 0.0000250 0.001170 60 ATMOSPHERE 60 mA 1000 ppm 0 1000 ppm 60 mA ON 533 0.0000228 0.001082 60-90 60 mA 1000 ppm 0 1000 ppm 60 mA ON 532 0.0000220 0.001042 60-90 30 mA 1000 ppm 0 1000 ppm 30 mA ON 532 0.0000200 0.000937 60-90 NOT ON 1000 ppm 0 1000 ppm NOT ON 534 0.0000194 0.000926 RT 60 mA 2000 ppm 0 2000 ppm 60 mA ON 534 0.0000150 0.000725 60 ATMOSPHERE 60 mA 2000 ppm 0 2000 ppm 60 mA ON 534 0.0000167 0.000795 60-90 60 mA 2000 ppm 0 2000 ppm 60 mA ON 534 0.0000160 0.000752 60-90 30 mA 2000 ppm 0 2000 ppm 30 mA ON 534 0.0000162 0.000789 60-90 NOT ON 2000 ppm 0 2000 ppm NOT ON 534 0.0000194 0.000917 RT 60 mA 1000 ppm 43 1000 ppm 60 mA ON 534 0.0000406 0.001853 60 ATMOSPHERE 60 mA 1000 ppm 41 1000 ppm 60 mA ON 535 0.0000388 0.001783 60-90 60 mA 1000 ppm 43 1000 ppm 60 mA ON 490 0.0000116 0 60-90 30 mA 1000 ppm 41 1000 ppm 30 mA ON 490 0.0000089 0 60-90 NOT ON 1000 ppm 41 1000 ppm NOT ON 532 0.0000203 0.000975 RT 60 mA 2000 ppm 41 2000 ppm 60 mA ON 536 0.0000278 0.001294 60 ATMOSPHERE 60 mA 2000 ppm 43 2000 ppm 60 mA ON 534 0.0000283 0.001270 60-90 60 mA 2000 ppm 41 2000 ppm 60 mA ON 490 0.0000054 0 60-90 30 mA 2000 ppm 41 2000 ppm 30 mA ON 490 0.0000079 0 60-90 NOT ON 2000 ppm 41 2000 ppm NOT ON 533 0.0000229 0.001092 RT 60 mA 1000 ppm 92 1000 ppm 60 mA ON 535 0.0000400 0.001829 60 ATMOSPHERE 60 mA 1000 ppm 92 1000 ppm 60 mA ON 534 0.0000371 0.001681 60-90 NOT ON 1000 ppm 92 1000 ppm NOT ON 534 0.0000197 0.000959 RT 60 mA 2000 ppm 92 2000 ppm 60 mA ON 536 0.0000252 0.001164 60 ATMOSPHERE 60 mA 2000 ppm 92 2000 ppm 60 mA ON 533 0.0000233 0.001042 60-90 NOT ON 2000 ppm 92 2000 ppm NOT ON 535 0.0000212 0.001015 RT 60 mA 1000 ppm 160 1000 ppm 60 mA ON 533 0.0000396 0.001795 60 ATMOSPHERE 60 mA 1000 ppm 160 1000 ppm 60 mA ON 532 0.0000354 0.001587 60-90 NOT ON 1000 ppm 160 1000 ppm NOT ON 534 0.0000200 0.000975 RT 60 mA 2000 ppm 160 2000 ppm 60 mA ON 534 0.0000237 0.001091 60 ATMOSPHERE 60 mA 2000 ppm 160 2000 ppm 60 mA ON 532 0.0000175 0.000783 60-90 NOT ON 2000 ppm 160 2000 ppm NOT ON 534 0.0000207 0.000998 RT 60 mA 1000 ppm 235 1000 ppm 60 mA ON 532 0.0000374 0.001695 60 ATMOSPHERE 60 mA 1000 ppm 235 1000 ppm 60 mA ON 532 0.0000313 0.001394 60-90 NOT ON 1000 ppm 235 1000 ppm NOT ON 535 0.0000191 0.000939 RT 60 mA 2000 ppm 235 2000 ppm 60 mA ON 534 0.0000189 0.000874 50 ATMOSPHERE 60 mA 2000 ppm 235 2000 ppm 60 mA ON 532 0.0000123 0.000553 60-90 NOT ON 2000 ppm 235 2000 ppm NOT ON 535 0.0000195 0.000936 EXCITATION RED PEAK RED HALF- LIGHT LIGHT EMISSION TOTAL GREEN HALF-VALUE WIDTH WAVELENGTH RED PEAK RED PEAK VALUE WIDTH WAVELENGTH EXCITATION EFFICIENCY LUMINOUS SAMPLE NAME (nm) (nm) INTENSITY AREA (nm) (nm) LIGHT AREA [Im/W] FLUX [Im] RT 60 mA 45 627 0.0000299 0.001149 33 445 0.010712 6.803299 1.234288 60 ATMOSPHERE 60 mA 46 627 