WO2017094832A1 - Feuille fluorescente, élément électroluminescent utilisant celle-ci, unité de source de lumière, affichage et procédé de production d'élément électroluminescent - Google Patents

Feuille fluorescente, élément électroluminescent utilisant celle-ci, unité de source de lumière, affichage et procédé de production d'élément électroluminescent Download PDF

Info

Publication number
WO2017094832A1
WO2017094832A1 PCT/JP2016/085710 JP2016085710W WO2017094832A1 WO 2017094832 A1 WO2017094832 A1 WO 2017094832A1 JP 2016085710 W JP2016085710 W JP 2016085710W WO 2017094832 A1 WO2017094832 A1 WO 2017094832A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
layer
transparent resin
phosphor sheet
fine particles
Prior art date
Application number
PCT/JP2016/085710
Other languages
English (en)
Japanese (ja)
Inventor
達也 神崎
卓哉 西山
長瀬　亮
石田　豊
広樹 関口
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020187014115A priority Critical patent/KR102419336B1/ko
Priority to CN201680066389.7A priority patent/CN108351444B/zh
Priority to JP2016571440A priority patent/JP6852401B2/ja
Publication of WO2017094832A1 publication Critical patent/WO2017094832A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Definitions

  • the present invention relates to a phosphor sheet, a light emitter using the phosphor sheet, a light source unit, a display, and a method for manufacturing the light emitter.
  • LEDs Light-emitting diodes
  • LCD liquid crystal display
  • LEDs Light Emitting Diodes
  • LCD Liquid Crystal Display
  • LEDs are expected to form a huge market in the general lighting field because of their low environmental impact.
  • Patent Document 1 discloses a Mn-activated double fluoride phosphor, which is a red phosphor having a narrow emission peak half-value width, and a Eu 2 + -activated alkaline earth siliconitride phosphor, which is a yellow phosphor or a green phosphor. A method for obtaining white light emission by use is described.
  • An object of the present invention is to solve such problems.
  • the phosphor sheet according to the present invention includes a phosphor layer including a red phosphor, a ⁇ -type sialon phosphor, and a resin.
  • It is Mn activation double fluoride represented by Formula (1), It is characterized by the above-mentioned.
  • a 2 MF 6 Mn (1)
  • A is one or more alkali metals selected from the group consisting of Li, Na, K, Rb and Cs and containing at least one of Na and K
  • M is Si
  • one or more tetravalent elements selected from the group consisting of Ti, Zr, Hf, Ge and Sn.
  • the phosphor layer is composed of a single layer or a plurality of layers including the red phosphor, the ⁇ -type sialon phosphor, and the resin.
  • the ⁇ -sialon phosphor and the resin are contained in the same layer.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin is 1.45 or more and 1.7 or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the resin is a silicone resin.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the proportion of the red phosphor in the total solid content in the phosphor layer is 20 wt% or more and 60 wt% or less. To do.
  • the total of the proportion of the red phosphor and the proportion of the ⁇ -sialon phosphor in the total solid content in the phosphor layer is 50% by weight or more. 90% by weight or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the D50 of the red phosphor is 10 ⁇ m or more and 40 ⁇ m or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, D10 of the red phosphor is 3 ⁇ m or more.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, (D90-D10) / D50 of the red phosphor is 0.5 or more and 1.5 or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the porosity in the phosphor layer is 0.1% or more and 3% or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the phosphor layer contains fine particles.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the fine particles are silicone fine particles.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, a transparent resin layer is further laminated on the phosphor layer.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin contained in the transparent resin layer is 1.3 or more and 1.6 or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin contained in the transparent resin layer is not more than the refractive index of the resin contained in the phosphor layer.
  • the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the transparent resin layer contains fine particles.
  • the fine particles contained in the transparent resin layer are one or more selected from silica fine particles, alumina fine particles, and silicone fine particles.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the transparent resin layer has a minimum transmittance of 80% or more at a wavelength of 400 nm to 800 nm.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the proportion of fine particles in the total solid content in the transparent resin layer is 0.1 wt% or more and 30 wt% or less. .
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the average particle size of the fine particles contained in the transparent resin layer is 1 nm or more and 1000 nm or less.
  • the manufacturing method of the light-emitting body which concerns on this invention picks up the said fluorescent substance sheet separated into the individualization process which separates the fluorescent substance sheet as described in any one of said invention, and individualized It includes a pick-up step and a pasting step of pasting the separated phosphor sheet to a light source.
  • a light emitter according to the present invention includes the phosphor sheet according to any one of the above inventions.
  • a light source unit according to the present invention is characterized by including the phosphor sheet according to any one of the above inventions.
  • a display according to the present invention is characterized by comprising the light source unit described in the above invention.
  • the present invention it is possible to provide a phosphor sheet that achieves both improved color reproducibility and high luminous flux.
  • the light emitting body, the light source unit, and the display including the phosphor sheet according to the present invention have an effect that both improvement in color reproducibility and high luminance can be achieved.
  • FIG. 1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
  • FIG. 1B is a side view showing another example of the phosphor sheet according to the embodiment of the present invention.
  • FIG. 2 is a process diagram showing an example of a method for manufacturing a light emitter using the phosphor sheet according to the embodiment of the present invention.
  • a phosphor sheet according to the present invention a light emitter using the phosphor sheet, a light source unit, a display, and a method for producing the light emitter will be described in detail.
  • the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application.
  • the phosphor sheet according to the embodiment of the present invention includes a phosphor layer containing a red phosphor, a ⁇ -type sialon phosphor, and a resin.
  • the red phosphor is a Mn-activated bifluoride represented by the general formula (1).
  • a 2 MF 6 Mn (1)
  • A is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and at least one of Na and K is selected.
  • M is at least one tetravalent element selected from the group consisting of silicon (Si), titanium (Ti), zirconium (Zr), hafnium (Hf), germanium (Ge), and tin (Sn).
  • FIG. 1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
  • the phosphor sheet 4 according to the embodiment of the present invention includes a phosphor layer 2 containing a phosphor 1 and a resin 14 on a support 3.
  • the phosphor layer 2 is a layer containing a plurality of phosphors 1 in the resin 14.
  • the phosphor layer 2 contains, as the phosphor 1, a red phosphor represented by the general formula (1) and a ⁇ -type sialon phosphor.
  • the phosphor layer 2 is formed on a support 3 to constitute a phosphor sheet 4.
  • the phosphor layer 2 may be composed of a single layer containing the red phosphor and the ⁇ -type sialon phosphor as the phosphor 1 and the resin 14.
  • the phosphor layer 2 may be composed of a plurality of layers containing the phosphor 1 and the resin 14.
  • the phosphor layer 1 contains a first phosphor layer containing the red phosphor as the phosphor 1 and the resin 14, and a ⁇ -sialon phosphor as the phosphor 1 and the resin 14.
  • One or more second phosphor layers may be laminated to form a plurality of layers of the phosphor layer 2.
  • the red phosphor and ⁇ -sialon phosphor as the phosphor 1 and the resin 14 are included in the same layer. This is due to the following reason.
  • the phosphor layer 2 is a laminate of a layer containing a red phosphor (first phosphor layer) and a layer containing a ⁇ -type sialon phosphor (second phosphor layer), color reproducibility Although it is possible to achieve both improvement and high luminous flux, in the phosphor layer 2, it is necessary to control the film thickness of each layer separately. For this reason, the chromaticity dispersion
  • FIG. 1B is a side view showing another example of the phosphor sheet according to the embodiment of the present invention.
  • the phosphor sheet 4 may further include a transparent resin layer 5 on the phosphor layer 2 formed on the support 3.
  • the transparent resin layer 5 is formed on the upper surface (surface opposite to the support 3) of the phosphor layer 2 composed of a single layer or a plurality of layers, for example. The presence of the transparent resin layer 5 as described above improves the durability of the phosphor sheet 4.
  • the phosphor sheet 4 is provided with a single layer or a plurality of phosphor layers 2 or is provided with the phosphor layer 2 and the transparent resin layer 5. From the standpoints of shape maintenance and ease of handling, it is normally in a state of being supported by the support 3. That is, in the present embodiment, the phosphor sheet 4 and the support 3 may be collectively referred to as “phosphor sheet”.
  • the phosphor layer 2 is a layer mainly including the phosphor 1 and the resin 14.
  • the phosphor 1 include at least a red phosphor represented by the general formula (1) and a ⁇ -type sialon phosphor.
  • the red phosphor is a phosphor having an emission peak at a wavelength of 590 nm to 750 nm.
  • the phosphor layer 2 includes a Mn-activated double fluoride (A 2 ) represented by the general formula (1) described above. It is necessary to include a red phosphor that is MF 6 : Mn).
  • the red phosphor which is this Mn activated double fluoride is referred to as “Mn activated double fluoride complex phosphor”.
  • the Mn-activated double fluoride complex phosphor is abbreviated as “red phosphor” as appropriate.
  • the Mn-activated double fluoride complex phosphor is a phosphor having manganese (Mn) as an activator and an alkali metal or alkaline earth metal fluoride complex salt as a base crystal.
  • the coordination center of the fluoride complex forming the host crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, Sn),
  • the number of coordinated fluorine atoms is preferably 6.
  • a preferred Mn-activated bifluoride complex phosphor is one in which A is K (potassium) and M is Si (silicon) in the general formula (1), that is, K 2 SiF 6 : Mn. This is called a KSF phosphor.
  • the ratio of the red phosphor (that is, the Mn-activated bifluoride complex phosphor) in the total solid content in the phosphor layer 2 is preferably 10% by weight or more, and more preferably 20% by weight or more. Further, this ratio is preferably 80% by weight or less, and more preferably 60% by weight or less. When this ratio is equal to or greater than the preferable lower limit value, the color reproduction range of the phosphor sheet 4 is further improved. On the other hand, when this ratio is 80% by weight or less, the chromaticity variation of the phosphor sheet 4 is improved, and when this ratio is 60% by weight or less, the chromaticity variation of the phosphor sheet 4 is further improved.
  • the D50 of the red phosphor as the phosphor 1 is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more. Further, D50 of the red phosphor is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less. When the D50 of the red phosphor is 5 ⁇ m or more, the phosphor sheet 4 having a high luminous flux can be obtained. When the D50 of the red phosphor is 40 ⁇ m or less, the chromaticity variation of the phosphor sheet 4 is improved.
  • D10 of the red phosphor as the phosphor 1 is preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more. Thereby, the durability of the phosphor sheet 4 is improved.
  • D10 of this red fluorescent substance it is preferable that it is 15 micrometers or less, and it is more preferable that it is 12 micrometers or less.
  • the value x is an index of the particle size distribution of the red phosphor.
  • a small value x means that there are few red phosphors having a small particle size (for example, KSF phosphor) that cause a decrease in durability, and a red phosphor having a large particle size that causes chromaticity variation (for example, KSF). This means that there is little phosphor.
  • the value x is 1.5 or less, the durability and chromaticity variation of the phosphor sheet 4 are further improved.
  • Yellow ring is a phenomenon in which the color appears different when the light emitter is viewed from the front and when viewed from an oblique direction. This yellow ring is a remarkable phenomenon when light scattering in the phosphor layer 2 is small.
  • the value x is preferably 0.5 or more.
  • D10, D50, and D90 are particle sizes measured by the following method.
  • the cross section of the phosphor layer 2 is observed with an SEM, and in the obtained two-dimensional image, the maximum distance among the distances between the two intersections of the straight line that intersects the outer edge of the particles of the phosphor 1 at two points. Is defined as the individual particle size of the particles.
  • the particle size of accumulated 10% from the small particle size side is D10
  • the particle size (average particle size) of accumulated 50% is D50.
  • a particle diameter of 90% of the accumulated portion is D90.
  • this fluorescence can be obtained by any of mechanical polishing, microtome, CP (Cross-section Polisher) and focused ion beam (FIB) processing.
  • CP Cross-section Polisher
  • FIB focused ion beam
  • the ⁇ -type sialon phosphor is a solid solution of ⁇ -type silicon nitride.
  • Aluminum (Al) is substituted and dissolved in the Si position of ⁇ -type silicon nitride crystal, and oxygen (O) is substituted and dissolved in the nitrogen (N) position. It is what. Since there are two types of atoms in the unit cell (unit cell) of the ⁇ -type sialon used in the ⁇ -type sialon phosphor, Si 6-z Al z O z N 8-z is used as a general formula of the ⁇ -type sialon. It is done. In this general formula, z is a value greater than 0 and less than 4.2.
  • the solid solution range of ⁇ -type sialon is very wide, and the molar ratio of (Si, Al) / (N, O) must be maintained at 3/4. is there.
  • a general method for producing ⁇ -sialon is a method in which, in addition to silicon nitride, silicon oxide and aluminum nitride, or aluminum oxide and aluminum nitride are added and heated.
  • ⁇ -type sialon is a ⁇ -type sialon that emits green light with a wavelength of 520 nm to 560 nm when excited by ultraviolet to blue light by incorporating a light emitting element such as rare earth (Eu, Sr, Mn, Ce, etc.) into the crystal structure. Becomes a phosphor. This is preferably used as a green light emitting component of a light emitting body such as a white LED.
  • europium is ⁇ -sialon phosphor which contains the Eu 2+ activated ⁇ -sialon phosphor, since the emission spectrum is very sharp, blue, green, red narrow band emission It is a material suitable for the backlight light source of the required image processing display device or liquid crystal display panel.
  • the D50 of the ⁇ -type sialon phosphor as the phosphor 1 is preferably 1 ⁇ m or more, and more preferably 10 ⁇ m or more. Further, D50 of this ⁇ -type sialon phosphor is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • D50 limiting in particular as a shape of (beta) type
  • the content of the ⁇ -sialon phosphor as the phosphor 1 in the phosphor layer 2 is preferably 3% by weight or more of the entire phosphor layer 2 from the viewpoint of expanding the color reproduction range. More preferably, it is 5% by weight or more. Further, the content of the ⁇ -type sialon phosphor is preferably 50% by weight or less of the entire phosphor layer 2, and more preferably 40% by weight or less of the entire phosphor layer 2.
