WO2017057074A1 - Phosphor composition, phosphor sheet, and molded article using same, led chip, led package, light-emitting device, backlight unit, display, and method for manufacturing led package - Google Patents

Phosphor composition, phosphor sheet, and molded article using same, led chip, led package, light-emitting device, backlight unit, display, and method for manufacturing led package Download PDF

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WO2017057074A1
WO2017057074A1 PCT/JP2016/077529 JP2016077529W WO2017057074A1 WO 2017057074 A1 WO2017057074 A1 WO 2017057074A1 JP 2016077529 W JP2016077529 W JP 2016077529W WO 2017057074 A1 WO2017057074 A1 WO 2017057074A1
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group
phosphor
phosphor sheet
general formula
organic compound
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PCT/JP2016/077529
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French (fr)
Japanese (ja)
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石田　豊
正明 梅原
田中　大作
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東レ株式会社
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Priority to KR1020187005201A priority Critical patent/KR102404622B1/en
Priority to CN201680051426.7A priority patent/CN107995920B/en
Priority to JP2016561880A priority patent/JP6760077B2/en
Publication of WO2017057074A1 publication Critical patent/WO2017057074A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • 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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7704—Halogenides
    • C09K11/7705—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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/77068—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/08—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a plurality of light emitting regions, e.g. laterally discontinuous light emitting layer or photoluminescent region integrated within the semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/54—Encapsulations having a particular shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/93—Batch processes
    • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L2224/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting

Definitions

  • the present invention relates to a phosphor composition, a phosphor sheet, and a formed article using them, an LED chip, an LED package, a light emitting device, a backlight unit, a display, and an LED package manufacturing method.
  • Color conversion refers to conversion of light emitted from a light emitter into light having a longer wavelength, and represents, for example, conversion of blue light emission into green light emission or red light emission.
  • the composition having this color conversion function is a phosphor composition, and the phosphor sheet is a phosphor sheet. By combining this phosphor sheet with, for example, a blue light source, it is possible to extract three primary colors of blue, green, and red from the blue light source, that is, to extract white light.
  • a white light source combining such a blue light source and a phosphor sheet is used as a backlight unit, and a combination of this backlight unit, a liquid crystal driving portion, and a color filter makes it possible to produce a full color display. Moreover, if there is no liquid crystal drive part, it can be used as a white light source as it is, for example, it can be applied as a white light source such as LED lighting.
  • an organic light emitting material is used as a component of the phosphor composition instead of quantum dots.
  • techniques using an organic light-emitting material as a component of a phosphor composition include those using a pyridine-phthalimide condensate (for example, see Patent Document 2) and those using a coumarin derivative (for example, see Patent Document 3).
  • the red light emitting material those using a perylene derivative so far (for example, see Patent Document 4), those using a rhodamine derivative (for example, see Patent Document 5), those using a pyromethene derivative (for example, Patent Document 6) To 7).
  • the objective is to make high color reproducibility and high durability compatible in the fluorescent substance composition and fluorescent substance sheet which are used for a liquid crystal display, LED lighting, etc. That is.
  • the phosphor composition according to the present invention converts the light emitted from the light emitter to light having a longer wavelength than the light emitted by the general formula (1).
  • R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from bery
  • M is boron
  • L is fluorine or a fluorine-containing aryl group
  • m ⁇ 1 is 2 is a feature.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, Ar 5 in the general formula (1) representing the organic compound is a group represented by the general formula (2).
  • R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
  • Ar 1 to Ar 4 in the general formula (1) representing the organic compound may be the same or different, and may be substituted or unsubstituted. It is a phenyl group.
  • At least one of Ar 1 to Ar 4 in the general formula (1) representing the organic compound is a group represented by the general formula (3). It is characterized by being.
  • R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group.
  • N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .
  • Ar 1 and Ar 2 in the general formula (1) representing the organic compound are groups having different structures, or Ar 3 and Ar 4 And is a group having a different structure.
  • Ar 1 to Ar 4 in the general formula (1) representing the organic compound may be the same or different, and may be substituted or unsubstituted. It is an alkyl group.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is hydrogen.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is an electron withdrawing group.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, r in the general formula (2) representing Ar 5 of the organic compound is an electron withdrawing group.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a ⁇ -type sialon phosphor.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the emission spectrum of the ⁇ -type sialon phosphor has a peak in the region of 535 to 550 nm.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the ⁇ -sialon phosphor has an average particle size of 16 ⁇ m or more and 19 ⁇ m or less.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a KSF phosphor.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the KSF phosphor has an average particle size of 10 ⁇ m or more and 40 ⁇ m or less.
  • the phosphor composition according to the present invention is characterized in that, in the above invention, the matrix resin is a silicone resin.
  • the phosphor sheet according to the present invention includes an organic compound represented by the general formula (1) and an inorganic phosphor, which converts light emitted from a light emitter into light having a longer wavelength than the light emitted; And a matrix resin that forms a continuous phase by mixing with an inorganic phosphor.
  • R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from bery
  • the phosphor sheet according to the present invention is the above-described invention, wherein the phosphor layer includes the inorganic phosphor and the matrix resin, and the organic light emitting material includes the organic compound represented by the general formula (1). It includes a laminated structure with a material layer.
  • M is boron
  • L is fluorine or a fluorine-containing aryl group
  • m ⁇ 1 is 2 It is characterized by being.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, Ar 5 in the general formula (1) representing the organic compound is a group represented by the general formula (2).
  • R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
  • Ar 1 to Ar 4 may be the same or different, and substituted or unsubstituted phenyl It is a group.
  • At least one of Ar 1 to Ar 4 in the general formula (1) representing the organic compound is a group represented by the general formula (3). It is characterized by being.
  • R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group.
  • N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .
  • Ar 1 and Ar 2 in the general formula (1) representing the organic compound are groups having different structures, or Ar 3 and Ar 4 Are groups having different structures.
  • Ar 1 to Ar 4 in the general formula (1) representing the organic compound in the above invention may be the same or different from each other, and may be substituted or unsubstituted alkyl. It is a group.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is hydrogen.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is an electron withdrawing group.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, r in the general formula (2) representing Ar 5 of the organic compound is an electron withdrawing group.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a ⁇ -type sialon phosphor.
  • the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the emission spectrum of the ⁇ -sialon phosphor has a peak in the region of 535 to 550 nm.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the ⁇ -sialon phosphor has an average particle diameter of 16 ⁇ m or more and 19 ⁇ m or less.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a KSF phosphor.
  • the phosphor sheet according to the present invention is characterized in that, in the above invention, the KSF phosphor has an average particle size of 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, the matrix resin is a silicone resin.
  • the formed product according to the present invention is characterized by containing the phosphor composition according to any one of the above inventions or a cured product thereof.
  • an LED chip according to the present invention is characterized in that the phosphor sheet according to any one of the above inventions or a cured product thereof is provided on a light emitting surface.
  • an LED package according to the present invention includes a cured product of the phosphor composition according to any one of the above-described inventions.
  • an LED package according to the present invention includes the phosphor sheet according to any one of the above inventions or a cured product thereof.
  • the manufacturing method of the LED package which concerns on this invention is a manufacturing method of the LED package using the fluorescent substance composition as described in any one of said invention, Comprising: On the package frame in which the LED chip is installed It includes at least an injection step of injecting the phosphor composition and a sealing step of sealing the LED chip with a sealing material after the injection step.
  • the manufacturing method of the LED package which concerns on this invention is a manufacturing method of the LED package using the fluorescent substance sheet as described in any one of said invention, Comprising: Said state in the state divided
  • a light-emitting device includes an LED package having an LED chip that is a light-emitting body in which emitted light is color-converted by a phosphor composition included in the above-described invention, and a phosphor composition included in the formation; It is characterized by providing.
  • a backlight unit according to the present invention includes the LED package according to any one of the above inventions.
  • a backlight unit according to the present invention includes the LED package according to any one of the above inventions.
  • the present invention it is possible to provide a phosphor composition and a phosphor sheet that satisfy both high color reproducibility and high durability.
  • the LED chip, the LED package, the light emitting device, the backlight unit, and the display including the phosphor composition or the phosphor sheet according to the present invention have an effect that both high color reproducibility and high durability can be achieved.
  • FIG. 1 is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing an example of a method for manufacturing an LED package using the phosphor composition according to the embodiment of the present invention.
  • FIG. 3A is a diagram showing an example of an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 3B is a diagram showing another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 3C is a diagram showing still another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 3A is a diagram showing an example of an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 3B is a diagram showing another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment
  • FIG. 4A is a diagram showing an example of an LED package using the phosphor composition according to the embodiment of the present invention.
  • FIG. 4B is a diagram showing Example 1 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4C is a diagram showing an example 2 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4D is a diagram showing an example 3 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4E is a diagram showing Example 4 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4F is a diagram illustrating Example 5 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4G is a diagram showing Example 6 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4H is a diagram illustrating Example 7 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4I is a diagram showing Example 8 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 4J is a diagram showing an example of an LED package using a formed article using the phosphor composition according to the embodiment of the present invention.
  • FIG. 5 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 5 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 6 is a diagram illustrating an example of a method of manufacturing an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 7 is a diagram showing another example of the method for manufacturing the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 8 is a diagram showing an example of a phosphor sheet attaching method according to the embodiment of the present invention.
  • FIG. 9 is a diagram showing another example of the phosphor sheet attaching method according to the embodiment of the present invention.
  • FIG. 10 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 11 is a diagram showing another example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • a phosphor composition a phosphor sheet and a formed article using them, an LED chip, an LED package, a light emitting device, a backlight unit, and an LED package manufacturing method according to the present invention will be described in detail. To do.
  • 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 composition which is one embodiment of the present invention contains an organic compound and an inorganic phosphor represented by the general formula (1), and a matrix resin.
  • the organic compound is an organic light-emitting material (that is, an organic light-emitting material), and these organic compound and inorganic phosphor respectively emit light (emitted light) emitted from the light emitter. The light is converted into light having a longer wavelength.