0.0000272 0.001055 34 445 0.009431 6.317462 1.125867 60-90 60 mA 45 627 0.0000258 0.001002 34 446 0.009542 6.024017 1.099665 60-90 30 mA 44 627 0.0000236 0.000911 33 445 0.008377 5.300151 0.972471 60-90 NOT ON 46 626 0.0000227 0.000887 34 446 0.008726 5.297202 0.982006 RT 60 mA 45 626 0.0000238 0.000931 34 446 0.003045 3.993342 0.720036 60 ATMOSPHERE 60 mA 45 626 0.0000220 0.000861 33 445 0.005075 4.557058 0.796676 60-90 60 mA 45 625 0.0000235 0.000907 33 446 0.003462 4.291789 0.743772 60-90 30 mA 46 626 0.0000250 0.000983 33 446 0.003292 4.495346 0.777971 60-90 NOT ON 45 627 0.0000254 0.000993 34 446 0.005094 5.236708 0.905877 RT 60 mA 43 629 0.0000323 0.001199 31 445 0.011079 9.349181 1.640419 60 ATMOSPHERE 60 mA 43 629 0.0000258 0.000981 32 445 0.010164 8.825713 1.527208 60-90 60 mA 9 621 0.0000012 0.000089 70 445 0.017261 3.247443 0.558714 60-90 30 mA 9 626 0.0000012 0.000083 69 444 0.014804 2.517846 0.456634 60-90 NOT ON 47 626 0.0000212 0.000840 33 445 0.007944 5.661649 0.980252 RT 60 mA 44 628 0.0000286 0.001099 32 445 0.003180 6.263972 1.090666 60 ATMOSPHERE 60 mA 42 630 0.0000207 0.000773 31 445 0.006424 6.170710 1.068242 60-90 60 mA 9 580 0.0000006 0.000000 82 445 0.006386 1.269261 0.226552 60-90 30 mA 13 581 0.0000019 0.000130 66 445 0.009195 2.305427 0.398572 60-90 NOT ON 45 626 0.0000260 0.001014 33 446 0.004416 5.704682 0.983647 RT 60 mA 43 629 0.0000303 0.001136 31 445 0.010923 9.233728 1.605952 60 ATMOSPHERE 60 mA 42 630 0.0000228 0.000862 31 445 0.010235 8.327016 1.438285 60-90 NOT ON 47 627 0.0000202 0.000818 33 446 0.007308 5.526385 0.952373 RT 60 mA 43 630 0.0000253 0.000963 32 446 0.003246 5.662095 0.979023 60 ATMOSPHERE 60 mA 42 631 0.0000176 0.000659 31 445 0.006431 5.249773 0.910596 60-90 NOT ON 45 627 0.0000238 0.000943 34 446 0.003847 5.345209 0.911598 RT 60 mA 42 629 0.0000296 0.001095 31 445 0.010844 8.995316 1.562622 60 ATMOSPHERE 60 mA 42 630 0.0000212 0.000797 32 445 0.010360 7.916904 1.353958 60-90 NOT ON 47 627 0.0000195 0.000795 34 446 0.006894 5.333972 0.945267 RT 60 mA 43 630 0.0000245 0.000921 32 445 0.003340 5.282379 0.918929 60 ATMOSPHERE 60 mA 42 630 0.0000150 0.000557 31 445 0.006768 4.382666 0.744848 60-90 NOT ON 45 627 0.0000230 0.000921 34 446 0.003766 5.267036 0.894614 RT 60 mA 43 630 0.0000276 0.001023 31 445 0.010718 8.672344 1.479071 60 ATMOSPHERE 60 mA 42 630 0.0000190 0.000717 31 445 0.010405 7.177321 1.225431 60-90 NOT ON 47 627 0.0000188 0.000778 34 446 0.006627 5.343000 0.913735 RT 60 mA 43 630 0.0000209 0.000784 31 445 0.003567 4.485485 0.767409 50 ATMOSPHERE 60 mA 43 631 0.0000117 0.000439 31 445 0.006795 3.484425 0.593527 60-90 NOT ON 45 627 0.0000225 0.000900 33 446 0.003594 5.023353 0.855408
(120)
(121)
(122) Table 2 below shows experiment results of samples 2-1 and 2-2.