  • the total of the proportion of the red phosphor and the proportion of the ⁇ -sialon phosphor in the total solid content in the phosphor layer 2 is preferably 50% by weight or more and 90% by weight or less.
  • the lower limit of the sum of these ratios is more preferably 65% by weight or more, and even more preferably 70% by weight or more.
  • the upper limit of the sum of these two ratios is more preferably 85% by weight or less, and further preferably 80% by weight or less.
  • the porosity in the phosphor layer 2 is preferably 3% or less. % Or less, more preferably 1% or less, still more preferably 0.5% or less. This is because, as the porosity in the phosphor layer 2 is smaller, the light extraction efficiency from the phosphor layer 2 is improved, so that the phosphor sheet 4 that gives a high luminous flux can be obtained. . Further, the porosity of the phosphor layer 2 is not particularly limited to a lower limit, but is preferably 0.1% or more.
  • the porosity is the ratio of the voids in the phosphor layer 2.
  • This porosity can be measured by the following method.
  • the phosphor sheet 4 and the cross section of the phosphor layer 2 are observed by any one of a mechanical polishing method, a microtome method, a CP method (Cross-section Polisher), and a focused ion beam (FIB) processing method. Grind. Thereafter, an area corresponding to the gap of the phosphor layer 2 is calculated from a two-dimensional image obtained by observing the obtained cross-section with an SEM, and the calculated area of the gap is calculated for the entire phosphor layer 2 in the section. Divide by area. Thereby, the porosity of the phosphor layer 2 is obtained.
  • the above-mentioned value x (see formula (11)) that is an index of the particle size distribution of the red phosphor is small. By doing so, the porosity of the phosphor layer 2 tends to be small.
  • the phosphor layer 2 may further contain a phosphor other than the phosphor 1 described above.
  • phosphors other than the phosphor 1 described above include other red phosphors, other green phosphors, yellow phosphors, and blue phosphors.
  • the green phosphor is a phosphor having an emission peak at a wavelength of 500 nm to 560 nm.
  • the yellow phosphor is a phosphor having an emission peak at a wavelength of 560 nm to 590 nm.
  • the blue phosphor is a phosphor having an emission peak at a wavelength of 430 nm to 500 nm.
  • red phosphors are other than the red phosphor (Mn-activated bifluoride complex phosphor) represented by the general formula (1).
  • examples of such other red phosphors include Y 2 O 2 S: Eu, La 2 O 2 S: Eu, Y 2 O 3 : Eu, and Gd 2 O 2 S: Eu.
  • green phosphors are other than ⁇ -type sialon phosphors.
  • SrAl 2 O 4 Eu
  • Y 2 SiO 5 Ce
  • Tb Ce
  • MgAl 11 O 19 Ce
  • Tb Ce
  • Sr 7 Al 12 O 25 Eu
  • (Mg, Ca , Sr, and Ba, at least one element) Ga 2 S 4 Eu, and the like.
  • yellow phosphors include yttrium / aluminum oxide phosphors activated with at least cerium, yttrium / gadolinium / aluminum oxide phosphors consolidated with at least cerium, and at least cerium-activated yttrium / gallium / Examples thereof include aluminum oxide phosphors.
  • blue phosphor for example, Sr 5 (PO 4 ) 3 Cl: Eu, (SrCaBa) 5 (PO 4 ) 3 Cl: Eu, (BaCa) 5 (PO 4 ) 3 Cl: Eu, (Mg, Ca, Sr , Ba, at least one element) 2 B 5 O 9 Cl: Eu, Mn, (at least one element of Mg, Ca, Sr, Ba) (PO 4 ) 6 Cl 2 : Eu, Mn Etc.
  • Examples of phosphors that emit light corresponding to the current mainstream blue LEDs include Y 3 (Al, Ga) 5 O 12 : Ce, (Y, Gd) 3 Al 5 O 12 : Ce, Lu 3 Al 5.
  • YAG phosphors such as O 12 : Ce, Y 3 Al 5 O 12 : Ce
  • TAG phosphors such as Tb 3 Al 5 O 12 : Ce
  • (Ba, Sr) 2 SiO 4 Eu phosphors
  • the refractive index of the resin 14 contained in the phosphor layer 2 is 1.45 or more and 1.7 or less.
  • the refractive index of the resin 14 is more preferably 1.5 or more, and more preferably 1.65 or less. Since the refractive index of the resin 14 is 1.45 or more, the refractive index of the Mn-activated double fluoride complex phosphor (red phosphor as the phosphor 1) having an average refractive index of around 1.4. The difference is increased, and light is easily scattered in the phosphor layer 2. Therefore, the optical path length from when light enters the phosphor layer 2 to when it exits becomes longer. By increasing the optical path length, the blue light emitted from the LED chip is easily color-converted by the phosphor 1 in the phosphor layer 2, so that the amount of phosphor for expressing desired chromaticity is reduced. Can do.
  • the refractive index of the resin 14 exceeds 1.7, the optical path length becomes longer than necessary due to excessive scattering of light in the phosphor layer 2. For this reason, the emitted light emitted from the phosphor 1 in the phosphor layer 2 is easily absorbed by the phosphor 1, and as a result, the intensity of the light emitted from the phosphor is reduced.
  • the material of the resin 14 is not particularly limited as long as the phosphor (such as the phosphor 1 shown in FIG. 1A) can be uniformly dispersed therein and the phosphor layer 2 can be formed.
  • the resin 14 include silicone resin, epoxy resin, polyarylate resin, PET-modified polyarylate resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, modified acrylic resin, Examples thereof include polystyrene resin and acrylonitrile / styrene copolymer resin. Of these, silicone resins and epoxy resins are preferred from the viewpoint of transparency. Furthermore, a silicone resin is particularly preferable from the viewpoint of heat resistance.
  • a curable silicone resin is preferable.
  • the curable silicone resin used as the resin 14 may be of one liquid type or two liquid type (three liquid type).
  • the curable silicone resin includes a dealcohol type, a deoxime type, a deacetic acid type, a dehydroxylamine type and the like as a type that causes a condensation reaction with moisture in the air or a catalyst.
  • the curable silicone resin includes an addition reaction type as a type that causes a hydrosilylation reaction by a catalyst. Any of these types of curable silicone resins may be used as the resin 14.
  • an addition reaction type silicone resin is more preferable because it has no by-products associated with the curing reaction, has a small curing shrinkage, and can easily be cured by heating.
  • the addition reaction type silicone resin as an example of the resin 14 is formed by, for example, a hydrosilylation reaction between a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom.
  • Examples of the “compound containing an alkenyl group bonded to a silicon atom” include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane Etc.
  • Examples of the “compound having a hydrogen atom bonded to a silicon atom” include, for example, methyl hydrogen polysiloxane, dimethyl polysiloxane-CO-methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, methyl hydrogen polysiloxane-CO-methyl. Examples thereof include phenyl polysiloxane. Examples of the addition reaction type silicone resin include those formed by hydrosilylation reaction of such materials. In addition, as the resin 14, other well-known resins as described in, for example, JP 2010-159411 A can be used.
  • a resin 14 it is also possible to use a commercially available product, for example, a general silicone sealing material for LED use.
  • a commercially available product for example, a general silicone sealing material for LED use.
  • Specific examples thereof include OE-6630A / B and OE-6336A / B manufactured by Toray Dow Corning, and SCR-1012A / B and SCR-1016A / B manufactured by Shin-Etsu Chemical Co., Ltd.
  • the silicone resin as the resin 14 may have heat-fusibility. This is because, when the resin 14 of the phosphor layer 2 is a silicone resin having heat-fusibility, the phosphor sheet 4 provided with the phosphor layer 2 has heat-fusibility. This is because the phosphor sheet 4 having the above can be heated and attached to the LED chip.
  • the heat fusibility here is a property of softening by heating. In the case where the phosphor sheet 4 has heat-fusibility, it is not necessary to use an adhesive for attaching the phosphor sheet 4 to the LED chip, so that the manufacturing process of the light emitter and the like can be simplified.
  • the storage elastic modulus at 25 ° C. is 0.1 MPa or more, and the storage elastic modulus at 100 ° C. is less than 0.1 MPa.
  • a cross-linked product obtained by hydrosilylation reaction of a cross-linkable silicone composition including the following components (A) to (D) is particularly preferable.
  • This crosslinked product can be preferably used as a matrix resin for the phosphor sheet 4 that does not require an adhesive because the storage elastic modulus decreases at 60 ° C. to 250 ° C. and high adhesive strength is obtained by heating.
  • the component (A) is an organopolysiloxane represented by the following average unit formula (21). (R 1 2 SiO 2/2 ) a (R 1 SiO 3/2 ) b (R 2 O 1/2 ) c (21)
  • R 1 is a phenyl group, an alkyl or cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
  • 65 mol% to 75 mol% of R 1 is a phenyl group
  • 10 mol% to 20 mol% of R 1 is an alkenyl group.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the component (B) is an organopolysiloxane represented by the following general formula (2).
  • This organopolysiloxane has a content of 5 to 15 parts by weight per 100 parts by weight of component (A).
  • R 3 is a phenyl group, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, or an alkenyl group having 2 to 6 carbon atoms.
  • 40 mol% to 70 mol% of R 3 is a phenyl group, at least one R 3 is an alkenyl group.
  • m is an integer in the range of 5-50.
  • Component (C) is an organotrisiloxane represented by the following general formula (3).
  • the molar ratio of silicon-bonded hydrogen atoms in component (C) to the sum of alkenyl groups in component (A) and alkenyl groups in component (B) is in the range of 0.5 to 2.
  • R 4 is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms. However, 30 mol% to 70 mol% of R 4 is a phenyl group.
  • component is a catalyst for hydrosilylation reaction.
  • This catalyst for hydrosilylation reaction is of an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in component (A) and component (B) and the silicon-bonded hydrogen atom in component (C). .
  • component (A) when the values of a, b, and c satisfy the above conditions, sufficient hardness at room temperature of the resulting crosslinked product is obtained, and at the high temperature of this crosslinked product. Can be obtained.
  • the resulting crosslinked product In the general formula (2) of the component (B), when the phenyl group content is less than the lower limit of the above range, the resulting crosslinked product is not sufficiently softened at high temperature. On the other hand, if the phenyl group content exceeds the upper limit of the above range, the resulting crosslinked product loses its transparency and its mechanical strength also decreases.
  • at least one of R 3 is an alkenyl group.
  • m is an integer in the range of 5-50.
  • the numerical range of m is a range in which handling workability can be maintained while maintaining the mechanical strength of the obtained cross-linked product.
  • the content of the component (B) is an amount in the range of 5 to 15 parts by weight with respect to 100 parts by weight of the component (A). This range of content is a range for obtaining sufficient softening of the obtained crosslinked product at a high temperature.
  • R 4 is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms.
  • alkyl group for R 4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a heptyl group.
  • cycloalkyl group represented by R 4 include a cyclopentyl group and a cycloheptyl group.
  • the phenyl group content is in the range of 30 mol% to 70 mol%. The range of the content is a range in which the obtained crosslinked product can be sufficiently softened at a high temperature, and the transparency and mechanical strength of the crosslinked product can be maintained.
  • the content of the component (C) is such that the molar ratio of silicon-bonded hydrogen atoms in the component (C) is 0. 0 with respect to the sum of the alkenyl groups in the component (A) and the alkenyl groups in the component (B).
  • the amount is in the range of 5 to 2.
  • the range of this content is a range in which sufficient hardness at room temperature of the obtained crosslinked product is obtained.
  • Component (D) is a hydrosilylation catalyst for promoting a hydrosilylation reaction between an alkenyl group in component (A) and component (B) and a silicon atom-bonded hydrogen atom in component (C).
  • component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Of these, platinum-based catalysts are preferred because they can significantly accelerate the curing of the silicone composition.
  • the platinum catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex.
  • the platinum-based catalyst is preferably a platinum-alkenylsiloxane complex.
  • alkenyl siloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
  • 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good.
  • the content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in the component (A) and the component (B) and the silicon atom-bonded hydrogen atom in the component (C).
  • the content of the component (D) is such that the metal atom in the component (D) is in the range of 0.01 ppm to 500 ppm in terms of mass unit with respect to the silicone composition.
  • the content of the component (D) is preferably such that the metal atom is in the range of 0.01 ppm to 100 ppm, and in particular, the metal atom is in the range of 0.01 ppm to 50 ppm.
  • An amount is preferred. This range of content is a range in which the resulting silicone composition is sufficiently crosslinked and does not cause problems such as coloring.
  • the ratio of the resin 14 to the total solid content in the phosphor layer 2 is preferably 10% by weight or more and 60% by weight or less. This is because, by setting the ratio of the resin 14 in the above range, both improvement in color reproducibility and high durability of the phosphor sheet 4 can be achieved.
  • the refractive index of the resin 14 can be measured by measuring the refractive index of the refractive index measurement sample using a refractive index / film thickness measuring device “Prism Coupler MODEL 2010 / M” (Metricon).
  • the refractive index measurement sample was prepared by stirring and defoaming the resin 14 for 10 minutes at 1000 rpm using a planetary stirring and degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to prepare a dispersion of the resin 14. After 5 cc of this dispersion is dropped on a PET film, it can be obtained by heating in an oven at 150 ° C. for 1 hour.
  • the phosphor sheet 4 according to the embodiment of the present invention contains fine particles in the phosphor layer 2 for the purpose of improving the dispersion stability of the phosphor 1 in the phosphor layer 2 in the resin 14. Also good.
  • the fine particles include fine particles composed of titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, barium titanate, and the like. These may be used alone or in combination of two or more.
  • the fine particles contained in the phosphor layer 2 are preferably silica fine particles, alumina fine particles, and silicone fine particles from the viewpoint of easy availability, and silicone fine particles are particularly preferable from the viewpoint of low hardness. Since the hardness of the fine particles is low, there is an effect of suppressing the crushing of the red phosphor in the step of dispersing the phosphor 1, and as a result, the phosphor sheet 4 having higher emission intensity can be obtained.
  • silicone fine particles include hydrolyzing and then condensing organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane.
  • organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane.
  • silicone fine particles obtained by the method.
  • organotrialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-proxysilane, methyltri-i-proxysilane, methyltri-n-butoxysilane, methyltri-i-butoxysilane, and methyltri-s.
  • organodialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- ( 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, Examples thereof include vinyl methyldiethoxysilane.