  • the matrix resin contained in the phosphor composition is a resin that forms a continuous phase by mixing with these organic compounds and inorganic phosphors.
  • R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group.
  • M represents an m-valent metal and is at least one selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum.
  • hydrogen may be deuterium. The same applies to an organic compound or a partial structure thereof described below.
  • a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl having 6 to 40 carbon atoms in total including the number of carbon atoms contained in the substituent substituted on the aryl group. It is a group. The same applies to other substituents that define the number of carbon atoms.
  • the substituents in the case of substitution include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups.
  • Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl Group and a phosphine oxide group are preferable, and specific substituents that are preferable in the description of each substituent are preferable. Moreover, these substituents may be further substituted with the above-mentioned substituents.
  • unsubstituted means that a hydrogen atom or a deuterium atom is substituted.
  • substituted or unsubstituted in an organic compound or a partial structure thereof described below.
  • the alkyl group is, for example, a saturated aliphatic group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
  • a hydrocarbon group is shown.
  • This alkyl group may or may not further have a substituent.
  • an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, This point is common also in the following description.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.
  • the cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent.
  • the number of carbon atoms in the alkyl group moiety is not particularly limited, but is preferably in the range of 3 or more and 20 or less.
  • the aralkyl group is an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. Any of these aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or may have a substituent.
  • alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent.
  • carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.
  • the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, which may have a substituent. You don't have to.
  • the alkynyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent.
  • carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.
  • the alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent. It may not have.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.
  • the alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
  • the hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Usually, it is the range of 1-20.
  • An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Good.
  • the number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.
  • the aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom.
  • the aromatic hydrocarbon group in the aryl thioether group may or may not have a substituent.
  • the number of carbon atoms of the arylthioether group is not particularly limited, but is usually in the range of 6 or more and 40 or less.
  • An aryl group refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group, or a terphenyl group.
  • the aryl group may or may not have a substituent.
  • the number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.
  • a heteroaryl group is one or more atoms other than carbon such as furanyl, thiophenyl, pyridyl, quinolinyl, pyrazinyl, pyrimidinyl, triazinyl, naphthyridyl, benzofuranyl, benzothiophenyl, indolyl, etc.
  • the cyclic aromatic group which has in an individual ring is shown, This may be unsubstituted or substituted.
  • the number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 or more and 30 or less.
  • the heterocyclic group refers to an aliphatic ring having atoms other than carbon, such as a pyran ring, a piperidine ring, and a cyclic amide, in the ring, which may or may not have a substituent. .
  • carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-20.
  • the carbonyl group, carboxyl group, and carbamoyl group may or may not have a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.
  • An amino group is a substituted or unsubstituted amino group.
  • the amino group may or may not have a substituent.
  • substituents in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group. .
  • aryl group and heteroaryl group a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted.
  • carbon number is not specifically limited, Preferably it is 2 or more and 50 or less, More preferably, it is 6 or more and 40 or less, Especially preferably, it is the range of 6 or more and 30 or less.
  • Halogen means fluorine, chlorine, bromine or iodine.
  • a haloalkyl group, a haloalkenyl group, or a haloalkynyl group is a group in which a part or all of the aforementioned alkyl group, alkenyl group, or alkynyl group such as a trifluoromethyl group is substituted with the aforementioned halogen, and the rest This part may be unsubstituted or substituted.
  • the aldehyde group, carbonyl group, ester group, and carbamoyl group include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like. The alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
  • the silyl group refers to, for example, a functional group having a bond to a silicon atom such as a trimethylsilyl group, which may or may not have a substituent.
  • carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20.
  • the number of silicon is usually 1 or more and 6 or less.
  • Siloxanyl group refers to a silicon compound group via an ether bond such as trimethylsiloxanyl group. Substituents on silicon may be further substituted.
  • the organic compound represented by the general formula (1) as described above exhibits a high fluorescence quantum yield and has a small peak half-value width of the emission spectrum, it achieves both efficient color conversion and high color purity. can do.
  • a complex in which M is boron is particularly preferable because of high fluorescence quantum yield.
  • a boron fluoride complex in which L is fluorine or a fluorine-containing aryl group and m-1 is 2 is particularly preferable from the viewpoint of easy availability of materials and ease of synthesis.
  • any adjacent two substituents may be bonded to each other to form a conjugated or non-conjugated condensed ring.
  • a constituent element of the condensed ring may contain an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon in addition to carbon.
  • the condensed ring may be further condensed with another ring.
  • the organic compound represented by the general formula (1) as described above has a light emitting efficiency, a color purity, a thermal stability, a light stability, a dispersibility and the like by introducing an appropriate substituent at an appropriate position. Various properties and physical properties can be adjusted.
  • the substituent Ar 5 greatly affects the durability of the organic compound represented by the general formula (1), that is, the decrease in the emission intensity of the organic compound over time. Specifically, when Ar 5 is hydrogen, the reactivity of this hydrogen is high, so that this hydrogen and moisture or oxygen in the air easily react. This causes the decomposition of Ar 5 . In addition, when Ar 5 is a substituent having a large degree of freedom of movement of a molecular chain such as an alkyl group, for example, the reactivity is certainly lowered, but the organic compounds aggregate in the sheet over time, and as a result In particular, the emission intensity is reduced due to concentration quenching.
  • Ar 5 is preferably a group that is rigid and has a low degree of freedom of movement and is unlikely to cause aggregation. Specifically, it is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It is preferable that it is either.
  • Ar 5 is preferably a substituted or unsubstituted aryl group from the viewpoint of giving a higher fluorescence quantum yield, being harder to thermally decompose, and from the viewpoint of light stability.
  • aryl group a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.
  • Ar 5 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group.
  • a phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group are more preferable. Particularly preferred is a substituted or unsubstituted phenyl group.
  • Ar 5 is preferably a moderately bulky substituent. Since Ar 5 has a certain amount of bulkiness, aggregation of molecules can be prevented. As a result, the luminous efficiency and durability of the organic compound are further improved.
  • a more preferred example of such a bulky substituent includes the structure of Ar 5 represented by the following general formula (2).
  • Ar 5 is preferably a group represented by the general formula (2).
  • r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl Ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, Selected from the group consisting of phosphine oxide groups.
  • k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
  • an oxycarbonyl group may or may not have a substituent.
  • substituents for the oxycarbonyl group include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and the like, and these substituents may be further substituted.
  • r is preferably a substituted or unsubstituted aryl group.
  • aryl groups a phenyl group and a naphthyl group are particularly preferable examples.
  • k in the general formula (2) is preferably 1 or 2, and k is more preferably 2 from the viewpoint of further preventing aggregation of molecules.
  • k is 2 or more, it is preferable that at least one of r is substituted with an alkyl group.
  • the alkyl group in this case, a methyl group, an ethyl group, and a tert-butyl group are particularly preferable from the viewpoint of thermal stability.
  • r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen.
  • a methyl group, an ethyl group, a tert-butyl group, and a methoxy group are more preferable.
  • a tert-butyl group and a methoxy group are particularly preferable.
  • Ar 1 to Ar 4 are all hydrogen
  • Ar 1 to Ar 4 when at least one of Ar 1 to Ar 4 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group It shows better thermal stability and light stability.
  • the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, more preferably a phenyl group or a biphenyl group. is there. Particularly preferred is a phenyl group.
  • the heteroaryl group is preferably a pyridyl group, a quinolinyl group, or a thiophenyl group, and more preferably a pyridyl group or a quinolinyl group. Particularly preferred is a pyridyl group.
  • Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Is preferred. This is because it shows better thermal stability and light stability.
  • the general formula (1) Ar 1 to Ar 4 may be the same or different from each other, more preferably a substituted or unsubstituted aryl group, and particularly preferably a phenyl group.
  • the inorganic phosphor converts the blue light to green light
  • the organic compound converts the blue light to the color of the inorganic phosphor.
  • Longer wavelength light that is, red light.
  • At least one of Ar 1 to Ar 4 is preferably a substituent represented by the general formula (3).
  • R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group.
  • n is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different.
  • R 3 when R 3 is an electron donating group, it is preferable because it mainly affects the color purity.
  • the electron donating group include an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group.
  • an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkylthio group having 1 to 8 carbon atoms is preferable.
  • R 3 is more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms because higher color purity can be obtained. Further, as the aryl group mainly affecting the luminous efficiency, an aryl group having a bulky substituent such as a t-butyl group or an adamantyl group is preferable.
  • Ar 1 and Ar 4 , Ar 2 and Ar 3 are preferably aryl groups having the same structure.
  • at least one of Ar 1 to Ar 4 is a group represented by the general formula (3), and R 3 is an alkyl group or alkoxy group having 4 or more carbon atoms. More preferred. Among them, a t-butyl group, a methoxy group, or a t-butoxy group is particularly preferable as at least one example of Ar 1 to Ar 4 .
  • n is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of availability of raw materials and ease of synthesis.
  • Ar 1 ⁇ Ar 2 or Ar 3 ⁇ Ar 4 is particularly preferable because dispersibility in the film is improved and high efficiency light emission is obtained.
  • “ ⁇ ” indicates a group having a different structure.
  • Ar 1 ⁇ Ar 2 indicates that Ar 1 and Ar 2 are groups having different structures.
  • Ar 3 ⁇ Ar 4 indicates that Ar 3 and Ar 4 are groups having different structures.
  • the aryl group represented by the general formula (3) affects various properties and physical properties of the organic compound represented by the general formula (1) such as luminous efficiency, color purity, heat resistance and light resistance. Some aryl groups improve multiple properties, but none have sufficient performance in all. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, if a plurality of types of aryl groups can be introduced into the organic compound represented by the general formula (1), it is expected to obtain an organic compound balanced in light emission characteristics and color purity.
  • the organic compound according to the embodiment of the present invention can arrange substituents having certain physical properties in a balanced manner on the left and right pyrrole rings, compared with the case where it is biased to one pyrrole ring. Therefore, it is possible to maximize the physical properties.