(123) TABLE-US-00002 TABLE 2 GREEN PEAK GRAPH WAVELENGTH GREEN PEAK GREEN PEAK SAMPLE NAME COMMENT TIME (h) CLASSIFICATION REMARKS (nm) INTENSITY AREA WITH StCa 60 mA 60-90 60 mA 0 60-90 60 mA ON 535 0.0000176 0.000918 WITH StCa 30 mA 60-90 30 mA 0 60-90 30 mA ON 535 0.0000249 0.001235 WITH StCa NOT ON 60-90 NOT ON 0 60-90 NOT ON 535 0.0000171 0.000809 WITH StCa RT RT 60 mA 0 ATMOSPHERE ON 60 mA ON 535 0.0000191 0.000918 WITH StCa 60 C 60 ATMOSPHERE 60 mA 0 ATMOSPHERE ON 60 mA ON 534 0.0000163 0.000844 No StCa 60 mA 60-90 60 mA 0 60-90 60 mA ON 534 0.0000202 0.001033 No StCa 30 mA 60-90 30 mA 0 60-90 30 mA ON 534 0.0000178 0.000934 No StCa NOT ON 60-90 NOT ON 60-90 NOT ON 533 0.0000147 0.000694 No StCa RT RT 60 mA 0 ATMOSPHERE ON 60 mA ON 533 0.0000144 0.000675 NO StCa 60
C 60 ATMOSPHERE 60 mA 0 ATMOSPHERE ON 60 mA ON 533 0.0000137 0.000713 FIRST TIME 2000 ppm 60-90 60 mA 2000 ppm 0 60-90 60 mA ON 534 0.0000205 0.001026 RETRY 60 mA RETRY WITH StCa 60 mA 60-90 60 mA 16 60-90 60 mA ON 490 0.0000091 0 WITH StCa 30 mA 60-90 30 mA 16 60-90 30 mA ON 527 0.0000134 0.000669 WITH StCa NOT ON 60-90 NOT ON 16 60-90 NOT ON 534 0.0000158 0.000769 WITH StCa RT RT 60 mA 16 ATMOSPHERE ON 60 mA ON 536 0.0000417 0.001943 WITH StCa 60
C 60 ATMOSPHERE 60 mA 16 ATMOSPHERE ON 60 mA ON 535 0.0000394 0.001832 No StCa 60 mA 60-90 60 mA 16 60-90 60 mA ON 490 0.0000106 0 No StCa 30 mA 60-90 30 mA 16 60-90 30 mA ON 490 0.0000086 0 No StCa NOT ON 60-90 NOT ON 16 60-90 NOT ON 535 0.0000156 0.0007694 No StCa RT RT 60 mA 16 ATMOSPHERE ON 60 mA ON 535 0.0000254 0.0011648 NO StCa 60
C 60 ATMOSPHERE 60 mA 16 ATMOSPHERE ON 60 mA ON 535 0.0000221 0.0010414 FIRST TIME 2000 ppm 60-90 60 mA 2000 ppm 16 60-90 60 mA ON 490 0.0000089 0 RETRY 60 mA RETRY WITH StCa 60 mA 60-90 60 mA 90 60-90 60 mA ON 490 0.0000096 0 WITH StCa 30 mA 60-90 30 mA 90 60-90 30 mA ON 490 0.0000115 0 WITH StCa NOT ON 60-90 NOT ON 90 60-90 NOT ON 535 0.0000177 0.0008694 WITH StCa RT RT 60 mA 90 ATMOSPHERE ON 60 mA ON 536 0.0000460 0.0021105 WITH StCa 60
C 60 ATMOSPHERE 60 mA 90 ATMOSPHERE ON 60 mA ON 532 0.0000358 0.0016431 No StCa NOT ON 60-90 NOT ON 90 60-90 NOT ON 534 0.0000139 0.0007008 No StCa RT RT 60 mA 90 ATMOSPHERE ON 60 mA ON 532 0.0000200 0.0009151 NO StCa 60