  • organotriacetoxy silane examples include methyl triacetoxy silane, ethyl triacetoxy silane, vinyl triacetoxy silane, and the like.
  • organodiacetoxysilane examples include dimethyldiacetoxysilane, methylethyldiacetoxysilane, vinylmethyldiacetoxysilane, vinylethyldiacetoxysilane, and the like.
  • organotrioxime silane include methyl trismethyl ethyl ketoxime silane and vinyl trismethyl ethyl ketoxime silane.
  • organodioxime silane examples include methyl ethyl bismethyl ethyl ketoxime silane.
  • Such fine particles are specifically the method reported in Japanese Patent Laid-Open No. 63-77940 and the method reported in Japanese Patent Laid-Open No. 6-248081. It can be obtained by the method reported in JP-A No. 2003-342370, the method reported in JP-A No. 4-88022, and the like. Also, at least one of organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and partial hydrolysates thereof is added to the alkaline aqueous solution.
  • organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and partial hydrolysates thereof is added to the alkaline aqueous solution.
  • At least one hydrolysis of the organosilane and its partial hydrolyzate by adding at least one of the organosilane and its partial hydrolyzate to water or an acidic solution.
  • a method in which alkali is added and the condensation reaction proceeds to obtain fine particles at least one of organosilane and a hydrolyzate thereof is used as an upper layer, and an alkali or a mixture of an alkali and an organic solvent is used as a lower layer
  • the method or the like to obtain the emissions and at least one by hydrolyzing and polycondensing microparticles hydrolyzate thereof are also known. In any of these methods, fine particles contained in the phosphor layer 2 can be obtained in the present invention.
  • organosilane and its partial hydrolyzate is hydrolyzed / condensed to produce spherical organopolysilsesquioxane fine particles, as reported in JP-A-2003-342370. It is preferable to use silicone fine particles obtained by a method in which a polymer dispersant is added to a reaction solution.
  • the average particle size of the silicone fine particles is represented by D50.
  • the lower limit of the average particle diameter is preferably 0.05 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • an upper limit of this average particle diameter it is preferable that it is 2.0 micrometers or less, and it is further more preferable that it is 1.0 micrometers or less.
  • the average particle diameter (D50) of the silicone fine particles can be obtained by the same method as the average particle diameter of the red phosphor as the phosphor 1 described above.
  • the proportion of fine particles in the total solid content in the phosphor layer 2 is preferably 0.1% by weight or more and 10% by weight or less.
  • the proportion of the fine particles is within the above range, the dispersion stability of the phosphor 1 in the phosphor layer 2 (in the resin 14) can be improved.
  • the color reproducibility of the phosphor sheet 4 is improved. Can achieve both high luminous flux and high durability.
  • the contents of the phosphor 1, the resin 14, and the silicone fine particles in the phosphor layer 2 in the present invention can also be obtained from the prepared phosphor layer 2 and the LED luminous body on which the phosphor layer 2 is mounted.
  • the phosphor layer 2 is embedded and cut with a predetermined resin, a sample whose cross section is polished is prepared, and the exposed cross section is observed with a scanning electron microscope (SEM). It is possible to clearly discriminate the particle portion of the phosphor 1, the silicone fine particle portion, and the resin 14 portion. From the area ratio of the cross-sectional image, it is possible to accurately measure the volume ratios of phosphor 1 (phosphor particles), silicone fine particles, and resin 14 occupying the entire phosphor layer 2.
  • the weight ratio of the phosphor 1 to the phosphor layer 2 can be calculated by dividing each volume ratio by the specific gravity. .
  • the composition of each component forming the phosphor layer 2 can be determined by analyzing the cross-section of the phosphor layer 2 with high-resolution micro-infrared spectroscopy or IPC emission analysis. . If the composition of each of these components is clarified, the specific gravity specific to the substance of the resin 14 or the phosphor 1 can be estimated with a considerable degree of accuracy, and the weight ratio can be obtained using this.
  • the phosphor layer 2 is preferably blended with a hydrosilylation reaction retarder in order to suppress curing at room temperature and lengthen the pot life.
  • a hydrosilylation reaction retarder examples include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol and the like.
  • Alcohol derivatives having a carbon-carbon triple bond enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, tetramethyltetravinylcyclotetrasiloxane, tetramethyl Low molecular weight siloxane containing alkenyl groups such as tetrahexenylcyclotetrasiloxane, methyl-tris (3-methyl-1-butyne-3-oxy) silane, vinyl-tris (3-methyl-1-butyne-3-oxy) silane, etc. And alkyne-containing silanes.
  • the phosphor layer 2 has an inorganic filler such as fumed silica, glass powder, quartz powder, etc., an inorganic filler such as zinc oxide, a flame retardant, and the like, as long as the effects of the present invention are not impaired.
  • the transparent resin layer 5 (see FIG. 1B) is a resin layer that has a total light transmittance of 90% or more at a wavelength of 450 nm and does not include the phosphor 1.
  • the transparent resin layer 5 is laminated on the phosphor layer 2 as shown in FIG. 1B, for example.
  • the minimum transmittance of the transparent resin layer 5 at a wavelength of 400 nm to 800 nm is preferably 80% or more.
  • the minimum transmittance is the smallest value of the light transmittance at wavelengths of 400 nm to 800 nm.
  • the phosphor sheet 4 can easily achieve both high luminous flux and high durability.
  • the presence of the transparent resin layer 5 on the phosphor layer 2 improves the durability of the phosphor 1 (for example, a red phosphor) in the phosphor layer 2, and as a result, the durability as the phosphor sheet 4. Will improve.
  • the transparent resin layer 5 may further contain fine particles. Since the transparent resin layer 5 contains fine particles, the film thickness uniformity of the transparent resin layer 5 is improved, so that the phosphor sheet 4 can be accurately picked up in the phosphor sheet 4 pick-up process described later. .
  • One of the causes for the non-uniform thickness of the transparent resin layer 5 is the flow of resin in the drying process when the transparent resin layer 5 is formed. In this drying step, the resin contained in the transparent resin layer 5 is easy to flow because the viscosity is lowered by being heated.
  • the resin contained in the transparent resin layer 5 is a silicone resin having heat-fusibility, since the viscosity of the resin is significantly reduced, the film thickness of the transparent resin layer 5 tends to be non-uniform.
  • a silicone resin having heat-fusibility is used for the transparent resin layer 5, it is particularly important that the transparent resin layer 5 contains fine particles in order to maintain the uniformity of the film thickness of the transparent resin layer 5.
  • Improvement of the uniformity of the film thickness of the transparent resin layer 5 also has an effect of enhancing the function of the transparent resin layer 5 as a protective layer.
  • this thin portion does not sufficiently function as a protective layer, so that the durability of the obtained light emitter is inferior. According to the present invention, such a situation can be suppressed.
  • the resin used for the transparent resin layer 5 examples include silicone resin, fluororesin, epoxy resin, polyarylate resin, PET-modified polyarylate resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, One or more resins selected from a modified acrylic resin, a polystyrene resin, and an acrylonitrile / styrene copolymer resin are preferable. Among these, one or more kinds of resins selected from silicone resins, fluororesins, and epoxy resins are more preferable, and silicone resins are particularly preferable from the viewpoint of heat resistance.
  • the silicone resin may have a heat-fusibility.
  • this silicone resin has heat-fusibility, when forming the transparent resin layer 5 by the transparent resin sheet method mentioned later, the fluorescent substance layer 2 and the transparent resin layer 5 can be adhere
  • the fine particles used for the transparent resin layer 5 are preferably those that absorb little visible light or emit light.
  • the fine particles include fine particles such as titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate.
  • one or more types of fine particles selected from silica fine particles, alumina fine particles, and silicone fine particles are more preferable from the viewpoint of easy availability, and silicone fine particles are particularly preferable from the viewpoint of easy control of the refractive index and particle size. .
  • the minimum transmittance of the transparent resin layer 5 at a wavelength of 400 nm to 800 nm is reduced. It can be 80% or more.
  • the average particle size of the fine particles contained in the transparent resin layer 5 is preferably 1 nm or more, and more preferably 3 nm or more.
  • the average particle size of the fine particles is preferably 1000 nm or less, and more preferably 300 nm or less.
  • the average particle diameter of the fine particles is equal to or more than a preferable lower limit value, the fine particles can be stably dispersed in the transparent resin layer 5. Since the average particle diameter of the fine particles is 1000 nm or less, light scattering in the transparent resin layer 5 can be suppressed, so that the high light transmittance of the transparent resin layer 5 can be maintained.
  • the average particle diameter of the fine particles is a median diameter (D50).
  • the average particle diameter of the fine particles can be obtained by the same method as the average particle diameter of the red phosphor as the phosphor 1 described above.
  • the proportion of fine particles in the total solid content in the transparent resin layer 5 is preferably 0.1% by weight or more, and more preferably 1% by weight or more. Further, the proportion of the fine particles is preferably 30% by weight or less, and more preferably 10% by weight or more.
  • the variation in the film thickness of the transparent resin layer 5 can be suppressed when the ratio of the fine particles is equal to or more than a preferable lower limit value. When the proportion of the fine particles is equal to or less than the preferable upper limit value, the high light transmittance of the transparent resin layer 5 can be maintained.
  • the light transmittance of the transparent resin layer 5 containing fine particles can be measured using a spectrophotometer.
  • a spectrophotometer For example, when U-4100 Spectrophotometer manufactured by Hitachi, Ltd. is used, the light transmittance of the sample of the transparent resin layer 5 can be measured with a basic configuration using an integrating sphere attached to this measuring apparatus.
  • the slit is 2 nm and the scanning speed is 600 nm / min.
  • the sample for light transmittance measurement of the transparent resin layer 5 (hereinafter referred to as “transmittance measurement sample”) can be prepared by the following method. For example, the resin and fine particles used for the transparent resin layer 5 are stirred and degassed to prepare a dispersion. The dispersion is applied onto quartz glass with a blade coater and then heated in an oven at 150 ° C. for 1 hour. In this way, a transmittance measurement sample can be produced.
  • the film thickness of the transmittance measurement sample can be measured by the following method. For example, the thickness at a predetermined position of quartz glass is measured in advance with a micrometer, and the measured position is marked. Next, after forming a transmittance measurement sample of the transparent resin layer 5 on the quartz glass by the above-described method, the thickness of the marking portion is again measured with a micrometer. By subtracting the previously measured thickness of the quartz glass from the obtained thickness, the film thickness of this transmittance measurement sample can be obtained.
  • the refractive index difference between the resin and the fine particles contained in the transparent resin layer 5 is preferably 0.5 or less, more preferably 0.3 or less, and particularly preferably 0.1 or less.
  • the refractive index of the resin contained in the transparent resin layer 5 is preferably 1.3 or more, and preferably 1.6 or less. Since the refractive index difference of the resin is 1.3 or more, the difference in refractive index between the transparent resin layer 5 and the phosphor layer 2 becomes relatively small. Therefore, the light extraction efficiency from the phosphor layer 2 to the transparent resin layer 5 is improved. Can be improved.
  • the refractive index of the resin is 1.6 or less, the difference in refractive index between the transparent resin layer 5 and the air layer becomes relatively small, so that the light extraction efficiency from the transparent resin layer 5 to the air layer is improved. Can be made. Further, from the viewpoint of further improving the light extraction efficiency, the refractive index of the resin contained in the transparent resin layer 5 is preferably equal to or lower than the refractive index of the resin contained in the phosphor layer 2.
  • the refractive index of the resin contained in the transparent resin layer 5 is measured by measuring the refractive index of the refractive index measurement sample using a refractive index / film thickness measuring device “Prism Coupler Model 2010 / M” (made by Metricon). can do.
  • this resin was stirred for 10 minutes at 1000 rpm using a planetary stirring deaerator “Mazerustar KK-400” manufactured by Kurabo Industries, and defoamed to prepare a dispersion. After dropping 5 cc on the film, it can be obtained by heating at 150 ° C. for 1 hour in an oven.
  • the phosphor sheet 4 according to the embodiment of the present invention may include another phosphor layer or a diffusion layer different from the phosphor layer 2 on at least one of the top and bottom of the phosphor layer 2.
  • the transparent resin layer formed under the phosphor layer 2 or another phosphor layer does not use an adhesive for the LED chip. It is preferable to have heat-fusibility so that it can be affixed to.
  • the refractive index of this LED chip surface and the transparent resin layer located under any phosphor layer As the refractive index difference is smaller, the light extraction efficiency from the LED chip surface to the transparent resin layer can be improved. Therefore, in this case, the refractive index of the transparent resin layer is preferably 1.56 or more.
  • the diffusion layer is a layer containing a predetermined resin and a diffusion material such as silica, titania or zirconia. By forming the diffusion layer, the directivity of emitted light can be weakened and more isotropic emitted light can be obtained. Therefore, the diffusion layer is preferably formed in the upper layer of the phosphor layer 2.
  • One method for producing the phosphor sheet 4 is to apply the phosphor layer 2 directly on the support 3.
  • a coating solution for forming the phosphor layer 2 a solution in which the phosphor 1 is dispersed in the resin 14 (hereinafter, referred to as “phosphor layer preparation resin solution”) is prepared.
  • the resin liquid for producing a phosphor layer is obtained by mixing phosphor 1 and resin 14 in a solvent.
  • the type of the solvent is not particularly limited as long as the viscosity of the resin 14 in a fluid state can be adjusted.
  • the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexane, acetone, terpineol, butyl carbitol, butyl carbitol acetate, glyme, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. Can be mentioned.
  • a resin solution for preparing a phosphor layer can be obtained by homogeneously mixing and dispersing with a stirrer / kneader such as a three-roller, ball mill, planetary ball mill, or bead mill. Defoaming is preferably performed after this mixing and dispersion or in the process of mixing and dispersion under vacuum or reduced pressure conditions.