  • This effect is particularly excellent in that the luminous efficiency and color purity are improved in a balanced manner. It is preferable that at least one aryl group that affects the color purity is present in each of the pyrrole rings on both sides, from the viewpoint that the conjugated system is expanded and light emission with high color purity is obtained.
  • the organic compound according to the embodiment of the present invention introduces one or more aryl groups that affect the color purity into each of the pyrrole rings on both sides, and the aryl group that affects the luminous efficiency at other positions. Can be introduced. For this reason, the organic compound which concerns on embodiment of this invention can improve the property of both color purity and luminous efficiency to the maximum, and is therefore preferable. Note that it is preferable to introduce an aryl group that affects the color purity at the positions Ar 2 and Ar 3 because the conjugated system is most expanded.
  • Ar 1 to Ar 4 When at least one of Ar 1 to Ar 4 is a substituted or unsubstituted alkyl group, examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert group An alkyl group having 1 to 6 carbon atoms such as a butyl group, a pentyl group or a hexyl group is preferred.
  • the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, this alkyl group is more preferably a sterically bulky tert-butyl group. On the other hand, from the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as the alkyl group.
  • all of Ar 1 to Ar 4 may be the same or different, and when they are substituted or unsubstituted alkyl groups, they are soluble in a binder resin or a solvent. Is preferable.
  • the alkyl group is preferably a methyl group from the viewpoints of ease of synthesis and availability of raw materials.
  • a general formula ( Ar 1 to Ar 4 represented by 1) may all be the same or different and each represents a substituted or unsubstituted alkyl group, preferably a methyl group.
  • the inorganic phosphor converts the blue light into red light
  • the organic compound converts the blue light into the color of the inorganic phosphor.
  • Shorter wavelength light that is, green light.
  • R 1 and R 2 are hydrogen. That is, R 1 and R 2 are preferably any one of hydrogen, an alkyl group, a carbonyl group, an oxycarbonyl group, and an aryl group, but from the viewpoint of thermal stability, they are hydrogen or an alkyl group. Is preferred. In particular, from the viewpoint of easily obtaining a narrow half-value width in the emission spectrum, at least one of R 1 and R 2 is more preferably hydrogen.
  • L is preferably an alkyl group, an aryl group, a heteroaryl group, fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group.
  • L is more preferably a fluorine or fluorine-containing aryl group because it is stable against excitation light and a higher fluorescence quantum yield is obtained.
  • L is more preferably fluorine in view of ease of synthesis.
  • the fluorine-containing aryl group is an aryl group containing fluorine, and examples thereof include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group.
  • the fluorine-containing heteroaryl group is a heteroaryl group containing fluorine, and examples thereof include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group.
  • the fluorine-containing alkyl group is an alkyl group containing fluorine, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.
  • R 1 , R 2 and Ar 1 to Ar 5 is an electron withdrawing group.
  • at least one of R 1 , R 2 and Ar 1 to Ar 4 is an electron withdrawing group
  • Ar 5 is an electron withdrawing group
  • R 1 , R 2 , Ar 1 to Ar 4 are preferably electron withdrawing groups
  • Ar 5 is preferably an electron withdrawing group.
  • the electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory.
  • Examples of the electron-withdrawing group include those that take a positive value as the Hammett's rule substituent constant ( ⁇ p (para)).
  • the Hammett's rule substituent constant ( ⁇ p (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380).
  • a phenyl group also has the example which takes the above positive values, in this invention, a phenyl group is not contained in an electron withdrawing group.
  • electron withdrawing groups include, for example, -F ( ⁇ p: +0.06), -Cl ( ⁇ p: +0.23), -Br ( ⁇ p: +0.23), -I ( ⁇ p: +0.18),- CO 2 R 12 ( ⁇ p: when R 12 is an ethyl group +0.45), —CONH 2 ( ⁇ p: +0.38), —COR 12 ( ⁇ p: when R 12 is a methyl group +0.49), —CF 3 ( ⁇ p: +0.50), —SO 2 R 12 (+0.69 when ⁇ p: R 12 is a methyl group), —NO 2 ( ⁇ p: +0.81), and the like.
  • R 12 each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, substituted or unsubstituted
  • a substituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms are represented. Specific examples of these groups include the same examples as described above.
  • Preferred electron withdrawing groups include fluorine, fluorine-containing aryl groups, fluorine-containing heteroaryl groups, fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, substituted or unsubstituted amide groups, and substituted groups. Or an unsubstituted sulfonyl group or a cyano group is mentioned. This is because they are difficult to decompose chemically.
  • More preferred electron withdrawing groups include fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, and cyano groups. This is because these lead to effects of preventing concentration quenching and improving the emission quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.
  • R 1 and R 2 are preferably an electron withdrawing group. This is because the stability of the organic compound represented by the general formula (1) to oxygen can be improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be improved. Because it can.
  • r is more preferably an electron withdrawing group. This is because the stability of the organic compound represented by the general formula (1) to oxygen is further improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be greatly improved. Because it can.
  • Ar 1 to Ar 4 may all be the same or different and each is a substituted or unsubstituted alkyl group, and Ar The case where 5 is group represented by General formula (2) is mentioned.
  • Ar 5 is particularly preferably a group represented by the general formula (2) in which r is included as a substituted or unsubstituted phenyl group.
  • Ar 1 to Ar 4 may be the same or different and are selected from the above general formula (3).
  • Ar 5 is a group represented by the general formula (2).
  • the organic compound represented by the general formula (1) can be produced, for example, by the method described in JP-T-8-509471 and JP-A-2000-208262. That is, the target pyromethene metal complex is obtained by reacting the pyromethene compound and the metal salt in the presence of a base.
  • a method of generating a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned.
  • the present invention is not limited to this.
  • introducing an amino group or a carbazolyl group for example, there is a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium.
  • the present invention is not limited to this.
  • the phosphor composition according to the embodiment of the present invention can appropriately contain other compounds as required in addition to the organic compound represented by the general formula (1).
  • an assist dopant such as rubrene may be contained in order to further increase the energy transfer efficiency from the excitation light to the organic compound represented by the general formula (1).
  • a desired organic light emitting material such as a coumarin dye, a perylene dye, a phthalocyanine dye, a stilbene dye, Compounds such as cyanine dyes, polyphenylene dyes, rhodamine dyes, pyridine dyes, pyromethene dyes, porphyrin dyes, oxazine dyes and pyrazine dyes can be added.
  • known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots can be added in combination.
  • organic light-emitting materials other than the organic compound represented by the general formula (1) are shown, but the present invention is not particularly limited thereto.
  • the content of the organic compound represented by the general formula (1) in the phosphor composition according to the embodiment of the present invention includes the molar absorption coefficient of the organic compound, the fluorescence quantum yield, the absorption intensity at the excitation wavelength, and the production.
  • it is usually 10 ⁇ 5 weight percent to 10 weight percent, more preferably 10 ⁇ 4 weight percent to 5 weight percent, based on the total weight of the phosphor composition.
  • it is 10 ⁇ 3 weight percent to 2 weight percent.
  • the inorganic phosphor in the embodiment of the present invention is an inorganic phosphor used in combination with the organic compound (organic light-emitting material) represented by the general formula (1) described above, and emits light emitted from the phosphor. The light is converted into light having a wavelength range different from that of the organic compound.
  • an inorganic phosphor having a peak in the region where the emission spectrum is 500 to 700 nm is particularly preferably used.
  • Such an inorganic phosphor is excited by excitation light in the range of 400 to 500 nm and emits light in the region of 500 to 700 nm.
  • examples of the inorganic phosphor include an inorganic phosphor that emits green light, an inorganic phosphor that emits yellow light, and an inorganic phosphor that emits red light.
  • an inorganic phosphor that emits green light an inorganic phosphor that emits yellow light
  • an inorganic phosphor that emits red light an inorganic phosphor that emits red light.
  • a shape of an inorganic fluorescent substance Various things, such as spherical shape and a column shape, can be used.
  • the inorganic phosphor is not particularly limited as long as it can finally reproduce a predetermined color, and a known phosphor can be used.
  • Examples of the inorganic phosphor as described above include YAG phosphor, TAG phosphor, silicate phosphor, nitride phosphor, oxynitride phosphor, nitride, oxynitride phosphor, Mn 4 + Activated fluoride complex phosphor and the like.
  • nitrides, oxynitride phosphors, and Mn 4+ activated fluoride complex phosphors are preferably used as the inorganic phosphors.
  • a ⁇ -type sialon phosphor and a KSF phosphor are preferably used as the inorganic phosphor.
  • ⁇ -type sialon phosphor ⁇ -type sialon is a solid solution of ⁇ -type silicon nitride.
  • Aluminum (Al) is substituted and dissolved in silicon (Si) position of ⁇ -type silicon nitride crystal, and oxygen (O) is substituted and dissolved in nitrogen (N) position. It is a thing. Since there are two types of atoms in the unit cell (unit cell) of ⁇ -type sialon, Si 6-Z Al z O z N 8-z is used as a general formula of ⁇ -type sialon.
  • composition z is 0 to 4.2, the solid solution range is very wide, and the molar ratio of (Si, Al) / (N, O) needs to be maintained at 3/4.
  • a general method for producing ⁇ -sialon is a method of heating by adding silicon oxide and aluminum nitride, or adding aluminum oxide and aluminum nitride in addition to silicon nitride.
  • ⁇ -Sialon is a ⁇ -Sialon fluorescence that emits green light of 520 to 550 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. Become a body.
  • the ⁇ -type sialon phosphor those having an emission spectrum having a peak in the region of 535 to 550 nm are preferably used. Within such a wavelength range of the emission spectrum, good emission characteristics can be obtained when a ⁇ -type sialon phosphor is used in an LED package.
  • the average particle size of the ⁇ -type sialon phosphor is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 16 ⁇ m or more. Further, the average particle diameter of the ⁇ -type sialon phosphor is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 19 ⁇ m or less.
  • ⁇ -type sialon phosphor is used in an LED package.
  • the ⁇ -sialon phosphor as described above is used, for example, in combination with an organic light-emitting material that is an organic compound represented by the general formula (1) and converts blue light emission from a light emitter into red light emission.