C 60 ATMOSPHERE 60 mA 90 ATMOSPHERE ON 60 mA ON 533 0.0000211 0.0009807 WITH StCa NOT ON 60-90 NOT ON 160 60-90 NOT ON 534 0.0000185 0.0009024 WITH StCa RT RT 60 mA 160 ATMOSPHERE ON 60 mA ON 535 0.0000439 0.0019995 WITH StCa 60
C 60 ATMOSPHERE 60 mA 160 60 mA ON 530 0.0000100 0.0004502 No StCa NOT ON 60-90 NOT ON 160 60-90 NOT ON 535 0.0000129 0.0006622 No StCa RT RT 60 mA 160 ATMOSPHERE ON 60 mA ON 532 0.0000177 0.0008148 NO StCa 60
C 60 ATMOSPHERE 60 mA 160 ATMOSPHERE ON 60 mA ON 532 0.0000191 0.0008784 WITH StCa NOT ON 60-90 NOT ON 523 60-90 NOT ON 535 0.0000184 0.0008976 WITH StCa RT RT 60 mA 523 ATMOSPHERE ON 60 mA ON 533 0.0000378 0.0017182 WITH StCa 60
C 60 ATMOSPHERE 60 mA 523 ATMOSPHERE ON 60 mA ON 528 0.0000129 0.0005967 No StCa NOT ON 60-90 NOT ON 523 60-90 NOT ON 535 0.0000112 0.0005616 No StCa RT RT 60 mA 523 ATMOSPHERE ON 60 mA ON 532 0.0000151 0.0006859 NO StCa 60
C 60 ATMOSPHERE 60 mA 523 ATMOSPHERE ON 60 mA ON 532 0.0000128 0.0005960 EXCITATION LIGHT RED PEAK RED HALF- LIGHT EMISSION TOTAL GREEN HALF-VALUE WAVELENGTH VALUE WIDTH WAVELENGTH EXCITATION EFFICIENCY LUMINOUS SAMPLE NAME WIDTH (nm) (nm) RED PEAK INTENSITY RED PEAK AREA (nm) (nm) LIGHT AREA [Im/W] FLUX [Im] WITH StCa 60 mA 52 626 0.0000248 0.001016 34 446 0.004749 5.280059 0.907280 WITH StCa 30 mA 48 627 0.0000341 0.001357 34 445 0.006267 6.908252 1.206617 WITH StCa NOT ON 46 627 0.0000244 0.000943 34 446 0.006766 5.239500 0.888772 WITH StCa RT 45 626 0.0000290 0.001135 33 446 0.005222 5.574886 0.948742 WITH StCa 60
C 54 627 0.0000223 0.000917 34 445 0.005292 4.981304 0.856424 No StCa 60 mA 50 627 0.0000257 0.001044 34 445 0.007598 6.002914 1.041193 No StCa 30 mA 54 627 0.0000219 0.000907 34 444 0.006729 5.329695 0.918784 No StCa NOT ON 46 627 0.0000189 0.000732 33 445 0.007521 4.417125 0.768209 No StCa RT 48 627 0.0000201 0.000775 33 446 0.007636 4.581739 0.783506 NO StCa 60
C 71 627 0.0000172 0.000729 34 446 0.005663 4.196566 0.757056 FIRST TIME 2000 ppm 48 627 0.0000277 0.001115 34 446 0.003783 5.596642 0.960721 RETRY 60 mA WITH StCa 60 mA 16 628 0.0000098 0.000413 34 445 0.009141 2.877867 0.494567 WITH StCa 30 mA 64 628 0.0000242 0.000927 32 445 0.011097 4.913075 0.887168 WITH StCa NOT ON 48 627 0.0000253 0.000978 32 446 0.006405 4.855154 0.858445 WITH StCa RT 43 628 0.0000405 0.001555 32 446 0.005611 9.477166 1.659095 WITH StCa 60