  • the Mn-activated bifluoride complex phosphor as the phosphor 1 has properties of low hardness and brittleness as compared with a phosphor produced by firing at a high temperature such as a ⁇ -type sialon phosphor. Therefore, when the Mn-activated double fluoride complex phosphor is dispersed with a stirrer / kneader or the like, the Mn-activated double fluoride complex phosphor can be dispersed by setting the dispersion conditions so that the impact applied to the Mn-activated double fluoride complex phosphor is as small as possible. It is preferable to suppress crushing of the fluoride complex phosphor. By suppressing the crushing of the Mn-activated double fluoride complex phosphor, the phosphor sheet 4 having a high emission intensity can be obtained.
  • the phosphor layer preparation resin solution prepared as described above is applied onto the support 3 and dried.
  • the phosphor layer 2 obtained on the support 3 is produced by heat curing.
  • Application of the resin liquid for preparing the phosphor layer on the support 3 is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, screen printing, natural roll coater, air knife coater, roll.
  • a blade coater, two stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater or the like can be used.
  • a slit die coater In order to obtain the uniformity of the film thickness of the phosphor layer 2, it is preferable to apply with a slit die coater.
  • the phosphor layer 2 can also be produced by using a printing method such as screen printing, gravure printing, or lithographic printing. In particular, screen printing is preferably used.
  • the drying of the phosphor layer forming resin liquid can be performed using a general heating device such as a hot air dryer or an infrared dryer.
  • a general heating device such as a hot air dryer or an infrared dryer is used.
  • the heat curing condition is usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 minutes to 3 hours.
  • the phosphor sheet 4 provided with at least the phosphor layer 2 can be produced by the method described above. As illustrated in FIG. 1A, the phosphor sheet 4 is in a state of being supported by the support body 3 as a single sheet.
  • the support 3 used in the present invention is not particularly limited, and examples thereof include known metals, resin films, glass, ceramics, paper, and cellulose acetate.
  • glass and a resin film are preferably used from the viewpoint of easy preparation of the phosphor sheet 4 and easy separation of the phosphor sheet 4.
  • the support 3 is preferably in the form of a flexible film because of the adhesion when the phosphor sheet 4 is attached to the LED chip.
  • a film having high strength is preferable as the support 3 so that there is no fear of breakage or the like when the film-shaped support 3 is handled.
  • a resin film is preferable as the support 3 in terms of these required characteristics and economy.
  • a plastic film selected from the group consisting of polyethylene terephthalate, polyphenylene sulfide, polypropylene, and polyimide is preferable from the viewpoints of economy and handleability.
  • a polyimide film is preferable from the viewpoint of heat resistance.
  • the surface of the support 3 may be subjected to a release treatment in advance from the ease of peeling off the phosphor sheet 4 from the support 3.
  • the forming method of the transparent resin layer 5 includes a direct coating method and a transparent resin sheet method.
  • a resin solution whose viscosity is adjusted with a transparent resin solvent for the production of the transparent resin layer 5 (hereinafter referred to as “resin solution for producing a transparent resin layer”) is directly applied onto the phosphor layer 2. Thereafter, drying and heat curing are performed.
  • the transparent resin layer preparation resin solution can be applied by the same method as the preparation of the phosphor layer 2 (application of the phosphor layer preparation resin solution).
  • a resin solution for preparing a transparent resin layer with a slit die coater can be applied using a general heating device such as a hot air dryer or an infrared dryer.
  • a general heating device such as a hot air dryer or an infrared dryer is used.
  • the heat curing condition is usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 minutes to 3 hours.
  • the transparent resin sheet method a transparent resin sheet is produced, and the phosphor layer 2 side of the phosphor sheet 4 and the transparent resin layer 5 side of the produced transparent resin sheet are bonded to each other on the phosphor layer 2.
  • the transparent resin sheet can be produced by the same method as the phosphor sheet 4 provided with the phosphor layer 2 described above. That is, using the “transparent resin layer preparation resin liquid” instead of the “phosphor layer preparation resin liquid”, a method similar to the method of manufacturing the phosphor sheet 4 described above is performed, and a predetermined support (for example, a support)
  • a transparent resin sheet can be produced by forming the transparent resin layer 5 on the same body 3.
  • the resin of at least one of the phosphor layer 2 and the transparent resin layer 5 needs to be in a semi-cured state.
  • the resin of at least one layer is in a semi-cured state, the phosphor layer 2 and the transparent resin layer 5 can be bonded.
  • the transparent resin sheet method at least the resin of the transparent resin layer 5 is more preferably semi-cured, and both the resin 14 of the phosphor layer 2 and the resin of the transparent resin layer 5 are in a semi-cured state. Particularly preferred.
  • the phosphor layer 2 and the transparent resin layer 5 are bonded together by heating.
  • the viscosity of each resin of the phosphor layer 2 and the transparent resin layer 5 is lowered, so that the phosphor layer 2 and the transparent resin layer 5 can be firmly bonded.
  • the heating condition is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher.
  • the resin in a semi-cured state (for example, the resin of the transparent resin layer 5) is cured before the phosphor layer 2 and the transparent resin layer 5 are bonded.
  • the heating condition is preferably 200 ° C. or less, more preferably 170 ° C. or less, and particularly preferably 150 ° C. or less.
  • the phosphor layer 2 and the transparent resin layer 5 are preferably bonded together in a vacuum atmosphere.
  • a vacuum atmosphere is an atmosphere whose pressure is a predetermined value or less. The pressure in this vacuum atmosphere is 100 hPa or less, more preferably 10 hPa or less, further preferably 5 hPa or less, and particularly preferably 1 hPa or less.
  • FIG. 2 is a process diagram showing an example of a method for manufacturing a light emitter using the phosphor sheet according to the embodiment of the present invention.
  • the following description is an example and the manufacturing method of the light-emitting body based on embodiment of this invention is not limited to what is demonstrated below.
  • the manufacturing method of the light emitter using the phosphor sheet 4 roughly includes three steps.
  • the first step is an individualization step for individualizing the phosphor sheet 4.
  • the second step is a pickup step for picking up the individual phosphor sheet 4.
  • the third step is a pasting step of pasting the picked up phosphor sheet 4 (individualized by the individualizing step) to a light source.
  • the manufacturing method of this light-emitting body may include the other process as needed.
  • the phosphor sheet 4 is composed of the phosphor layer 2 formed on the support 3, and the phosphor layer 2 as the phosphor sheet 4 is separated into individual pieces, and an LED chip which is an example of a light source A method for manufacturing a light emitter according to an embodiment of the present invention will be described with reference to FIG.
  • the phosphor sheet 4 can be singulated by a method such as punching with a mold, processing with a laser, dicing or cutting.
  • the phosphor layer 2 as the phosphor sheet 4 may be in a semi-cured state or may be cured in advance. Processing with a laser imparts high energy to the phosphor layer 2, so that the resin of the phosphor layer 2 (for example, the resin 14 shown in FIG. 1A) is burnt or the phosphor (for example, the phosphor 1 shown in FIG. 1A) is deteriorated. It is very difficult to avoid. Therefore, as a method for dividing the phosphor sheet 4 into pieces, cutting or cutting with a blade is desirable.
  • the phosphor layer 2 as the phosphor sheet 4 is in a state of being supported by the support 3.
  • the phosphor layer 2 on the support 3 is cut by the blade 6 (state S1).
  • the phosphor layer 2 is divided into a plurality of pieces and processed into the individual phosphor layers 7 (state S2).
  • the individualized phosphor layer 7 remains attached to the support 3.
  • the blade 6 is, for example, a rotary blade.
  • a device for cutting the phosphor layer 2 with a rotary blade a device called a dicer used for cutting (dicing) a semiconductor substrate into individual chips can be suitably used. If the dicer is used, the width of the dividing line of the phosphor layer 2 can be precisely controlled by the thickness of the rotary blade and the condition setting, so that higher processing accuracy can be obtained than cutting the phosphor layer 2 by pushing a simple blade. .
  • the phosphor layer 2 may be singulated together with the support 3. Alternatively, the support 3 may not be cut while the phosphor layer 2 is separated. Under the present circumstances, it is preferable to perform what is called a half cut with respect to the support body 3 in which the notch line which does not penetrate enters.
  • the phosphor layer 2 is preferably cut by dry cutting.
  • Dry cutting is a cutting method that does not use liquid such as water during cutting.
  • the cutting of the phosphor layer 2 in the singulation process is not limited to this, and examples thereof include cutting with a Thomson blade. Dry cutting is particularly effective when the phosphor layer 2 contains a phosphor whose luminous efficiency is reduced by reacting with water, such as K 2 SiF 6 : Mn.
  • the phosphor sheet 4 may be subjected to perforation processing of the phosphor layer 2 before or after the individualization step or simultaneously with the individualization step.
  • a known method such as laser processing or punching with a mold can be suitably used.
  • laser processing causes scorching of the resin of the phosphor layer 2 and deterioration of the phosphor, punching with a mold is possible. Processing is more desirable.
  • the phosphor sheet 4 singulated by the singulation process described above is picked up by a pickup process that is the next process of the singulation process.
  • a pickup process that is the next process of the singulation process.
  • the singulated phosphor layer 7 is in a state of being stuck on the support 3.
  • the singulated phosphor layer 7 is peeled off and picked up from the support 3 by a pickup device (not shown) provided with a suction device such as a collet 8 (state S3).
  • the individualized phosphor layer 7 (an example of the individualized phosphor sheet 4) picked up by the pickup process described above is attached to the light source by the application process which is the next process of the pickup process.
  • the singulated phosphor layer 7 is picked up by a collet 8.
  • the collet 8 is transported together with the individualized phosphor layer 7 to the position of the LED chip 9 (an example of a light source) mounted on the substrate 11, thereby the light extraction surface of the LED chip 9 and the individualized phosphor layer 7.
  • the adhesive surface (for example, the lower surface) is made to oppose.
  • the collet 8 presses and adheres the adhesive surface of the singulated phosphor layer 7 to the light extraction surface of the LED chip 9 (state S4).
  • the reflector 10 may be formed around the LED chip 9 on the substrate 11.
  • an adhesive (not shown) for attaching the singulated phosphor layer 7 and the LED chip 9 in the attaching step.
  • this adhesive a well-known die bond agent and an adhesive agent can be used.
  • acrylic resin, epoxy resin, urethane resin, silicone resin, modified silicone resin, phenol resin, polyimide, polyvinyl alcohol, polymethacrylate resin, melamine resin, urea resin adhesive can be used.
  • the phosphor layer 2 has adhesiveness
  • the individualized phosphor layer 7 and the LED chip 9 may be attached using this adhesiveness.
  • the sticking step is a step of heating the individual phosphor layer 7 and sticking it to the LED chip 9
  • this sticking step is performed in the atmosphere, the LED chip 9 and the individual phosphor layer 7 are not separated. Air bubbles may be caught in When bubbles are bitten, light is irregularly reflected at the interface between the bubbles and the LED chip 9 and at the interface between the bubbles and the singulated phosphor layer 7. Thereby, the light extraction efficiency from the LED chip 9 is lowered, and as a result, the luminance of the light emitter (for example, the light emitter 13 shown in FIG. 2) manufactured using the phosphor sheet 4 is lowered. From the viewpoint of preventing such bubble entrapment, this sticking step is preferably performed in a vacuum atmosphere.
  • the light emitting body manufacturing method described above may further include a connection step of electrically connecting the LED chip 9 and the substrate 11 which is an example of a circuit board as other steps.
  • this connection step the electrode of the LED chip 9 and the wiring of the substrate 11 are electrically connected by a known method. Thereby, the light emitter 13 can be obtained.
  • the LED chip 9 has an electrode on the light extraction surface side, the electrode on the upper surface of the LED chip 9 and the wiring of the substrate 11 are connected by wire bonding.
  • the LED chip 9 is a flip chip type having an electrode pad on the surface opposite to the light emitting surface, the electrode surface of the LED chip 9 is opposed to the wiring of the substrate 11 and these are connected by batch bonding.
  • the substrate 11 and the LED chip 9 may be connected before the individualized phosphor sheet 4 (for example, the individualized phosphor layer 7) is attached.
  • the individual phosphor layer 7 When the individual phosphor layer 7 is attached to the LED chip 9 in a semi-cured state, the individual phosphor layer 7 can be cured at a suitable timing before or after the connection step described above. For example, when thermocompression bonding is performed so that the flip chip type LED chip 9 is bonded to the substrate 11 at once, the individualized phosphor layer 7 may be simultaneously cured by the heating. In the case where the package in which the LED chip 9 and the substrate 11 are connected is surface-mounted on a larger circuit board, the individualized phosphor layer 7 may be cured simultaneously with soldering by solder reflow. .
  • the individual phosphor layer 7 When the LED chip 9 is attached in a state where the individual phosphor layer 7 is cured, after the individual phosphor layer 7 and the LED chip 9 are attached, the individual phosphor layer 7 There is no need to provide a curing process.
  • the case where the individualized phosphor layer 7 is affixed to the LED chip 9 in a cured state includes, for example, a case where a separate adhesive layer is formed on the cured individualized phosphor layer 7, or an individualized phosphor layer. This is the case when the body layer 7 has heat-fusibility after curing.
  • the manufacturing method of the light emitting body described above may further include a sealing step of sealing the LED chip 9 after the pasting step is performed as another step.
  • a sealing step of sealing the LED chip 9 after the pasting step is performed as another step.
  • the transparent sealing material 12 is placed on the substrate 11 (in detail, a reflector so as to cover the LED chip 9 after the individualized phosphor layer 7 is attached). 10).
  • this LED chip 9 is sealed by the transparent sealing material 12 (state S5).
  • the transparent sealing material 12 a silicone resin is suitably used from the viewpoint of transparency and heat resistance.