  • the Mn-activated double fluoride complex phosphor is an inorganic 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), and fluorine atoms coordinated around the center.
  • the number of is preferably 6.
  • This inorganic phosphor is represented by a general formula of A 2 MF 6 : Mn, and in this general formula, K 2 SiF 6 : Mn is a KSF phosphor.
  • A is one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and including at least one of Na and K These are alkali metals.
  • M is one or more tetravalent elements selected from the group consisting of Si, titanium (Ti), zirconium (Zr), hafnium (Hf), germanium (Ge), and tin (Sn).
  • the average particle size of the KSF phosphor is preferably 1 ⁇ m or more, and may be 20 ⁇ m or more, but more preferably 10 ⁇ m or more.
  • the average particle size of the KSF phosphor is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, and even more preferably 40 ⁇ m or less.
  • the average particle size is within such a range, good light emission characteristics can be obtained when the KSF phosphor is used in an LED package.
  • limiting in particular as a shape of KSF fluorescent substance Although various things, such as spherical shape and a column shape, can be used, The thing which is not grind
  • the KSF phosphor as described above is, for example, an organic compound represented by the general formula (1) and used in combination with an organic light emitting material that converts blue light emission from a light emitter to green light emission.
  • the average particle diameter is the median diameter (D50) and can be measured by SEM observation. From the two-dimensional image obtained by observing the phosphor layer, the one having the maximum distance between the two intersections of the straight line intersecting the outer edge of the particle at two points is calculated and defined as the average particle diameter. For example, measurement is performed on 200 particles observed to obtain a particle size distribution, and in the particle size distribution obtained therefrom, a particle size of 50% of the accumulated amount from the small particle size side is obtained as a median diameter (D50).
  • D50 median diameter
  • the average particle diameter can be calculated from a two-dimensional image obtained by observing the obtained cross section with an SEM. .
  • the matrix resin is a resin that forms a continuous phase by mixing with the organic compound represented by the general formula (1) and the inorganic phosphor, or at least by mixing with the inorganic phosphor.
  • the matrix resin may be a material that is excellent in molding processability, transparency, heat resistance, and the like.
  • matrix resins examples include photocurable resist materials having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvinyl cinnamate, and ring rubber, epoxy resins, silicone resins (silicone rubber, silicone Organopolysiloxane cured product (cross-linked product) such as gel), urea resin, fluororesin, polycarbonate resin, acrylic resin, urethane resin, melamine resin, polyvinyl resin, polyamide resin, phenol resin, polyvinyl alcohol resin, cellulose resin, Known materials such as aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins, and aromatic polyolefin resins can be used. Further, these copolymer resins may be used as the matrix resin. By appropriately designing these resins, a matrix resin useful for the phosphor composition according to the embodiment of the present invention and the phosphor sheet described below can be obtained.
  • photocurable resist materials having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvin
  • thermosetting resin is more preferable because the film forming process is easy.
  • an epoxy resin, a silicone resin, an acrylic resin, or a mixture thereof can be suitably used as the matrix resin.
  • the thermosetting resin contained in the matrix resin may be one type or a combination of two or more types.
  • the matrix resin may contain a curing agent as necessary. For example, by combining an epoxy resin and a curing agent, curing of the epoxy resin as the matrix resin can be accelerated and cured in a short time.
  • the matrix resin is most preferably a silicone resin from the viewpoint of heat resistance.
  • silicone resins addition reaction curable silicone compositions are preferred as the matrix resin.
  • the addition reaction curable silicone composition is heated and cured at room temperature or 50 to 200 ° C., and is excellent in transparency, heat resistance, and adhesiveness.
  • a composition containing a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a catalytic amount of a platinum-based catalyst can be used. .
  • a silicone resin containing a silicon atom having a siloxane bond and having an aryl group directly bonded thereto is preferably used.
  • a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group is preferable as a matrix resin in the present invention because it can achieve both a high refractive index, heat resistance, and light resistance.
  • the silicone resin having a siloxane bond and containing a silicon atom directly bonded to an aryl group includes a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a phenyl group, a siloxane bond, and a methyl resin. And a silicone resin containing a silicon atom in which a group and a phenyl group are directly connected.
  • a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a methyl group and a naphthyl group, and a siloxane bond
  • a silicone resin containing a silicon atom having a methyl group, a phenyl group and a naphthyl group directly bonded to each other a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group
  • a silicone resin containing a silicon atom in which a methyl group and a phenyl group are directly bonded a case in which a methyl group and a phenyl group are directly bonded to one silicon atom, and a silicon atom and a phenyl group in which a methyl group is directly bonded And each having a silicon atom directly connected to each other.
  • An addition reaction curable silicone composition comprising a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a platinum-based catalyst as a hydrosilylation reaction catalyst is a matrix resin (silicone resin).
  • a matrix resin silicone resin
  • sealing materials “OE6630” and “OE6636” manufactured by Toray Dow Corning Co., Ltd., “SCR-1012” and “SCR1016” manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • the matrix resin of the phosphor composition according to the embodiment of the present invention is a cross-linked product obtained by hydrosilylation reaction of a cross-linkable silicone composition including the compositions (A) to (D) described later.
  • This crosslinked product can be preferably used as a matrix resin for a phosphor sheet that does not require an adhesive because the storage elastic modulus decreases at 60 ° C. to 250 ° C. and a high adhesive force is obtained by heating.
  • this crosslinked product is appropriately referred to as a heat-sealing resin.
  • composition of (A) is an organo represented by an average unit formula of (R 1 2 SiO 2/2 ) a (R 1 SiO 3/2 ) b (R 2 O 1/2 ) c Polysiloxane.
  • 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 to 75 mol% of R 1 is a phenyl group, 10-20 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 composition (B) (component (B)) is an organopolysiloxane represented by the general formula R 3 3 SiO (R 3 2 SiO) m SiR 3 3 .
  • the component (B) is 5 to 15 parts by weight based on 100 parts by weight of the 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 to 70 mol% of R 3 is a phenyl group, at least one R 3 is an alkenyl group.
  • m is an integer of 5 to 50.
  • the composition of (C) is an organotrisiloxane represented by the general formula of (HR 4 2 SiO) 2 SiR 4 2 .
  • the component (C) is an amount such that the molar ratio of silicon-bonded hydrogen atoms in the component (C) to the total of alkenyl groups in the component (A) and the component (B) is 0.5 to 2.
  • R 4 is a phenyl group, or an alkyl or cycloalkyl group having 1 to 6 carbon atoms. However, 30 to 70 mol% of R 4 is a phenyl group.
  • composition (component (D)) is a hydrosilylation catalyst.
  • This component (D) has a catalytic amount sufficient to promote the hydrosilylation reaction between the alkenyl group in component (A) and component (B) and the silicon atom-bonded hydrogen atom in component (C). .
  • the resulting crosslinked product when the values of a, b, and c satisfy the above conditions, sufficient hardness of the resulting crosslinked product at room temperature can be obtained, and softening at high temperature can be obtained.
  • the resulting crosslinked product when the content of the phenyl group is less than the lower limit of the above range, the resulting crosslinked product is not sufficiently softened at a high temperature. On the other hand, when the content of the phenyl group exceeds the upper limit of the above range, the resulting crosslinked product loses its transparency and its mechanical strength also decreases.
  • at least one R 3 is an alkenyl group.
  • m is an integer in the range of 5 to 50 as described above. This is a range for making it possible to maintain handling workability while maintaining the mechanical strength of the resulting crosslinked 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 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 to 70 mol% as described above. This is a range for obtaining sufficient softening at a high temperature of the obtained crosslinked product and maintaining transparency and mechanical strength.
  • the content of the component (C) is, as described above, the molar ratio of silicon-bonded hydrogen atoms in the component (C) to the total of alkenyl groups in the component (A) and the component (B). Is an amount in the range of 0.5-2.
  • the range of this content is a range for obtaining sufficient hardness at room temperature of the obtained crosslinked product.
  • 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).
  • the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the silicone composition.
  • platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable.
  • 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.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1 can be added to this complex.
  • 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). If it is, it will not be specifically limited.
  • the content of such component (D) is preferably an amount such that the metal atom in component (D) is in the range of 0.01 to 500 ppm by mass with respect to the silicone composition, The amount is preferably in the range of 0.01 to 100 ppm, and particularly preferably in the range of 0.01 to 50 ppm. This is a range for allowing the obtained silicone composition to be sufficiently crosslinked and not to cause problems such as coloring.
  • the silicone resin (silicone composition) as the matrix resin is composed of at least the above component (A), component (B), component (C) and component (D), but as other optional components, alkyne alcohol, enyne compound, You may contain reaction inhibitor.
  • alkyne alcohol include ethynylhexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol.
  • the enyne compound include 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne.
  • 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7- Examples include tetrahexenylcyclotetrasiloxane and benzotriazole.
  • the content of the reaction inhibitor is not particularly limited, but is preferably in the range of 1 to 5,000 ppm with respect to the weight of the silicone composition.
  • the storage elastic modulus of the obtained crosslinked product can be adjusted by adjusting the content of the reaction inhibitor.
  • the phosphor composition according to the embodiment of the present invention may contain a solvent.
  • the solvent is not particularly limited as long as it can adjust the viscosity of the resin in a fluid state.
  • toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like can be mentioned.
  • the phosphor composition according to the embodiment of the present invention includes a dispersing agent and a leveling agent for stabilizing a coating film, and an adhesion assistant such as a silane coupling agent as a sheet surface modifier when a phosphor sheet is used. Etc. may be contained.
  • the phosphor composition according to the embodiment of the present invention may contain fine particles.
  • the fine particles include silicone fine particles, titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate. From the viewpoint of easy availability, silicone fine particles, silica fine particles, and alumina fine particles are preferably used as the fine particles.
  • the phosphor composition according to the embodiment of the present invention may contain a silanol group-containing methylphenyl silicone resin as a heating adhesive in order to reduce the storage elastic modulus (G ′) at 100 ° C. .