C 43 629 0.0000273 0.001043 31 445 0.007231 8.483070 1.500969 No StCa 60 mA 12 627 0.0000021 0.000145 72 444 0.014692 2.993103 0.544424 No StCa 30 mA 17 629 0.0000021 0.000152 73 443 0.011790 2.636867 0.467248 No StCa NOT ON 47 627 0.0000181 0.000723 33 445 0.006371 4.400288 0.778178 No StCa RT 44 629 0.0000227 0.000856 32 445 0.007962 6.296877 1.085817 NO StCa 60
C 45 630 0.0000176 0.000700 33 446 0.007125 5.613560 0.964300 FIRST TIME 2000 ppm 13 625 0.0000020 0.000137 71 445 0.010257 2.523555 0.435049 RETRY 60 mA WITH StCa 60 mA 10 580 0.0000012 0.000000 72 445 0.012295 2.587598 0.444087 WITH StCa 30 mA 10 624 0.0000029 0.000165 46 445 0.016115 3.290306 0.565801 WITH StCa NOT ON 47 627 0.0000255 0.001006 33 446 0.005587 5.068178 0.898528 WITH StCa RT 43 629 0.0000395 0.001492 32 446 0.005761 10.156078 1.722674 WITH StCa 60
C 43 630 0.0000211 0.000805 31 445 0.008628 7.760513 1.329635 No StCa NOT ON 49 628 0.0000161 0.000673 34 445 0.005070 3.845607 0.698393 No StCa RT 43 630 0.0000205 0.000759 32 445 0.007841 5.335926 0.904669 NO StCa 60
C 44 631 0.0000147 0.000581 33 446 0.007647 5.235426 0.903222 WITH StCa NOT ON 47 627 0.0000241 0.000955 33 446 0.005059 5.209650 0.892179 WITH StCa RT 43 629 0.0000375 0.001407 32 446 0.005777 9.598700 1.633024 WITH StCa 60
C 48 631 0.0000101 0.000383 32 445 0.006877 3.086920 0.526169 No StCa NOT ON 49 628 0.0000148 0.000630 35 445 0.004535 3.701075 0.646252 No StCa RT 43 630 0.0000196 0.000719 32 445 0.007802 4.845653 0.832520 NO StCa 60
C 43 631 0.0000131 0.000520 33 446 0.007888 4.862974 0.836706 WITH StCa NOT ON 46 628 0.0000213 0.000866 33 447 0.004085 4.608143 0.838659 WITH StCa RT 43 630 0.0000324 0.001213 32 446 0.006031 8.264959 1.412551 WITH StCa 60
C 58 631 0.0000097 0.000385 33 445 0.009715 3.949004 0.680410 No StCa NOT ON 49 628 0.0000128 0.000548 35 444 0.003676 3.155570 0.549997 No StCa RT 43 631 0.0000185 0.000679 31 446 0.007934 4.373495 0.754944 NO StCa 60
C 48 632 0.0000089 0.000363 34 446 0.007767 3.688968 0.638253
(124)
(125) Next, Table 3 below shows experiment results when sample 3 was irradiated with light emitted under a temperature of 60 C., humidity of 90% and at 30 mA, and Table 4 shows experiment results under other conditions.