  • the phosphor sheet 4 includes the phosphor layer 2 on the support 3 is illustrated. It is not limited to. That is, the phosphor sheet 4 used in this method for manufacturing a phosphor may be composed of the phosphor layer 2, or the phosphor layer 2 and the transparent resin layer 5 illustrated in FIG. 1B. It may consist of a laminated body, or may further include other layers such as the diffusion layer described above.
  • the phosphor sheet 4 includes the phosphor layer 2 and the transparent resin layer 5
  • both the phosphor layer 2 and the transparent resin layer 5 on the support 3 are singulated in the individualization step. .
  • the pick-up process the laminated body obtained by dividing the phosphor layer 2 and the transparent resin layer 5 is picked up from the support 3. In the sticking step, the picked-up laminate (separated) is stuck on the light extraction surface of the LED chip 9.
  • the light emitter according to the embodiment of the present invention includes the phosphor sheet 4 described above.
  • the light emitter 13 shown in FIG. 2 includes an individualized phosphor layer 7 as the phosphor sheet 4 on the light extraction surface of the LED chip 9.
  • Such a light emitter can be widely applied to an in-vehicle headlight, a backlight of a television or a smartphone, illumination, and the like.
  • the phosphor sheet 4 and a phosphor using the phosphor sheet are preferably applied to a light source unit such as a backlight because they are excellent in color reproducibility and have high luminous flux and high durability.
  • the light source unit according to the embodiment of the present invention includes the phosphor sheet 4 described above.
  • the light source unit includes a light source having a phosphor having the phosphor sheet 4.
  • Such a light source unit can be applied to displays for televisions, smartphones, tablet computers, and game machines.
  • the display according to the embodiment of the present invention includes a light source unit having the phosphor sheet 4 described above.
  • This display includes a display provided with a light source unit having a light emitter (light emitter manufactured using the phosphor sheet 4) in the present invention.
  • a display is a liquid crystal display.
  • the color reproduction range of a liquid crystal display when a light-emitting body produced using the phosphor sheet 4 is used as a backlight of a liquid crystal display can be evaluated by a DCI ratio.
  • the DCI ratio is an area ratio in the chromaticity region when the area of the DCI chromaticity region according to the DCI (Digital Cinema Initiative) standard is used as a reference (100%).
  • the DCI ratio can be measured by the following procedure.
  • a color filter that transmits red light produced by a known method is placed on the produced illuminant, and 1 W of electric power is applied to the illuminant to turn on the illuminant, and the total luminous flux measurement system (HM) -3000, manufactured by Otsuka Electronics Co., Ltd.) to measure the chromaticity of the emitted light.
  • the chromaticity of the emitted light is measured for each of a case where a color filter that transmits green light is placed on the light emitter and a case where a color filter that transmits blue light is placed.
  • the DCI ratio can be calculated by dividing the area of the triangle having the obtained three chromaticities as vertices by the area of the DCI chromaticity region.
  • Silicone resin T11 is OE-6351A / B (manufactured by Toray Dow Corning). The refractive index of the silicone resin T11 is 1.41. Silicone resin T12 is KER6075LV A / B (made by Shin-Etsu Chemical Co., Ltd.). The refractive index of the silicone resin T12 is 1.45. The silicone resin T13 is XE14-C2860 (manufactured by Momentive Performance Materials). The refractive index of the silicone resin T13 is 1.50. Silicone resin T14 is OE6630 A / B (made by Toray Dow Corning Co., Ltd.). The refractive index of the silicone resin T14 is 1.53.
  • Silicone resin T15 contains 75 parts by weight of the following component (E), 10 parts by weight of component (F), 25 parts by weight of component (G), 0.025 parts by weight of reaction inhibitor, and 0.01% of platinum catalyst. It was obtained by mixing parts by weight.
  • the transparent resin sheet produced using the silicone resin T15 had a storage elastic modulus at 25 ° C. of 1 Mpa, a storage elastic modulus at 100 ° C. of 0.01 MPa, and exhibited good heat-fusibility.
  • the refractive index of the silicone resin T15 is 1.56.
  • the component (E) is (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 0.45 (HO 1/2 ) 0.03 .
  • the component (F) is ViMe 2 SiO (MePhSiO) 17.5 SiMe 2 Vi.
  • the component (G) is (HMe 2 SiO) 2 SiPh 2 .
  • Me is a methyl group
  • Vi is a vinyl group
  • Ph is a phenyl group.
  • the reaction inhibitor is 1-ethynylhexanol.
  • the platinum catalyst is a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.
  • the platinum content of this solution is 5% by weight.
  • Silicone resin T16 was obtained by the following preparation method.
  • the refractive index of the silicone resin T16 is 1.60.
  • silicone resin T16 In the preparation method of silicone resin T16, 1-naphthyltrimethoxysilane (892.8 g) and 1,3-divinyl-1,3-diphenyldimethyldisiloxane (372.0 g) were charged into a reaction vessel and mixed in advance. Thereafter, trifluoromethanesulfonic acid (6.15 g) was added, and water (213.84 g) was added with stirring, followed by heating under reflux for 2 hours. Then, heating and normal pressure distillation were performed until it became 85 degreeC.
  • 1-naphthyltrimethoxysilane 50 g was charged into a reaction vessel, heated and melted, and trifluoromethanesulfonic acid (0.06 g) was added. Subsequently, acetic acid (9.3 g) was added dropwise while heating to 45 ° C. to 50 ° C. After completion of dropping, the mixture was heated and stirred at 50 ° C. for 30 minutes. Low boiling point substances were distilled off under normal pressure by heating until the reaction temperature reached 80 ° C. Thereafter, the mixture was cooled to room temperature, 1,3,3-tetramethyldisiloxane (4.4 g) was added dropwise and heated until the reaction temperature reached 45 ° C.
  • acetic acid (18 g) was added dropwise at 45 ° C. to 50 ° C. After completion of dropping, the mixture was heated and stirred at 50 ° C. for 30 minutes.
  • Acetic anhydride (15.5 g) was added dropwise while keeping the temperature at 60 ° C. or lower by air cooling or water cooling, and after completion of the dropwise addition, the mixture was stirred at 50 ° C. for 30 minutes. Next, toluene and water were added, and stirring, standing, and extraction of the lower layer were repeated, followed by washing with water.
  • organopolysiloxane resin P1 52.0 parts by mass of organopolysiloxane resin P1, 30.0 parts by mass of organopolysiloxane P2, 14.0 parts by mass of organotrisiloxane represented by the formula: HMe 2 SiOPh 2 SiOSiMe 2 H, and platinum-1 , 3-Divinyl-1,1,3,3-tetramethyldisiloxane complex 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane solution (0.
  • a curable silicone composition was prepared by mixing 0.25 part by mass of a solution containing 1% by mass.
  • Silicone resin T17 was obtained by the following preparation method.
  • the refractive index of the silicone resin T17 is 1.65.
  • silicone resin T17 methyltrimethoxysilane (16.6 g), phenyltrimethoxysilane (56.2 g), “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, Catalyst Kasei Kogyo Co., Ltd.) )
  • Composition Titanium oxide particles 20% by weight, methanol 80% by weight (194 g), propylene glycol monomethyl ether acetate (126.9 g) are placed in a reaction vessel, and water (21.9 g) and phosphoric acid ( 0.36 g) was added dropwise with stirring so that the reaction temperature did not exceed 40 ° C.
  • silicone resin T14 (8.00 g) was mixed with the obtained titanium oxide particles (50.00 g), and a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries Co., Ltd.) was used. The mixture was stirred and degassed for 20 minutes, thereby producing a silicone resin T17. As a result of measuring the refractive index, the average refractive index of the silicone resin T17 was 1.65.
  • Silicone resin T18 was obtained by the following preparation method.
  • the refractive index of the silicone resin T18 is 1.70.
  • silicone resin T18 In the preparation method of silicone resin T18, silicone resin T14 (3.0 g) is mixed with titanium oxide particles (60.0 g) grafted with polysiloxane in the same manner as the preparation method of silicone resin T17 described above, and planetary type Using a stirring / degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring / degassing was performed at 1000 rpm for 20 minutes. Thereby, silicone resin T18 was produced. As a result of measuring the refractive index, the refractive index of the silicone resin T18 was 1.70.
  • the fluororesin T21 is AF2400S (Mitsui / DuPont Fluorochemical).
  • the refractive index of the fluororesin T21 is 1.30.
  • the fluororesin T22 is CTX-800 (CT-solv 180 solution) (manufactured by Asahi Glass Co., Ltd.).
  • the refractive index of the fluororesin T22 is 1.35.
  • the green phosphor is a ⁇ -sialon phosphor called GR-MW540K (manufactured by Denka Co., Ltd.).
  • the yellow phosphor is a Ce-doped YAG phosphor called NYAG-02 (manufactured by Intematix).
  • the red phosphor T1 is KSF phosphor sample A (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the red phosphor T2 is KSF phosphor sample B (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the red phosphor T3 is a KSF phosphor sample C (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the red phosphor T4 is a KSF phosphor sample D (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the red phosphor T5 is a KSF phosphor sample E (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the red phosphor T6 is a KSF phosphor sample F (manufactured by Nemoto Lumi Material Co., Ltd.).
  • the D10, D50 and D90 of the red phosphors T1 to T6 used in this example were measured by the following method. The measurement results are shown in Table 1. Table 1 also shows a value x calculated based on the above equation (11) based on the measured D10, D50, and D90.
  • a phosphor sheet (for example, phosphor sheet 4 shown in FIGS. 1A and 1B) is prepared as described later, and the cross section of the phosphor layer is SEM.
  • the maximum distance is calculated from the distance between the two intersections of the straight line that intersects the outer edge of the particle at two points, and this is defined as the individual particle size of the particle. did.
  • the particle size of 10% of the accumulated portion from the small particle size side is D10
  • the particle size of 50% of the accumulated portion is D50
  • the accumulated portion was designated as D90.
  • a base film is an example of the support body (For example, support body 3 shown to FIG. 1A and 1B) of the fluorescent substance sheet in this invention.
  • the base film was a PET film.
  • This PET film is “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd.), and its film thickness is 50 ⁇ m.
  • Silicone fine particles were obtained by the following production method.
  • a 2 L four-necked round bottom flask is equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel, and this flask is 2.5% containing 10,000 ppm of polyether-modified siloxane “BYK333” as a surfactant.
  • ammonia water (2 L) was added, and the temperature was raised by an oil bath while stirring at 300 rpm. When the internal temperature reached 50 ° C., a mixture of methyltrimethoxysilane and phenyltrimethoxysilane (22/78 mol%) (200 g) was dropped from the dropping funnel over 30 minutes.
  • the obtained silicone fine particles were observed with an SEM and confirmed to be monodispersed spherical fine particles.
  • As a result of calculating the average particle diameter of the silicone fine particles from the obtained SEM image it was 50 nm.
  • the refractive index of the silicone fine particles was measured by a liquid immersion method and found to be 1.54.
  • As a result of observing the silicone fine particles with a cross-sectional TEM it was confirmed that the particles were single-structured fine particles.
  • the silica fine particles T31 are Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.). The average particle diameter of the silica fine particles T31 is 12 nm. The refractive index of the silica fine particles T31 is 1.46.
  • the silica fine particles T32 are “Admanano” YA050C (manufactured by Admatechs Co., Ltd.). The average particle diameter of the silica fine particles T32 is 50 nm. The refractive index of the silica fine particles T32 is 1.46.
  • the silica fine particles T33 are “Admanano” YA100C (manufactured by Admatechs Co., Ltd.).
  • the average particle diameter of the silica fine particles T33 is 100 nm.
  • the refractive index of the silica fine particles T33 is 1.46.
  • Silica fine particles T34 are “Admafine” SO-E1 (manufactured by Admatechs Co., Ltd.).
  • the average particle diameter of the silica fine particles T34 is 250 nm.
  • the refractive index of the silica fine particles T34 is 1.46.
  • Silica fine particles T35 are HPS-1000 (manufactured by Toa Gosei Co., Ltd.).
  • the average particle diameter of the silica fine particles T35 is 1000 nm.
  • the refractive index of the silica fine particles T35 is 1.46.
  • Silica fine particles T36 are “Admafine” SO-E5 (manufactured by Admatechs Co., Ltd.). The average particle diameter of the silica fine particles T36 is 1500 nm. The refractive index of the silica fine particles T36 is 1.46.
  • the alumina fine particles are Aeroxide AluC (manufactured by Nippon Aerosil Co., Ltd.).
  • the average particle diameter of the alumina fine particles is 12 nm.
  • the refractive index of the alumina fine particles is 1.77.
  • the titania fine particles are MT-01 (manufactured by Teika Co., Ltd.).
  • the average particle diameter of the titania fine particles is 10 nm.
  • the refractive index of the titania fine particles is 2.50.
  • ⁇ Preparation of phosphor sheet> silicone resin, silicone fine particles, red phosphor, and green phosphor were mixed in a predetermined ratio in a polyethylene container having a volume of 300 mL. Furthermore, 8 wt% of toluene was added as a solvent, and a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries) was used to stir and degas at 1000 rpm to obtain a resin solution for preparing a phosphor layer. . Then, the fluorescent substance layer preparation resin liquid was apply
  • ⁇ Measurement of film thickness of phosphor layer In the measurement of the thickness of the phosphor layer in this example, the thickness at a predetermined position of the PET film for producing the phosphor layer was measured in advance with a micrometer and marked. Next, a phosphor layer was formed on this PET film, and then the thickness of the marking portion was measured again with a micrometer. The thickness of the phosphor layer was obtained by subtracting the thickness of the PET film previously measured from the obtained thickness. In this example, the film thickness was measured at 25 points in a grid pattern at intervals of 10 mm, and the average value of these was taken as the film thickness of the phosphor layer.
  • a phosphor sheet provided with a transparent resin layer on the phosphor layer was obtained.
  • the “phosphor sheet having a transparent resin layer on the phosphor layer” is appropriately referred to as a “phosphor sheet with a transparent resin layer”.
  • a transparent resin layer-forming resin solution is applied onto a PET film using a slit die coater and dried at 130 ° C. for 30 minutes, whereby a transparent resin sheet is formed.
  • a vacuum laminator V130 manufactured by Nikko Materials Co., Ltd.
  • the phosphor layer of the phosphor sheet and the transparent resin layer of the transparent resin sheet are thermocompression bonded at 100 ° C. for 30 seconds in a vacuum atmosphere of 1 hPa. By pasting together.
  • the PET film on the transparent resin sheet side was peeled off, thereby forming a transparent resin layer on the phosphor layer.
  • a phosphor sheet with a transparent resin layer was obtained.
  • ⁇ Porosity measurement> the phosphor sheet was cut by a focused ion beam (FIB) processing method, and the cross section of the phosphor layer was observed by SEM. 20 cross-sections were observed per phosphor sheet, and the total cross-sectional area corresponding to the voids of the 20 obtained two-dimensional images was calculated. By dividing the total cross-sectional area corresponding to the void by the total cross-sectional area of these 20 two-dimensional images, the porosity of the phosphor layer was obtained.