  • the structure of this silanol group-containing methylphenyl silicone resin is particularly preferably the one represented by the following general formula (E). (R 5 SiO 3 ) d (PhSiO 3 ) e (R 5 OHSiO 2 ) f (PhOHSiO 2 ) g (R 6 SiO 2 ) h ...
  • E General formula (E)
  • R 5 and R 6 are each an alkyl group or cycloalkyl group having 1 to 6 carbon atoms.
  • Ph is a phenyl group.
  • ⁇ Method for producing phosphor composition> an example of the manufacturing method of the phosphor composition which concerns on embodiment of this invention is demonstrated.
  • the organic compound represented by the general formula (1), the inorganic phosphor and the matrix resin, and the silicone fine particles and the solvent as required are mixed in a predetermined amount.
  • the phosphor composition is uniformly mixed and dispersed with an agitator / kneader such as a homogenizer, a self-revolving stirrer, a 3-roller, a ball mill, a planetary ball mill, or a bead mill. A thing is obtained.
  • Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing. Further, a specific component may be mixed in advance or a process such as aging may be performed. It is also possible to remove the solvent with an evaporator to obtain a desired solid content concentration.
  • the formed product according to the embodiment of the present invention is a phosphor formed product containing the above-described phosphor composition or a cured product thereof.
  • a formed product according to one embodiment of the present invention contains the above-described inorganic phosphor and the organic compound represented by the general formula (1), and a matrix resin or a cured product thereof.
  • These inorganic phosphors, the organic compound represented by the general formula (1), the matrix resin, and other components that may be contained in the formed product of the present invention are the same as those in the phosphor composition described above. It is.
  • This formed product can be obtained by molding the above-described phosphor composition or a phosphor sheet described later.
  • the matrix resin may be cured in the molding process of the phosphor composition or the phosphor sheet, if necessary.
  • the form of the formed product of the present invention is not particularly limited, and examples thereof include a cap shape and a sheet shape according to the light emitting diode shape.
  • the phosphor composition according to the embodiment of the present invention may be formed into a cap shape by using a mold and a heat press.
  • the manufacturing method of the fluorescent substance sheet mentioned later can be used.
  • the formation according to the embodiment of the present invention can be used as a formation for a remote phosphor.
  • the remote phosphor technique is a technique in which a three-dimensional shape formed with a phosphor is kneaded at a position away from a blue LED serving as a light source.
  • the remote phosphor technology is characterized in that since the phosphor is separated from the blue LED, there is little deterioration of the phosphor due to heat, the optical characteristics are stable, and the product variation is extremely small.
  • the formed product according to the embodiment of the present invention can be used for an LED module using a remote phosphor technology, for example, an LED illumination such as a torch, a spotlight, and a clip light.
  • the phosphor sheet according to the embodiment of the present invention is a film obtained by forming the above-described phosphor composition into a film (molded into a sheet shape), an organic compound represented by the general formula (1), and inorganic fluorescence. And a matrix resin or a cured product thereof.
  • these organic compounds and inorganic phosphors each convert light emitted from the light emitter into light having a longer wavelength than the light emitted.
  • the matrix resin contained in the phosphor sheet is a resin that forms a continuous phase by mixing with at least the inorganic phosphor.
  • inorganic phosphors the organic compound represented by the general formula (1), the matrix resin, and other components that may be contained in the phosphor sheet of the present invention are the same as those in the phosphor composition described above. It is the same. Further, the color conversion relationship between the organic light emitting material (organic compound represented by the general formula (1)) and the inorganic phosphor in the phosphor sheet is the same as that in the phosphor composition described above.
  • the thickness of the phosphor sheet is not particularly limited, but is preferably in the range of 10 to 1000 ⁇ m.
  • the thickness of the phosphor sheet is smaller than 10 ⁇ m, it is difficult to form a uniform sheet of the phosphor sheet due to the unevenness caused by the phosphor particles. If the thickness of the phosphor sheet exceeds 1000 ⁇ m, cracks are likely to occur, and it is difficult to mold the phosphor sheet.
  • a more preferable thickness of the phosphor sheet is 30 to 100 ⁇ m.
  • the thickness of the phosphor sheet is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the phosphor sheet preferably has high elasticity near room temperature from the viewpoints of storage properties, transportability, and processability.
  • the phosphor sheet is deformed so as to follow the shape of the LED chip and is in close contact with the light extraction surface of the LED chip. It is preferable to exhibit fluidity.
  • the viscoelastic behavior of such a phosphor sheet it is desirable to satisfy the following conditions (i) to (iii).
  • Condition (i) is: “At 25 ° C., the storage elastic modulus G ′ of the phosphor sheet is 1.0 ⁇ 10 4 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 6 Pa and the loss tangent of the phosphor sheet (Tan ⁇ ) is tan ⁇ ⁇ 1 ”.
  • Condition (ii) is: “At a temperature of 100 ° C., the storage elastic modulus G ′ is 1.0 ⁇ 10 2 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 4 Pa, and the loss tangent of the phosphor sheet is tan ⁇ ⁇ 1. Is.
  • Condition (iii) is: “At a temperature of 200 ° C., the storage elastic modulus G ′ is 1.0 ⁇ 10 4 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 6 Pa, and the loss tangent of the phosphor sheet is tan ⁇ ⁇ 1. Is.
  • the storage elastic modulus G ′ of the phosphor sheet is a storage elastic modulus when the dynamic viscoelasticity measurement (temperature dependence) of the phosphor sheet is performed with a rheometer.
  • Dynamic viscoelasticity measurement is a stress component whose phase matches the shear stress that appears when a steady state is reached when shear strain is applied to a material at a certain sine frequency. This is a technique for analyzing the dynamic mechanical properties of a material by breaking it down into (elastic component) and a stress component (viscous component) whose phase is delayed by 90 °.
  • Dynamic viscoelasticity measurement (temperature dependence) can be performed using a general viscosity / viscoelasticity measuring apparatus.
  • the storage elastic modulus G ′ of the phosphor sheet is a value when dynamic viscoelasticity measurement (temperature dependence) is performed under the following conditions.
  • the measuring device is a viscosity / viscoelasticity measuring device HAAKE MARSIII (manufactured by Thermo Fisher SCIENTIFIC).
  • the measurement condition is OSC temperature-dependent measurement.
  • the geometry is a parallel disk type (20 mm).
  • the measurement time is 1980 seconds.
  • the angular frequency is 1 Hz.
  • the angular velocity is 6.2832 rad / sec.
  • the temperature range is 25 to 200 ° C. (with low temperature temperature control function).
  • the heating rate is 0.08333 ° C./second.
  • the sample shape is circular (diameter 18 mm).
  • the storage elastic modulus G ′ of the phosphor sheet is obtained by dividing the stress component whose phase is coincident with the shear strain of the phosphor sheet by the shear strain. Since the storage elastic modulus G ′ represents the elasticity of the material against dynamic strain at each temperature, it is closely related to the hardness of the phosphor sheet, that is, processability.
  • the loss elastic modulus G ′′ of the phosphor sheet is obtained by dividing the stress component whose phase is delayed by 90 ° from the shear strain of the phosphor sheet by the shear strain. This loss elastic modulus G ′′ is the viscosity of the material. Therefore, it is closely related to the fluidity of the phosphor sheet, that is, the adhesion.
  • the loss tangent (tan ⁇ ) of the phosphor sheet is obtained by dividing the loss elastic modulus G ′′ by the storage elastic modulus G ′.
  • This tan ⁇ is an index indicating the state in which the material is placed. If tan ⁇ is less than 1, the elasticity is dominant and the phosphor sheet is in a solid state, whereas if tan ⁇ is 1 or more, the viscosity is dominant and the phosphor sheet is liquid. State.
  • the phosphor sheet satisfies the above-mentioned condition (i) “1.0 ⁇ 10 4 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 6 Pa and tan ⁇ ⁇ 1 at 25 ° C.” Therefore, it is sufficiently elastic at room temperature (25 ° C.). For this reason, the phosphor sheet is cut without deformation of the surroundings even with a fast shearing stress such as a cutting process with a blade, and as a result, the processability of the phosphor sheet with high dimensional accuracy can be obtained.
  • the storage elastic modulus G ′ at 25 ° C. of the phosphor sheet is more preferably 9.0 ⁇ 10 5 Pa or less from the viewpoint of crack prevention during handling and workability.
  • the tan ⁇ at room temperature of the phosphor sheet is more preferably 0.7 or less from the viewpoint of lowering the attaching temperature.
  • the lower limit of tan ⁇ is not particularly limited, but is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.25 or more.
  • the phosphor sheet satisfies the above-mentioned condition (ii) “1.0 ⁇ 10 2 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 4 Pa and tan ⁇ ⁇ 1 at 100 ° C.” It is sufficiently viscous at 100 ° C. and has high fluidity. Therefore, if the phosphor sheet having this physical property is heated to 100 ° C. or higher and attached to the LED chip, the phosphor sheet quickly flows and deforms according to the shape of the light emitting surface of the LED chip. High adhesion between the phosphor sheet and the LED chip can be obtained. Thereby, the light extraction property from the LED chip is improved, and the luminance is improved.
  • the storage elastic modulus G ′ at 100 ° C.
  • the tan ⁇ at 100 ° C. of the phosphor sheet is more preferably 1.6 or more from the viewpoint of adhesion.
  • the upper limit of tan ⁇ is not particularly limited, but is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably 3.3 or less.
  • the phosphor sheet satisfies the above-mentioned condition (iii) “1.0 ⁇ 10 4 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 6 Pa and tan ⁇ ⁇ 1 at 200 ° C.”
  • the LED chip can be stably operated. Because, if the phosphor sheet attached to the LED chip is heated at 200 ° C. or higher, complete curing of the phosphor sheet is completed, and the entire resin contained in the phosphor sheet is integrated. This is because the phosphor sheet is not affected by thermal factors such as heat when the LED chip is lit.