(126) TABLE-US-00003 TABLE 3 SAMPLE TIME GREEN PEAK GREEN PEAK NAME COMMENT (h) REMARKS WAVELENGTH (nm) AREA sample 1-1 1st 0 30 mA ON 534 0.001174 sample 2-1 2nd 0 30 mA ON 535 0.000852 sample 3 3rd 0 30 mA ON 533 0.001070 sample 1-1 1st 6 30 mA ON 531 0.000833 sample 2-1 2nd 6 30 mA ON 530 0.001018 sample 3 3rd 6 30 mA ON 532 0.000830 sample 1-1 1st 19 30 mA ON 490 0 sample 2-1 2nd 19 30 mA ON 490 0 sample 3 3rd 19 30 mA ON 490 0 sample 1-1 1st 43 30 mA ON 490 0 sample 2-1 2nd 43 30 mA ON 490 0 sample 3 3rd 43 30 mA ON 490 0 sample 1-1 1st 70 30 mA ON 490 0 sample 2-1 2nd 70 30 mA ON 490 0 sample 3 3rd 70 30 mA ON 490 0 GREEN RED RED EXCITATION HALF- PEAK HALF- LIGHT LIGHT VALUE WAVE- RED VALUE WAVE- EMISSION TOTAL SAMPLE WIDTH LENGTH PEAK WIDTH LENGTH EXCITATION EFFICIENCY LUMINOUS NAME (nm) (nm) AREA (nm) (nm) LIGHT AREA [Im/W] FLUX [Im] sample 1-1 43 625 0.001245 33 445 0.004170 6.237870 1.075474 sample 2-1 46 626 0.000971 33 446 0.005431 5.027159 0.874938 sample 3 46 626 0.001203 34 445 0.007055 6.399195 1.092613 sample 1-1 47 629 0.000681 31 445 0.008232 4.876146 0.838764 sample 2-1 46 628 0.000928 32 445 0.006763 5.646894 0.971158 sample 3 50 628 0.001030 31 445 0.008908 5.514578 0.938792 sample 1-1 14 627 0.000198 36 444 0.012484 2.919376 0.502875 sample 2-1 61 628 0.000496 32 445 0.008174 3.187827 0.546200 sample 3 45 629 0.000452 33 445 0.013290 3.723622 0.633726 sample 1-1 10 625 0.000082 72 444 0.013419 2.573664 0.443293 sample 2-1 12 626 0.000250 35 445 0.010769 2.726104 0.466771 sample 3 12 628 0.000238 36 445 0.015104 3.355242 0.570699 sample 1-1 10 581 0.000071 66 444 0.013235 2.517751 0.432032 sample 2-1 11 627 0.000146 43 445 0.011718 2.596728 0.444422 sample 3 10 628 0.000149 51 445 0.015928 3.222996 0.547856
(127) TABLE-US-00004 TABLE 4 GREEN TIME GREEN PEAK PEAK SAMPLE NAME COMMENT (h) REMARKS WAVELENGTH (nm) AREA 60-90 60 mA ON Hex 0 60 mA ON 534 0.001004 60-90 NOT ON Hex 0 NOT ON 534 0.001217 RT 60 mA ON Hex 0 60 mA ON 534 0.000989 60 ATMOSPHERE 60 mA ON Hex 0 60 mA ON 534 0.001056 60-90 60 mA ON Hex 19 60 mA ON 490 0 60-90 NOT ON Hex 19 NOT ON 533 0.001359 RT 60 mA ON Hex 19 60 mA ON 536 0.001570 60 ATMOSPHERE 60 mA ON Hex 19 60 mA ON 536 0.001802 60-90 60 mA ON Hex 39 60 mA ON 490 0 60-90 NOT ON Hex 39 NOT ON 535 0.001313 RT 60 mA ON Hex 39 60 mA ON 537 0.001608 60 ATMOSPHERE 60 mA ON Hex 39 60 mA ON 536 0.001909 60-90 60 mA ON Hex 88 60 mA ON 490 0 60-90 NOT ON Hex 88 NOT ON 535 0.001377 RT 60 mA ON Hex 88 60 mA ON 536 0.001743 60 ATMOSPHERE 60 mA ON Hex 88 60 mA ON 536 0.001982 60-90 NOT ON Hex 165 NOT ON 535 0.001371 RT 60 mA ON Hex 165 60 mA ON 535 0.001826 60 ATMOSPHERE 60 mA ON Hex 165 60 mA ON 535 0.001964 60-90 NOT ON Hex 262 NOT ON 535 0.001248 RT 60 mA ON Hex 262 60 mA ON 535 0.001832 60 ATMOSPHERE 60 mA ON Hex 262 60 mA ON 535 0.001891 GREEN RED RED EXCITATION HALF- PEAK HALF- LIGHT LIGHT VALUE WAVE- RED VALUE WAVE- EMISSION TOTAL WIDTH LENGTH PEAK WIDTH LENGTH EXCITATION EFFICIENCY LUMINOUS SAMPLE NAME (nm) (nm) AREA (nm) (nm) LIGHT AREA [Im/W] FLUX [m] 60-90 60 mA ON 44 626 0.001052 33 445 0.007676 6.065723 1.041244 60-90 NOT ON 44 626 0.001272 34 445 0.007204 6.930717 1.193018 RT 60 mA ON 45 625 0.001030 34 445 0.008797 6.151587 1.051387 60 ATMOSPHERE 60 mA ON 44 626 0.001055 34 444 0.006719 5.932898 1.023193 60-90 60 mA ON 11 628 0.000241 34 445 0.012314 2.782612 0.477940 60-90 NOT ON 44 626 0.001270 33 445 0.006375 6.964275 1.253319 RT 60 mA ON 43 628 0.001155 32 445 0.008539 8.322008 1.419300 60 