  • FIB focused ion beam
  • the phosphor sheet or the phosphor sheet with a transparent resin layer (1 cm square) produced as described above was cut with a cutting device (GCUT manufactured by UHT), thereby producing a 1 mm square.
  • 100 individual sheets were prepared.
  • the individual sheet is obtained by dividing a phosphor sheet or a phosphor sheet with a transparent resin layer.
  • a die bonding apparatus manufactured by Toray Engineering
  • a 1 mm square piece sheet was vacuum-adsorbed with a collet and peeled from the base film.
  • the phosphor layer of this individual sheet was aligned and pasted on the surface of the blue LED chip of the LED package in which the flip chip type blue LED chip was mounted and the reflector was formed around the blue LED chip. .
  • an adhesive was applied in advance on the blue LED chip, and a phosphor layer was attached via the adhesive. Silicone resin T15 was used for this adhesive.
  • Total luminous flux retention (%) (total luminous flux after 300 hours / total luminous flux immediately after the start of the test) ⁇ 100
  • ⁇ Color reproduction range measurement> In the measurement of the color reproduction range in this example, a color filter that transmits red light produced by a known method was placed on the luminous body produced as described above, and the chromaticity of the emitted light was measured. Similarly, the chromaticity of the emitted light was measured for each of the case where a color filter that transmits green light was placed on the light emitter and the case where a color filter that transmitted blue light was placed. The DCI ratio was calculated by dividing the area of the triangle with the three chromaticities obtained as vertices by the area of the DCI chromaticity region. The higher the DCI ratio, the better the color reproducibility.
  • the refractive index of the refractive index measurement sample is measured using a refractive index / film thickness measuring device “prism coupler MODEL 2010 / M” (manufactured by Metricon Co., Ltd.). The refractive index of the cured fluororesin was measured.
  • ⁇ Preparation of refractive index measurement sample> In the preparation of the refractive index measurement sample in this example, the resin contained in the phosphor sheet was stirred for 10 minutes at 1000 rpm using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), and defoamed. Thus, a dispersion of this resin was produced. After 5 cc of this dispersion was dropped onto a PET film, it was heated in an oven at 150 ° C. for 1 hour, thereby producing an average refractive index measurement sample as a refractive index measurement sample.
  • the light transmittance of the transparent resin layer containing fine particles is a basic configuration using an integrating sphere attached to a spectrophotometer (U-4100 Spectrophotometer (manufactured by Hitachi, Ltd.)). It was obtained by measuring the light transmittance of the measurement sample.
  • the transmittance measurement sample used in each example was used.
  • the slit was 2 nm and the scanning speed was 600 nm / min.
  • the smallest value among the light transmittances at wavelengths of 400 nm to 800 nm was defined as the minimum transmittance.
  • the silicone resin and fine particles used for the transparent resin layer are mixed in a polyethylene container having a volume of 300 mL, and the planetary stirring deaerator “Mazerustar KK-400” (manufactured by Kurabo Industries Co., Ltd.) Was stirred at 1000 rpm for 10 minutes and defoamed to prepare a dispersion.
  • the dispersion is applied onto quartz glass with a blade coater and then heated in an oven at 150 ° C. for 1 hour.
  • permeability measurement sample was produced about each Example.
  • ⁇ Measurement of film thickness of transmittance measurement sample> In the film thickness measurement of the transmittance measurement sample in this example, the thickness at a predetermined position of the quartz glass was previously measured with a micrometer, and the measured position was marked. Next, after forming a transmittance measurement sample of the transparent resin layer on the quartz glass, the thickness of the marking portion was again measured with a micrometer. The film thickness of this transmittance measurement sample was obtained by subtracting the thickness of the quartz glass previously measured from the obtained thickness. The film thickness was measured at 25 points in a grid pattern at intervals of 10 mm, and the average value of these was taken as the film thickness of the transmittance measurement sample.
  • Examples 1 to 6 (Examples 1 to 6) -Effect of phosphor particle size- In Examples 1 to 6, a phosphor sheet having a phosphor layer having the composition shown in Table 2 was prepared, and the porosity was measured by the method described above. Also, a phosphor (light emitting device) was prepared using the phosphor sheets obtained in each of Examples 1 to 6, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. did. These measurement results are shown in Table 3. As can be seen with reference to Tables 2 and 3, when the phosphor sheet according to the present invention was used, all of Examples 1 to 6 were able to obtain a light emitter with excellent color reproducibility and high luminous flux. .
  • the D50 of the red phosphor is 10 ⁇ m or more like the D50 of the red phosphors T2 to T6 shown in Table 1, the total luminous flux is further improved, and the D10 of the red phosphors T3 to T6 shown in Table 1 is improved.
  • the D10 of the red phosphor is 5 ⁇ m or more, the total luminous flux retention rate is further improved.
  • the porosity of the phosphor sheet tended to decrease as the D10 and D50 of the red phosphor increased.
  • Example 7 to 13 Effect of phosphor concentration-
  • a phosphor sheet having a phosphor layer having the composition shown in Table 4 was prepared, and the porosity was measured by the method described above.
  • a phosphor was prepared using the phosphor sheet obtained in each of Examples 7 to 13, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 5.
  • Table 4 shows the composition of Example 6 again, and Table 5 shows the result of Example 6 again. From Tables 4 and 5, it was found that the higher the concentration of the phosphors such as the red phosphor T6 and the green phosphor, the higher the total luminous flux retention rate.
  • Examples 14 to 17 Effect of silicone fine particles
  • a phosphor sheet having a phosphor layer having the composition shown in Table 6 was produced, and the porosity was measured by the method described above.
  • a phosphor was prepared using the phosphor sheets obtained in each of Examples 14 to 17, and the chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 7. From Tables 6 and 7, it was found that the chromaticity variation ( ⁇ (Cx)) was further improved by containing the silicone fine particles.
  • a phosphor sheet was produced with a composition in which the silicone resin T15 was 50 wt% and the red phosphor T6 was 50 wt%.
  • a phosphor sheet was produced with a composition in which the silicone resin T15 was 50 wt% and the green phosphor was 50 wt%.
  • Example 19 to 25 Effect of refractive index of phosphor layer resin-
  • phosphor sheets having phosphor layers having the compositions shown in Table 9 were produced. Further, the film thickness of the phosphor layer of the phosphor sheet produced in each of Examples 19 to 25 was measured by the method described above. Moreover, also about the fluorescent substance sheet of Example 10, the film thickness of the fluorescent substance layer was measured. Further, a phosphor was produced using the phosphor sheet produced in each of Examples 19 to 25, and chromaticity, total luminous flux, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 10. Table 9 shows the composition of Example 10 again, and Table 10 shows the measurement result of Example 10 again.
  • Example 26 to 36 Effect of refractive index of transparent resin layer-
  • a resin solution for preparing a transparent resin layer was applied onto the phosphor sheet prepared in Example 6 using a slit die coater, and this resin solution for preparing a transparent resin layer was applied.
  • a phosphor resin sheet having a transparent resin layer on a phosphor layer is prepared by preparing a transparent resin sheet by the above-described method using silicone resin T15 and bonding the phosphor layer and the transparent resin layer. Produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 26 to 36 was measured by the method described above.
  • the phosphor layer side of the phosphor sheet with the transparent resin layer produced in each of Examples 26 to 36 is attached on the LED chip to produce a light emitter, and the chromaticity, total luminous flux is obtained by the above-described method.
  • the total luminous flux retention and the color reproduction range were measured.
  • Table 11 shows the types of resins used in the production of the resin liquid for producing the transparent resin layer in each of Examples 26 to 36 and the measurement results in Examples 26 to 36.
  • Examples 37 to 42-Refractive index of fine particles- resin solutions for preparing a transparent resin layer having the compositions shown in Table 12 were prepared. Next, the transparent resin layer preparation resin solution prepared in each of Examples 37 to 42 was applied on the phosphor sheet prepared in Example 10, and the transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 37 to 42 was measured by the method described above. Next, the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 37 to 42 is attached on the LED chip to produce a light emitter. The luminous flux, total luminous flux retention, and color reproduction range were measured. Further, a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing the transparent resin layer prepared in each of Examples 37 to 42, and the light transmittance of the transparent resin layer was measured by the above-described method. . Table 13 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 37 to 42 and the measurement results thereof.
  • Example 43 to 47 Additional amount of silica fine particles-
  • resin solutions for preparing a transparent resin layer having the compositions shown in Table 14 were prepared.
  • the transparent resin layer preparation resin solution prepared in each of Examples 43 to 47 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 43 to 47 was measured by the method described above.
  • the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 43 to 47 is attached on the LED chip to produce a light emitter.
  • the luminous flux, total luminous flux retention, and color reproduction range were measured.
  • a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 43 to 47, and the light transmittance of the transparent resin layer was measured by the method described above.
  • Table 15 shows the refractive index difference between the resin and fine particles of the transparent resin layer in each of Examples 43 to 47, and the measurement results thereof.
  • Table 14 shows the compositions of Examples 38 and 39 again, and Table 15 shows the results of Examples 38 and 39 again.
  • the content of the silica fine particles T31 is preferably 30% by weight or less and more preferably 10% by weight or less from the viewpoint of the minimum transmittance. Further, it was found that the content of the silica fine particles T31 is preferably 0.1% by weight or more and more preferably 1% by weight or more from the viewpoint of suppressing variation in the thickness of the transparent resin layer. .
  • Example 48 to 52 Alumina fine particle addition amount-
  • resin solutions for preparing a transparent resin layer having the compositions shown in Table 16 were prepared.
  • the transparent resin layer preparation resin solution prepared in each of Examples 48 to 52 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 48 to 52 was measured by the method described above.
  • the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 48 to 52 is attached on the LED chip to produce a light emitter.
  • the luminous flux, total luminous flux retention, and color reproduction range were measured.
  • a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing the transparent resin layer prepared in each of Examples 48 to 52, and the light transmittance of the transparent resin layer was measured by the method described above.
  • Table 17 shows the difference in refractive index between the resin and fine particles of the transparent resin layer in each of Examples 48 to 52 and the measurement results thereof.
  • Table 16 shows the compositions of Examples 38 and 41 again, and Table 17 shows the results of Examples 38 and 41 again.
  • the content of the alumina fine particles is preferably 30% by weight or less, and more preferably 10% by weight or less from the viewpoint of the minimum transmittance.
  • the content of the alumina fine particles is preferably 0.1% by weight or more, and more preferably 1% by weight or more, from the viewpoint of suppressing variation in the thickness of the transparent resin layer.
  • Example 53 to 57 -Addition amount of silicone fine particles-
  • a resin liquid for preparing a transparent resin layer having the composition shown in Table 18 was prepared.
  • the transparent resin layer preparation resin solution prepared in each of Examples 53 to 57 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 53 to 57 was measured by the method described above.
  • the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 53 to 57 is attached on the LED chip to produce a light emitter.
  • the luminous flux, total luminous flux retention, and color reproduction range were measured.
  • a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 53 to 57, and the light transmittance of the transparent resin layer was measured by the method described above.
  • Table 19 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 53 to 57 and the measurement results thereof.
  • Table 18 shows the compositions of Examples 38 and 40 again, and Table 19 shows the results of Examples 38 and 40 again.
  • Example 58 to 62 Particle size of fine particles-
  • resin solutions for preparing a transparent resin layer having the compositions shown in Table 20 were prepared.
  • the transparent resin layer preparation resin solution prepared in each of Examples 58 to 62 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
  • the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 58 to 62 was measured by the method described above.
  • the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 58 to 62 is attached on the LED chip to produce a light emitter.
  • the luminous flux, total luminous flux retention, and color reproduction range were measured.
  • a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 58 to 62, and the light transmittance of the transparent resin layer was measured by the method described above. .
  • Table 21 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 58 to 62 and the measurement results thereof.
  • Table 20 shows the compositions of Examples 38 and 39 again, and Table 21 shows the results of Examples 38 and 39 again. From Tables 20 and 21, it was found that the smaller the particle size of the fine particles, the higher the minimum transmittance and the smaller the variation in the thickness of the transparent resin layer.
  • a phosphor sheet was prepared with a composition in which the silicone resin T15 was 40 wt% and the yellow phosphor (YAG yellow phosphor) was 60 wt%, and the porosity was obtained by the method described above. Was measured. Further, a phosphor was prepared using the obtained phosphor sheet, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 22. From Table 22, it was found that when a YAG yellow phosphor was used, the color reproduction range was 70%, which was not suitable for a backlight for a liquid crystal display.
  • the phosphor sheet according to the present invention, the light emitter using the phosphor sheet, the light source unit, the display, and the method for producing the light emitter are a phosphor sheet that achieves both improved color reproducibility and high luminous flux, and Is suitable for a manufacturing method of a light emitter, a light source unit, a display, and a light emitter.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Led Device Packages (AREA)
  • Luminescent Compositions (AREA)
  • Optical Filters (AREA)