  • the storage elastic modulus G ′ at 200 ° C. of the phosphor sheet is more preferably 9.0 ⁇ 10 5 Pa or less from the viewpoint of preventing cracks.
  • the tan ⁇ at 200 ° C. of the phosphor sheet is more preferably 0.08 or less from the viewpoint of thermal stability.
  • the lower limit of tan ⁇ is not particularly limited, but is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more.
  • the resin contained therein may be in an uncured state.
  • the resin contained in the phosphor sheet is preferably in a state of being cured to some extent rather than being completely cured as a whole.
  • the curing of the phosphor sheet-containing resin has progressed to such an extent that the storage elastic modulus G ′ does not change for a long period of time of one month or longer when stored at room temperature.
  • FIG. 1 is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
  • the phosphor sheet 2 according to the embodiment of the present invention is a sheet-like phosphor including a laminated structure of a phosphor layer 34 and an organic light emitting material layer 35.
  • the phosphor layer 34 is a layer containing the inorganic phosphor 36 and the matrix resin in the present invention.
  • the organic light emitting material layer 35 is a layer containing an organic compound represented by the general formula (1).
  • the phosphor sheet 2 is formed by forming the phosphor layer 34 and the organic light emitting material layer 35 on the base material 14.
  • Such a phosphor sheet 2 and the substrate 14 constitute a phosphor sheet laminate 33 having a laminated structure in which the phosphor layer 34 and the organic light emitting material layer 35 are sequentially laminated on the substrate 14. .
  • Preliminarily laminating the phosphor layer 34 and the organic light emitting material layer 35 on the substrate 14 is a process rather than forming each of these layers separately when the phosphor sheet 2 is used in an LED package. It leads to reduction.
  • the phosphor sheet 2 may be a laminate including other layers in addition to the phosphor layer 34 and the organic light emitting material layer 35.
  • a barrier layer etc. are mentioned as another layer.
  • the phosphor layer (for example, the phosphor layer 34 shown in FIG. 1) is a layer containing an inorganic phosphor (particulate inorganic phosphor 36, etc.) and a matrix resin, and preferably mainly an inorganic phosphor and a matrix. It is a layer mixed with resin.
  • the inorganic phosphor, the matrix resin, and other components that may be contained in the phosphor layer of the present invention are the same as those in the phosphor composition described above.
  • the organic light emitting material layer (for example, the organic light emitting material layer 35 shown in FIG. 1) is a layer containing an organic compound represented by the general formula (1), and is preferably represented mainly by the general formula (1). It is a layer in which an organic compound and a matrix resin are mixed.
  • the organic compound and matrix resin represented by the general formula (1) are the same as those in the above-described phosphor composition.
  • the organic light-emitting material layer is a bonding agent such as a dispersing agent or leveling agent for stabilizing the coating film, and a silane coupling agent as a surface modifier when used as an organic light-emitting material layer. It may contain adjuvants and the like.
  • the organic light emitting material layer may contain fine particles.
  • the fine particles include titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate.
  • silica fine particles, alumina fine particles, and silicone fine particles are preferably used from the viewpoint of easy availability.
  • a known metal, film, glass, ceramic, paper, or the like can be used without particular limitation.
  • metal including aluminum alloy), zinc, copper, iron, and other metal plates and foils, cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene , Polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, plastic film such as tetrafluoroethylene and ethylene copolymer (ETFE), ⁇ -polyolefin resin, polycaprolactone resin, acrylic resin, silicone Plastic film made of a resin and a copolymer resin of these with ethylene, paper laminated with the plastic, or coated with the plastic Paper was, said metal laminated or vapor-deposited paper, the metals and plastic film laminate
  • glass and resin films are preferably used because of the ease of producing a phosphor sheet (for example, the phosphor sheet 2 shown in FIG. 1) and the ease of individualizing the phosphor sheet.
  • the substrate is preferably a flexible film.
  • a film with high strength is preferable so that there is no fear of breakage when handling a film-like substrate.
  • Resin films are preferred in terms of their required characteristics and economy, and among these, plastic films selected from the group consisting of PET, polyphenylene sulfide, and polypropylene are preferred in terms of economy and handleability.
  • a polyimide film is preferable at a heat resistant surface.
  • the surface of the base material may be subjected to a mold release treatment in advance for ease of peeling of the sheet.
  • the thickness of the substrate is not particularly limited, but the lower limit is preferably 25 ⁇ m or more, and more preferably 38 ⁇ m or more. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.
  • a barrier layer is mentioned as an example of the other layer mentioned above contained in a fluorescent substance sheet.
  • the barrier layer is not particularly limited and is appropriately used in the case where the gas barrier property is improved with respect to the phosphor sheet.
  • Examples of the film having a barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and acrylonitrile, and various resins such as fluorine resins. Mention may be made of membranes.
  • auxiliary layer having a shield function, an infrared cut function, an ultraviolet cut function, a polarization function, and a toning function may be further provided as the other layers described above.
  • the phosphor sheet according to the embodiment of the present invention can be obtained from the phosphor composition described above. That is, in this phosphor sheet manufacturing method, the phosphor composition produced by the above-described method is applied onto a substrate, dried, and heat-cured. As a result, a phosphor sheet can be produced.
  • the phosphor composition is coated on the substrate by reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade.
  • a coater a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used.
  • it is preferably applied by a slit die coater.
  • the phosphor sheet can be dried 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 heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
  • examples of a simple method include a method of performing replacement using a hot plate and a method using a vacuum laminator or a dry film laminator.
  • a phosphor composition in which an inorganic phosphor is dispersed in a matrix resin is prepared as a coating solution for forming a phosphor layer.
  • a predetermined amount of the aforementioned inorganic phosphor, matrix resin, silicone fine particles, solvent and the like are mixed.
  • these mixtures are homogeneously mixed and dispersed with a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a bead mill.
  • a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a 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 phosphor composition produced by the method described above is applied onto a substrate, dried, and heat-cured. As a result, a phosphor layer can be produced.
  • the phosphor composition is coated on the substrate by reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade.
  • a coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used.
  • the phosphor layer can be dried 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 heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
  • an organic light emitting material layer is formed on the phosphor layer produced as described above.
  • a phosphor sheet having a phosphor layer and an organic light emitting material layer can be obtained by directly applying a coating liquid containing an organic light emitting material on the phosphor layer, followed by drying and heat curing.
  • an organic light emitting composition in which an organic light emitting material is dispersed in a matrix resin is prepared as a coating liquid for forming an organic light emitting material layer.
  • a predetermined amount of the aforementioned organic light emitting material, matrix resin, solvent and the like are mixed.
  • these mixtures are homogeneously mixed and dispersed with a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a bead mill.
  • a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a 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.
  • organic light emitting material on the phosphor layer is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade.
  • a coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used.
  • it is preferably applied by a slit die coater.
  • the organic light emitting material layer can be dried 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 for heating the organic light emitting material layer.
  • the heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
  • the phosphor composition according to the embodiment of the present invention can be preferably used for an LED chip having a general structure such as lateral, vertical, and flip chip.
  • the LED chip may process the light emitting surface into a texture or the like based on an optical design.
  • the light emitting surface is a surface from which light from the LED chip is extracted.
  • Such an LED chip is metal-wired, and then the LED chip is sealed using the phosphor composition according to the embodiment of the present invention, whereby the LED chip is packaged into an LED package. It is possible.
  • the LED chip in the LED package is a light emitting body whose emitted light is color-converted by the phosphor composition in a state of covering the light emitting surface. And this LED package is equipped with the hardened
  • the LED package can be suitably used for various LED light emitting devices such as various illuminations, liquid crystal backlights, and headlamps.
  • FIG. 2 is a diagram showing an example of a method for manufacturing an LED package using the phosphor composition according to the embodiment of the present invention.
  • the present invention is not limited to the manufacturing method shown in FIG.
  • a particularly preferable method is an injection step of injecting the phosphor composition into a package frame in which the LED chip is installed, After the injection step, at least a sealing step of sealing the LED chip in the package frame with a sealing material is included.
  • a preparation process for preparing the mounting substrate 7 with the reflector 5 as the package frame 12 is performed (state A1).
  • a mounting process for mounting and installing the LED chip 1 on the mounting substrate 7 is performed (state A2).
  • an injection step of injecting a desired amount of the phosphor composition 4 according to the embodiment of the present invention into the package frame 12 on which the LED chip 1 is installed is performed (state A3).
  • the method for injecting the phosphor composition 4 include, but are not limited to, injection molding, compression molding, cast molding, transfer molding, coating, potting (dispensing), printing, and transfer. Particularly preferably, potting (dispensing) can be used.
  • a heat curing step is performed in which the phosphor composition 4 is heat cured.
  • cured material of the fluorescent substance composition 4 can be provided on the LED chip 1 in the form suitable for the shape of the package frame 12.
  • FIG. the heat curing treatment of the phosphor composition 4 can be performed using a general heating device such as a hot air dryer or an infrared dryer.
  • the heat curing conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. In this case, it is possible to perform heat curing stepwise such as step cure.
  • cured material is performed (state A4).
  • the injection method and heat curing conditions for the transparent sealing material 6 are based on the above-described injection method and heat cure conditions for the phosphor composition 4.
  • the LED package 13 is manufactured through the above steps. Thereafter, the LED package 13 may be provided with an overcoat layer made of a transparent resin, a lens, or the like, if necessary.
  • the phosphor sheet according to the embodiment of the present invention is preferably attached to the light emitting surface of an LED chip having a general structure such as lateral, vertical, and Philip chip.
  • the LED chip with a phosphor sheet in which the phosphor sheet is laminated on the surface of the LED chip can be formed.
  • the phosphor sheet can be suitably used particularly for vertical and flip chip type LED chips having a large light emitting area.
  • the light emitting surface is a surface from which light from the LED chip is extracted.
  • the light emitting surface from the LED chip may be a single plane or not a single plane.
  • LED chips mainly having only an upper light emitting surface can be mentioned.
  • a vertical type LED chip, an LED chip whose side surface is covered with a reflective layer, and light is extracted only from the upper surface are exemplified.