ATMOSPHERE 60 mA ON 43 629 0.001125 32 444 0.006882 8.680588 1.493393 60-90 60 mA ON 10 627 0.000125 43 445 0.013540 2.729361 0.466460 60-90 NOT ON 44 626 0.001257 33 445 0.006056 7.080454 1.215414 RT 60 mA ON 43 628 0.001117 32 445 0.008119 8.361491 1.421672 60 ATMOSPHERE 60 mA ON 43 629 0.001101 32 444 0.006973 8.983096 1.543791 60-90 60 mA ON 9 624 0.000075 70 445 0.013886 2.672744 0.456374 60-90 NOT ON 45 627 0.001273 34 445 0.005666 7.207451 1.245468 RT 60 mA ON 43 629 0.001127 32 445 0.008248 8.806561 1.498058 60 ATMOSPHERE 60 mA ON 43 629 0.001049 31 444 0.007058 9.183614 1.575884 60-90 NOT ON 44 626 0.001258 34 445 0.005343 7.158549 1.230510 RT 60 mA ON 42 629 0.001126 32 445 0.008401 9.051997 1.541294 60 ATMOSPHERE 60 mA ON 42 629 0.001017 31 444 0.007322 8.984315 1.546295 60-90 NOT ON 45 627 0.001184 33 446 0.004920 6.512652 1.126485 RT 60 mA ON 42 630 0.001089 32 446 0.008285 8.992976 1.536733 60 ATMOSPHERE 60 mA ON 42 630 0.000952 31 444 0.007393 8.635300 1.492157
(128)
(129) In each graph, the smaller the time variation in light emission intensity, that is, the gentler the gradient of reduction over an elapsed time, the more the durability against environmental variations improves. As is obvious from each graph, it is appreciated that when the LED is turned on under severe environmental conditions such as 60 C., 90RH, fluorescence intensity decreases rapidly. On the other hand, it is appreciated that when the LED is turned on indoors, when the LED is turned on under a 60 C. atmosphere or when the LED is not turned on, fluorescence intensity gradually attenuates or the initial intensity level can be maintained.
(130) Next, a time variation in fluorescence intensity of sample 2-1 mixed with calcium stearate (StCa) was compared with that of sample 2-2 without being mixed with calcium stearate (StCa).
(131) Furthermore, the time variations in fluorescence intensity in
(132) [Injection Molding]
(133) The following injection molding machine was used. Electric injection molding machine: J110AD 110H Name of manufacturer: Japan Steel Works, Ltd. Specification: Injection pressure: 225 MPa Mold clamping force: 1080 kN
(134) Pellets of samples 4-1 to 4-3 obtained through extrusion molding were introduced to an injection molding machine under a cylinder temperature of 200 C. to 240 C., injected into a physical property specimen creation metal die to mold a specimen of a predetermined shape.
(135) [Durability Test on Injection Molded Product]
(136) The respective specimens were heated to 90 C., 110 C., 130 C., respectively, and then annealed. The specimen in size of 5 cm1 cm4 mm was held by a sample holder, and subjected to a durability test under 60 C., 90RH. Influences of the above-described annealing were thereby studied.
(137)
(138) As shown in
(139) [Experiment of Dispersion State]
(140) The dispersed state of quantum dots in resin was examined using sample A. Sample A was formed based on sample 1-1. Both
(141) It has been proved from this experiment that a plurality of quantum dots form each aggregate and aggregates are dispersed in resin.
INDUSTRIAL APPLICABILITY
(142) The resin molded product of the present invention is applicable to a light-guiding board for an LED light source, a backlight or the like, and an illumination device, a fluorescence member or the like.
(143) The present application is based on Japanese Patent Application No. 2014-160299 filed on Aug. 6, 2014, entire content of which is expressly incorporated by reference herein.