Abstract

La présente invention concerne une feuille fluorescente pourvue d'une couche récente contenant des corps fluorescents rouges, des corps fluorescents de β-SiAlON et une résine. Les corps fluorescents rouges sont un composé de fluorure activé par Mn représentée par la formule générale (1). Formule générale (1) : A2MF6:Mn (dans la formule générale (1) : A représente un ou plusieurs métaux alcalins choisis dans le groupe constitué de Li, Na, K, Rb et Cs, et comprend au moins l'un de Na et K ; et M représente un ou plusieurs éléments tétravalents choisis dans le groupe constitué de Si, Ti, Zr, Hf, Ge et Sn).
PCT/JP2016/085710 2015-12-04 2016-12-01 Feuille fluorescente, élément électroluminescent utilisant celle-ci, unité de source de lumière, affichage et procédé de production d'élément électroluminescent WO2017094832A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187014115A KR102419336B1 (ko) 2015-12-04 2016-12-01 형광체 시트, 그것을 사용한 발광체, 광원 유닛, 디스플레이 및 발광체의 제조 방법
CN201680066389.7A CN108351444B (zh) 2015-12-04 2016-12-01 荧光体片、使用其的发光体、光源单元、显示器及发光体的制造方法
JP2016571440A JP6852401B2 (ja) 2015-12-04 2016-12-01 蛍光体シート、それを用いた発光体、光源ユニット、ディスプレイ、および発光体の製造方法

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015237232 2015-12-04
JP2015-237232 2015-12-04
JP2015247004 2015-12-18
JP2015-247004 2015-12-18
JP2016088896 2016-04-27
JP2016-088896 2016-04-27

Publications (1)

Publication Number Publication Date
WO2017094832A1 true WO2017094832A1 (fr) 2017-06-08

Family

ID=58796994

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/085710 WO2017094832A1 (fr) 2015-12-04 2016-12-01 Feuille fluorescente, élément électroluminescent utilisant celle-ci, unité de source de lumière, affichage et procédé de production d'élément électroluminescent

Country Status (5)