  • an LED chip having an upper light emitting surface and a side light emitting surface and an LED chip having a curved light emitting surface can be mentioned.
  • the light emitting surface is not a single plane because the light emitted from the side can be used and brightened.
  • a flip chip type LED chip having an upper light emitting surface and a side light emitting surface is preferable because the light emitting area can be increased and the chip manufacturing process is easy.
  • the LED chip may process the light emitting surface into a texture or the like based on an optical design in order to improve the light emission efficiency.
  • the phosphor sheet according to the embodiment of the present invention can be pasted using an adhesive such as a transparent resin without being directly pasted on the LED chip.
  • an adhesive such as a transparent resin
  • covering the light emitting surface of the LED chip with the phosphor sheet allows the light from the LED chip to be directly incident on the phosphor sheet that is the color conversion layer without losing light by reflection or the like. preferable. Thereby, uniform white light with little color variation and high efficiency can be obtained.
  • the color conversion layer here refers to a layer that absorbs light emitted from the LED chip, converts the wavelength, and emits light having a wavelength different from that of the LED chip.
  • the LED chip with a phosphor sheet obtained by these methods can be an LED package packaged by metal wiring or sealing. After that, by incorporating this LED package into the module, the phosphor sheet according to the embodiment of the present invention, that is, the LED chip with the phosphor sheet using this, can be used for various illuminations, liquid crystal backlights, and headlamps. It can use suitably for various LED light-emitting devices including the first.
  • FIG. 3A to FIG. 3C are views showing a suitable example of the LED chip with a phosphor sheet according to the embodiment of the present invention.
  • FIG. 3A is a diagram showing an example of an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • the LED chip 31 with a phosphor sheet illustrated in FIG. 3A is obtained by attaching the phosphor sheet 2 to the upper surface (light emitting surface) of the LED chip 1.
  • FIG. 3B is a diagram showing another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 3B is obtained by attaching the phosphor sheet 2 to not only the upper surface (upper light emitting surface) but also the side surface (side light emitting surface) of the LED chip 1. .
  • This type of LED chip 31 with a phosphor sheet is preferable because it can perform color conversion with respect to light emission from the side surface of the LED chip 1.
  • FIG. 3C is a diagram showing still another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • the LED chip 31 with a phosphor sheet illustrated in FIG. 3C uses a flip chip type LED chip 1 having an electrode 3 on the lower surface, and the phosphor sheet 2 has an upper surface and a side that are light emitting surfaces of the LED chip 1. It is coated.
  • FIG. 4A to FIG. 4J are views showing a suitable example of the LED package according to the embodiment of the present invention.
  • FIG. 4A is a diagram showing an example of an LED package using the phosphor composition according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4A is obtained by injecting the phosphor composition 4 into the mounting substrate 7 with the reflector 5 on which the LED chip 1 is installed, and then sealing the LED chip 1 with the transparent sealing material 6. It is.
  • This LED package 13 is a suitable example as a thing provided with the hardened
  • FIG. 4A is a diagram showing an example of an LED package using the phosphor composition according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4A is obtained by injecting the phosphor composition 4 into the mounting substrate 7 with the reflector 5 on which the LED chip 1 is installed, and then sealing the LED chip 1 with the transparent sealing material 6. It is.
  • This LED package 13 is a suitable example as a
  • FIG. 4B is a view showing Example 1 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4B has a phosphor sheet 2 attached on the LED chip 1 installed on the mounting substrate 7 with the reflector 5, and then the LED chip 1 and the phosphor sheet 2 together with a transparent sealing material. 6 is sealed.
  • FIG. 4C is a diagram showing an example 2 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4C has the phosphor sheet 2 attached to the LED chip 1 placed on the mounting substrate 7 with the reflector 5 not only on the top surface but also on the side surface. A lens according to 6 is also attached. This type of LED package 13 is preferable because the phosphor sheet 2 can perform color conversion for light emitted from the side surface of the LED chip 1.
  • FIG. 4D is a view showing Example 3 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4D is obtained by sealing the LED chip 1 together with the phosphor sheet 2 by using a lens molding of the transparent sealing material 6 without using the reflector 5. Except this, it is the same as the LED package 13 illustrated in FIG. 4B.
  • FIG. 4E is a diagram showing Example 4 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4E is the same as the LED package 13 illustrated in FIG. 4C except that the reflector 5 is not used.
  • FIG. 4F is a view showing Example 5 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4F uses a flip chip type LED chip 1 having electrodes 3 and gold bumps 8 on the lower surface, and the upper surface and side surfaces, which are the light emitting surfaces of the LED chip 1, are covered with the phosphor sheet 2. It is a thing. Except this, it is the same as the LED package 13 illustrated in FIG. 4C. When the side surface of the LED chip 1 is covered with the phosphor sheet 2, the phosphor sheet 2 may extend to the upper surface of the mounting substrate 7 as shown in FIG. 4F.
  • FIG. 4G is a diagram showing Example 6 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4G is obtained by sealing the flip chip type LED chip 1 (see FIG. 4F) together with the phosphor sheet 2 by using a lens molding of the transparent sealing material 6 without using the reflector 5. is there. Except this, it is the same as the LED package 13 illustrated in FIG. 4E.
  • FIG. 4H is a view showing Example 7 of the LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4H is obtained by pasting the LED chip 1 and the phosphor sheet 2 with the transparent adhesive 9. Except this, it is the same as the LED package 13 illustrated in FIG. 4B.
  • FIG. 4I is a diagram showing Example 8 of an LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4I uses a phosphor sheet 2 with a base material 10 prepared in advance. In this type of LED package 13, the base material 10 is used without being peeled from the phosphor sheet 2. Except this, it is the same as the LED package 13 illustrated in FIG. 4H. As a material of the base material 10, glass is preferable.
  • the LED package 13 illustrated in FIG. 4B to FIG. 4I is a preferred example as a phosphor sheet 2 or a cured product thereof.
  • FIG. 4J is a diagram showing an example of an LED package using a formed product using the phosphor composition according to the embodiment of the present invention.
  • the LED package 13 illustrated in FIG. 4J uses a flip chip type LED chip 1 (see FIG. 4F), and covers the light emitting surface of the LED chip 1 with the transparent encapsulant 6, The transparent sealing material 6 is covered with a formed article 11 using a phosphor composition. Except this, it is the same as the LED package 13 illustrated in FIG. 4G.
  • This LED package 13 is a suitable example as a thing provided with the formation 11 (phosphor formation) containing the phosphor composition 4 or its hardened
  • the LED package to which the present invention can be applied is not limited to these.
  • the transparent sealing material 6 has a shape as shown in FIG. 4C, and the phosphor sheet 2 is attached not only to the top surface of the LED chip 1 but also to the side surface. It doesn't matter.
  • the structure of each part of the LED package 13 illustrated in FIGS. 4A to 4J can be appropriately combined.
  • each part of the LED package 13 may be replaced with a known part other than these, or may be combined.
  • the transparent sealing material 6 is a material excellent in moldability, transparency, heat resistance, adhesiveness, etc.
  • epoxy resin silicone resin (organopolysiloxane cured product such as silicone rubber and silicone gel (crosslinked) And the like)
  • known resins such as urea resins, fluororesins, and polycarbonate resins can be used.
  • the transparent adhesive 9 the transparent sealing material 6 mentioned above can be used.
  • a typical method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention there are mainly two methods for manufacturing an LED chip with a phosphor sheet used for manufacturing an LED package.
  • One is a method of cutting the phosphor sheet into individual pieces and then attaching the separated phosphor sheets to individual LED chips.
  • the other is a method in which a phosphor sheet is affixed to a wafer on which LED chips are formed before dicing, and then dicing of the wafer and cutting of the phosphor sheet are performed in a lump. Details of these two methods will be described later.
  • the manufacturing method of the LED package using the phosphor sheet according to the embodiment of the present invention is not limited to these two methods.
  • a particularly preferable method is that the phosphor sheet is divided into a plurality of sections and is divided into the plurality of sections.
  • An adhesion step of applying pressure while heating with a crimping tool is an alignment step of causing one section of the phosphor sheet to face the light emitting surface of one LED chip, and heating one section of the phosphor sheet and the light emitting surface of the one LED chip opposed to each other.
  • the phosphor sheet according to the embodiment of the present invention can be attached to the LED chip using an adhesive such as a transparent resin without being attached directly to the LED chip.
  • an adhesive such as a transparent resin
  • the phosphor sheet is adhered by pressure bonding by applying pressure while heating at a desired temperature when adhering to the LED chip.
  • the heating temperature is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 60 ° C. or higher and 160 ° C. or lower.
  • the positional accuracy of the pasting is important.
  • any existing apparatus can be used as long as it can be bonded at a desired temperature.
  • a thermocompression bonding tool such as a mounter or a flip chip bonder can be used.
  • the phosphor sheets when they are stuck together on the wafer level LED chips, they can be stuck using a vacuum laminator or a thermocompression bonding tool having a heating portion of about 100 mm to 200 mm square.
  • the phosphor sheet is pressure-bonded to the LED chip at a desired temperature and thermally fused, and then allowed to cool to room temperature, and the substrate is peeled from the phosphor sheet.
  • the phosphor sheet after being allowed to cool to room temperature after heat fusion is easily peeled off from the substrate while firmly adhering to the LED chip. It becomes possible.
  • the method for cutting the phosphor sheet will be described.
  • the phosphor sheet is cut into individual pieces before being attached to the LED chip, and the individual phosphor chips are attached to the individual LED chips, and the wafer.
  • a phosphor sheet is attached to a level LED chip and then the phosphor sheet is cut simultaneously with wafer dicing.
  • the uniformly formed phosphor sheet is processed into a predetermined shape by laser processing or cutting with a blade and divided. Since processing with a laser imparts high energy, it is very difficult to avoid scorching of the resin in the phosphor sheet and deterioration of the phosphor, so cutting with a blade is desirable.
  • a cutting method with a blade there are a method of cutting a phosphor sheet by pushing a simple blade, and a method of cutting a phosphor sheet with a rotary blade, both of which can be suitably used.