Country Link
JP (1) JP6852401B2 (fr)
KR (1) KR102419336B1 (fr)
CN (1) CN108351444B (fr)
TW (1) TWI728011B (fr)
WO (1) WO2017094832A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107731996A (zh) * 2017-09-28 2018-02-23 惠州市华瑞光源科技有限公司 Led灯珠及其制备方法
JP2019001986A (ja) * 2017-06-14 2019-01-10 デンカ株式会社 フッ化物蛍光体とそれを用いた発光装置
JP2019001985A (ja) * 2017-06-14 2019-01-10 デンカ株式会社 フッ化物蛍光体とそれを用いた発光装置
JP2019064136A (ja) * 2017-09-29 2019-04-25 日亜化学工業株式会社 透光性シートの製造方法
JP2019164302A (ja) * 2018-03-20 2019-09-26 株式会社タムラ製作所 波長変換部材及び波長変換素子
JP2019186537A (ja) * 2018-03-30 2019-10-24 日亜化学工業株式会社 波長変換部材及び発光装置
WO2019218337A1 (fr) * 2018-05-18 2019-11-21 Rohm And Haas Electronic Materials Llc Film de phosphore à deux couches pour led
CN110753735A (zh) * 2017-06-14 2020-02-04 电化株式会社 氟化物荧光体和使用其的发光装置
JPWO2019021926A1 (ja) * 2017-07-28 2020-07-30 デュポン・東レ・スペシャルティ・マテリアル株式会社 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法
US11114589B2 (en) 2017-06-14 2021-09-07 Denka Company Limited Fluoride phosphor and light-emitting device using same
WO2022044860A1 (fr) * 2020-08-25 2022-03-03 デンカ株式会社 Luminophore de fluorure, complexe, et dispositif électroluminescent
WO2022075293A1 (fr) * 2020-10-06 2022-04-14 シャープ株式会社 Élément de conversion de longueur d'onde, équipement optique et procédé de fabrication d'élément de conversion de longueur d'onde
WO2022255173A1 (fr) * 2021-06-02 2022-12-08 東レ株式会社 Composition de conversion de couleur, feuille de conversion de couleur, unité de source de lumière comprenant celle-ci, affichage et dispositif d'éclairage
WO2023037831A1 (fr) * 2021-09-09 2023-03-16 信越化学工業株式会社 Phosphore ksf enrobé, son procédé de fabrication, composition de silicone polymérisable le contenant, et dispositif opto-semiconducteur
JP7530019B2 (ja) 2020-08-31 2024-08-07 日亜化学工業株式会社 発光装置の製造方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6690721B2 (ja) * 2017-07-28 2020-04-28 東レ株式会社 色変換組成物、色変換フィルムならびにそれを含む光源ユニット、ディスプレイおよび照明
US11094530B2 (en) 2019-05-14 2021-08-17 Applied Materials, Inc. In-situ curing of color conversion layer
US11239213B2 (en) 2019-05-17 2022-02-01 Applied Materials, Inc. In-situ curing of color conversion layer in recess
DE102022131065A1 (de) * 2022-11-23 2024-05-23 Ams-Osram International Gmbh Modifizierung von silikonen mit polysilsesquioxanpartikeln

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010093132A (ja) * 2008-10-09 2010-04-22 Sharp Corp 半導体発光装置およびそれを用いた画像表示装置、液晶表示装置
JP2012178574A (ja) * 2010-10-15 2012-09-13 Mitsubishi Chemicals Corp 白色発光装置及び照明器具
JP2013168480A (ja) * 2012-02-15 2013-08-29 Konica Minolta Inc Ｌｅｄ装置の製造方法
JP2014022704A (ja) * 2012-07-24 2014-02-03 Toray Ind Inc 蛍光体含有樹脂シートと発光装置及びその製造方法
WO2014077240A1 (fr) * 2012-11-13 2014-05-22 電気化学工業株式会社 Luminophore, élément électroluminescent et dispositif d'éclairage
JP2015052648A (ja) * 2013-09-05 2015-03-19 日亜化学工業株式会社 カラーフィルター及び発光装置の組合せの選択方法並びに画像表示装置の製造方法
WO2015056590A1 (fr) * 2013-10-15 2015-04-23 シャープ株式会社 Dispositif électroluminescent et son procédé de fabrication
JP2015091915A (ja) * 2013-10-04 2015-05-14 三菱化学株式会社 発光装置、及び波長変換部材
JP2015212360A (ja) * 2014-04-17 2015-11-26 パナソニックＩｐマネジメント株式会社 樹脂組成物およびその製造方法並びに半導体装置

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5332673B2 (ja) * 2008-02-07 2013-11-06 三菱化学株式会社 半導体発光装置、バックライトおよびカラー画像表示装置
KR101592836B1 (ko) * 2008-02-07 2016-02-05 미쓰비시 가가꾸 가부시키가이샤 반도체 발광 장치, 백라이트, 컬러 화상 표시 장치, 및 그들에 사용하는 형광체
WO2009110285A1 (fr) * 2008-03-03 2009-09-11 シャープ株式会社 Dispositif émetteur de lumière
JP5682104B2 (ja) * 2008-09-05 2015-03-11 三菱化学株式会社 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置
JP5391946B2 (ja) * 2009-09-07 2014-01-15 日亜化学工業株式会社 蛍光体及びそれを用いた発光装置並びに蛍光体の製造方法
JP5953797B2 (ja) * 2012-02-17 2016-07-20 東レ株式会社 半導体発光装置の製造方法
JP2013252637A (ja) * 2012-06-06 2013-12-19 Toray Ind Inc 蛍光体シート積層体
TWI625378B (zh) * 2012-10-25 2018-06-01 東麗股份有限公司 含有螢光體樹脂片與其製造方法、發光裝置與其製造方法以及螢光體分散樹脂組成物的製造方法
JP6119623B2 (ja) * 2014-01-30 2017-04-26 信越化学工業株式会社 複フッ化物蛍光体の製造方法
JP5804149B2 (ja) * 2014-01-30 2015-11-04 信越化学工業株式会社 複フッ化物蛍光体の製造方法及び処理方法
JP6008017B2 (ja) * 2015-06-12 2016-10-19 日亜化学工業株式会社 蛍光体及びこれを用いた発光装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010093132A (ja) * 2008-10-09 2010-04-22 Sharp Corp 半導体発光装置およびそれを用いた画像表示装置、液晶表示装置
JP2012178574A (ja) * 2010-10-15 2012-09-13 Mitsubishi Chemicals Corp 白色発光装置及び照明器具
JP2013168480A (ja) * 2012-02-15 2013-08-29 Konica Minolta Inc Ｌｅｄ装置の製造方法
JP2014022704A (ja) * 2012-07-24 2014-02-03 Toray Ind Inc 蛍光体含有樹脂シートと発光装置及びその製造方法
WO2014077240A1 (fr) * 2012-11-13 2014-05-22 電気化学工業株式会社 Luminophore, élément électroluminescent et dispositif d'éclairage
JP2015052648A (ja) * 2013-09-05 2015-03-19 日亜化学工業株式会社 カラーフィルター及び発光装置の組合せの選択方法並びに画像表示装置の製造方法
JP2015091915A (ja) * 2013-10-04 2015-05-14 三菱化学株式会社 発光装置、及び波長変換部材
WO2015056590A1 (fr) * 2013-10-15 2015-04-23 シャープ株式会社 Dispositif électroluminescent et son procédé de fabrication
JP2015212360A (ja) * 2014-04-17 2015-11-26 パナソニックＩｐマネジメント株式会社 樹脂組成物およびその製造方法並びに半導体装置

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110753735A (zh) * 2017-06-14 2020-02-04 电化株式会社 氟化物荧光体和使用其的发光装置
JP2019001986A (ja) * 2017-06-14 2019-01-10 デンカ株式会社 フッ化物蛍光体とそれを用いた発光装置
JP2019001985A (ja) * 2017-06-14 2019-01-10 デンカ株式会社 フッ化物蛍光体とそれを用いた発光装置
CN110753735B (zh) * 2017-06-14 2023-01-06 电化株式会社 氟化物荧光体和使用其的发光装置
US11114589B2 (en) 2017-06-14 2021-09-07 Denka Company Limited Fluoride phosphor and light-emitting device using same
US10982139B2 (en) 2017-06-14 2021-04-20 Denka Company Limited Fluoride phosphor and light-emitting device using same
JP7004721B2 (ja) 2017-07-28 2022-01-21 デュポン・東レ・スペシャルティ・マテリアル株式会社 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法
US12060472B2 (en) 2017-07-28 2024-08-13 Dupont Toray Specialty Materials Kabushiki Kaisha Optical member resin sheet, optical member, layered body, or light-emitting device comprising optical member resin sheet, and method for manufacturing optical member resin sheet
JPWO2019021926A1 (ja) * 2017-07-28 2020-07-30 デュポン・東レ・スペシャルティ・マテリアル株式会社 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法
CN107731996A (zh) * 2017-09-28 2018-02-23 惠州市华瑞光源科技有限公司 Led灯珠及其制备方法
JP2019064136A (ja) * 2017-09-29 2019-04-25 日亜化学工業株式会社 透光性シートの製造方法
US11398587B2 (en) 2017-09-29 2022-07-26 Nichia Corporation Method of manufacturing light-transmissive sheet
JP2019164302A (ja) * 2018-03-20 2019-09-26 株式会社タムラ製作所 波長変換部材及び波長変換素子
JP7178074B2 (ja) 2018-03-20 2022-11-25 国立研究開発法人物質・材料研究機構 波長変換部材及び波長変換素子、並びに波長変換部材の製造方法
WO2019181478A1 (fr) * 2018-03-20 2019-09-26 株式会社タムラ製作所 Membre de conversion de longueur d'onde et élément de conversion de longueur d'onde
JP2019186537A (ja) * 2018-03-30 2019-10-24 日亜化学工業株式会社 波長変換部材及び発光装置
WO2019218337A1 (fr) * 2018-05-18 2019-11-21 Rohm And Haas Electronic Materials Llc Film de phosphore à deux couches pour led
WO2022044860A1 (fr) * 2020-08-25 2022-03-03 デンカ株式会社 Luminophore de fluorure, complexe, et dispositif électroluminescent
JP7554833B2 (ja) 2020-08-25 2024-09-20 デンカ株式会社 フッ化物蛍光体、複合体および発光装置
JP7530019B2 (ja) 2020-08-31 2024-08-07 日亜化学工業株式会社 発光装置の製造方法
US12117691B2 (en) 2020-08-31 2024-10-15 Nichia Corporation Method of producing light-emitting device and planar light source
WO2022075293A1 (fr) * 2020-10-06 2022-04-14 シャープ株式会社 Élément de conversion de longueur d'onde, équipement optique et procédé de fabrication d'élément de conversion de longueur d'onde
WO2022255173A1 (fr) * 2021-06-02 2022-12-08 東レ株式会社 Composition de conversion de couleur, feuille de conversion de couleur, unité de source de lumière comprenant celle-ci, affichage et dispositif d'éclairage
WO2023037831A1 (fr) * 2021-09-09 2023-03-16 信越化学工業株式会社 Phosphore ksf enrobé, son procédé de fabrication, composition de silicone polymérisable le contenant, et dispositif opto-semiconducteur

Also Published As

Publication number Publication date
JPWO2017094832A1 (ja) 2018-09-20
TW201728744A (zh) 2017-08-16
JP6852401B2 (ja) 2021-03-31
KR20180090260A (ko) 2018-08-10
KR102419336B1 (ko) 2022-07-12
CN108351444B (zh) 2021-10-26
TWI728011B (zh) 2021-05-21
CN108351444A (zh) 2018-07-31

Similar Documents

Publication Publication Date Title
WO2017094832A1 (fr) Feuille fluorescente, élément électroluminescent utilisant celle-ci, unité de source de lumière, affichage et procédé de production d'élément électroluminescent
KR101967623B1 (ko) 형광체 시트, 이것을 사용한 ｌｅｄ 및 발광 장치, 그리고 ｌｅｄ의 제조 방법
KR101713087B1 (ko) 형광체 함유 실리콘 경화물, 그 제조 방법, 형광체 함유 실리콘 조성물, 그 조성물 전구체, 시트상 성형물, ｌｅｄ 패키지, 발광 장치 및 ｌｅｄ 실장 기판의 제조 방법
JP5488761B2 (ja) 積層体および波長変換層付き発光ダイオードの製造方法
TWI657599B (zh) 螢光體組成物、螢光體片、螢光體片積層體及使用它們的ｌｅｄ晶片、ｌｅｄ封裝及其製造方法
JP6287212B2 (ja) 蛍光体含有樹脂シートおよび発光装置
TWI693730B (zh) 發光裝置的製造方法
KR20130079496A (ko) 형광체 함유 시트, 그것을 사용한 ｌｅｄ 발광 장치 및 그 제조 방법
JP2014116587A (ja) 蛍光体含有樹脂シート、これを用いたｌｅｄ素子およびその製造方法
JP2014114446A (ja) ポリオルガノシロキサン組成物、その硬化物、蛍光体シート、その製造方法、発光デバイスおよびその製造方法
JP2013252637A (ja) 蛍光体シート積層体
TW202027302A (zh) 被覆有螢光體層之光半導體元件及其製造方法
WO2017094618A1 (fr) Composition de résine, article moulé en forme de feuille de celle-ci, dispositif électroluminescent l'utilisant, et procédé de fabrication associé
JP2013144770A (ja) 熱硬化性シリコーン樹脂組成物、該組成物から成形された成形物、光半導体装置、及び熱硬化性シリコーン樹脂組成物の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2016571440

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16870769

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20187014115

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16870769

Country of ref document: EP

Kind code of ref document: A1