  • an apparatus for cutting with a rotary blade an apparatus used for cutting (dicing) a semiconductor substrate (wafer) called a dicer into individual chips can be suitably used. If the dicer is used, the width of the dividing line of the phosphor sheet can be precisely controlled by the thickness of the rotary blade and the condition setting, so that higher processing accuracy can be obtained than when the phosphor sheet is cut by pushing a simple blade.
  • the phosphor sheet When cutting the phosphor sheet in a state of being laminated on the substrate, the phosphor sheet may be separated into the entire substrate, or the phosphor sheet is separated into pieces and the substrate is not cut. It doesn't matter. Alternatively, the substrate may be subjected to a so-called half cut in which a cut line that does not penetrate is entered. The phosphor sheet thus separated is heat-sealed on the light emitting surface of each individual LED chip.
  • FIG. 5 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • the LED package manufacturing method includes steps such as cutting the phosphor sheet, attaching the phosphor sheet to the LED chip, and dicing when the phosphor sheet is separated into individual substrates.
  • This LED package manufacturing method includes a step of cutting the phosphor sheet into individual pieces together with a base material, and a step of pressing the phosphor sheet cut into the individual pieces at a desired temperature and attaching them to the LED chip. It is.
  • a temporary fixing step of fixing the phosphor sheet 2 laminated on the base material 14 to the temporary fixing sheet 15 is performed (state B1).
  • the phosphor sheet 2 and the base material 14 are both separated into pieces, they are fixed to the temporary fixing sheet 15 so as to be easy to handle.
  • disconnects both the fluorescent substance sheet 2 and the base material 14, and separates the fluorescent substance sheet 2 with the base material 14 is performed (state B2).
  • an alignment process is performed for aligning the laminated body (individual laminated body) of the phosphor sheet 2 and the base material 14 separated on the LED chip 1 mounted on the mounting substrate 7 ( State B3).
  • This LED chip 1 is obtained by a wafer dicing process, and is mounted in advance on a mounting substrate 7 with a reflector 5 constituting a package frame 12.
  • thermocompression bonding tool 16 the individual laminate of the phosphor sheet 2 and the base material 14 in a state where the light emitting surface of the LED chip 1 and the phosphor sheet 2 are opposed to each other by the above alignment process. Then, a bonding process is performed in which the pressure is applied while heating at a desired temperature to bond (crimp) the LED frame 1 on the mounting substrate 7 of the package frame 12 (state B4). At this time, it is preferable to perform the bonding step under vacuum or under reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip 1.
  • the LED chip 1 in the package frame 12, the phosphor sheet 2, and the individual laminate of the base material 14 are allowed to cool to room temperature, and from the phosphor sheet 2 in a state of being bonded to the LED chip 1.
  • a cooling step for peeling the base material 14 is performed (state B5).
  • the base material 14 is a transparent member such as glass, in the cooling step, the base material 14 may be left as it is without being peeled from the phosphor sheet 2 (state B6).
  • FIG. 6 is a diagram illustrating an example of a method of manufacturing an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • the phosphor sheet 2 is cut when the phosphor sheet 2 is separated into pieces while the base material 14 is continuous, and the phosphor sheet 2 to a wafer level LED chip. Steps such as pasting and dicing are included.
  • a step of cutting the phosphor sheet 2 into individual pieces without dividing the substrate 14 into individual pieces, and a phosphor sheet 2 cut into the individual pieces in a desired manner includes pressure bonding at a temperature and attaching the wafer level LED chip to the wafer level LED chip.
  • a lamination process for laminating the phosphor sheet 2 on the base material 14 is performed in advance, and then the base material 14 is laminated.
  • a cutting process is performed in which the phosphor sheet 2 in a state is cut into pieces (state C2).
  • the base material 14 is not singulated.
  • the base material 14 is not cut at all, but the base material 14 may be partially cut as long as the base material 14 is continuous.
  • an alignment step is performed in which the separated phosphor sheet 2 is opposed to the LED wafer 17 before dicing and aligned with an LED chip (not shown) of the LED wafer 17 (state C3). ).
  • the LED wafer 17 is a wafer having a plurality of LED chips formed on the surface thereof.
  • the LED chip on the surface of the LED wafer 17 before dicing is a wafer level LED chip.
  • an adhesion process is performed in which these phosphor sheets 2 and the LED wafer 17 before dicing are pressed and bonded (crimped) while being heated at a desired temperature using the thermocompression bonding tool 16 (state C4). ).
  • the bonding step under vacuum or under reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip on the surface of the LED wafer 17.
  • the phosphor sheet 2 (separated) and the LED chip (wafer level LED chip) on the surface of the LED wafer 17 are pressure-bonded.
  • the phosphor sheet 2, the LED wafer 17 and the base material 14 are allowed to cool to room temperature, and a cooling step is performed in which the base material 14 is peeled off from the phosphor sheet 2 in a state of being adhered to the LED wafer 17. (State C5). Thereafter, a dicing process is performed in which the LED wafer 17 is diced into individual LED chips (state C6). As a result, a desired number (for example, a plurality) of LED chips 18 with phosphor sheets that are separated into individual pieces are obtained.
  • FIG. 7 is a diagram showing another example of the method for manufacturing the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention.
  • FIG. 7 shows an example of a process in the case where the phosphor sheet 2 and the LED wafer 17 are collectively diced after being bonded.
  • a phosphor sheet 2 is pressure-bonded to a plurality of LED chips (wafer level LED chips) before dicing and bonded together at a desired temperature, and phosphor A step of dicing the sheet 2 and the wafer level LED chips together is included.
  • the manufacturing method of the LED package with a phosphor sheet shown in FIG. 7 first, after the lamination process of laminating the phosphor sheet 2 on the base material 14 is performed, the phosphor sheet 2 is not cut in advance, An alignment step is performed in which the phosphor sheet 2 with the base material 14 is opposed to the LED wafer 17 before dicing, and the phosphor sheet 2 and the LED wafer 17 are aligned (state D1). Thereby, the phosphor sheet 2 and the LED chip (not shown) on the surface of the LED wafer 17 are aligned.
  • an adhesion process is performed in which the phosphor sheet 2 and the LED wafer 17 before dicing are pressed and bonded (crimped) while being heated at a desired temperature by the thermocompression bonding tool 16 (state D2).
  • the phosphor sheet 2, the LED wafer 17 and the base material 14 are allowed to cool to room temperature, and a cooling step is performed in which the base material 14 is peeled off from the phosphor sheet 2 in a state of being adhered to the LED wafer 17. (State D3). Thereafter, the LED wafer 17 is diced to be separated into LED chips, and at the same time, a dicing process (cutting process) for cutting the phosphor sheet 2 into pieces is performed (state D4). As a result, a desired number (for example, a plurality) of LED chips 18 with phosphor sheets that are separated into individual pieces are obtained.
  • the base material 14 is not peeled off from the phosphor sheet 2 adhered to the LED wafer 17, and the phosphor sheet 2, the LED wafer 17, and the base material 14 are allowed to cool to room temperature.
  • a process may be performed (state D5).
  • the LED wafer 17 is diced into individual LED chips, and at the same time, a dicing process (cutting process) is performed in which the phosphor sheet 2 is cut into individual pieces together with the base material 14 (state D6).
  • a desired number for example, a plurality
  • the LED chip 18 with a phosphor sheet thus obtained may be used as it is without peeling off the base material 14. Further, when the base material 14 is an opaque member such as a plastic film other than glass, the LED chip 18 with a phosphor sheet with the base material separated is mounted on the substrate, and then the LED chip with the phosphor sheet is mounted. 18 may be peeled off.
  • the electrode joint portion on the LED chip inside and outside the 1 mm square is desirably 500 ⁇ m or less so as not to reduce the area of the light emitting surface.
  • the hole is formed with a thickness of 500 ⁇ m or less in accordance with the size of the electrode joint portion.
  • the electrode for performing wire bonding or the like needs to have a certain size, and is at least about 50 ⁇ m.
  • the hole is formed with a size of about 50 ⁇ m according to the size of the electrode. If the size of the hole is too large compared to the electrode, the light emitting surface is exposed, light leakage occurs, and the color characteristics of the LED package deteriorate.
  • the storage elastic modulus G ′ of the phosphor sheet at 25 ° C. is 1.0 ⁇ 10 4 Pa ⁇ G ′ ⁇ 1.0 ⁇ 10 6 Pa and tan ⁇ ⁇ 1 is very important.
  • an affixing device having an optical alignment mechanism is required. At this time, it is difficult to align the phosphor sheet and the LED chip in terms of work, and practically, it is possible to align the phosphor sheet and the LED chip in a lightly contacted state. Often done. In this alignment, if the phosphor sheet has adhesiveness, it is very difficult to move the phosphor sheet in contact with the LED chip. If the phosphor sheet according to the embodiment of the present invention is aligned at room temperature, it is not sticky, so that it is easy to align the phosphor sheet and the LED chip in a light contact state. .
  • FIG. 8 is a diagram showing an example of a phosphor sheet attaching method according to the embodiment of the present invention.
  • FIG. 8 shows a bonding method in which the phosphor sheets 2 are bonded to the LED chips 1 one by one using the phosphor sheet laminate 20 singulated for each LED chip.
  • the phosphor sheet laminate 20 which is a laminate of the base material 19 and the phosphor sheet 2 has a plurality of LED chips 1 mounted on the package substrate 21. Each is individually cut into pieces. Each of the plurality of LED chips 1 is mounted in advance on the package substrate 21 by connecting the gold bump 8 and the package electrode 22.
  • the separated phosphor sheet laminate 20 is positioned so that the LED chip 1 and the phosphor sheet 2 on the package substrate 21 face each other (state E1).
  • the phosphor sheet 2 (separated) of the phosphor sheet laminate 20 is sequentially attached to at least the light emitting surface (for example, the upper surface and the side surface) of the LED chip 1 on the package substrate 21 by thermocompression bonding or the like. Attached (state E2).
  • FIG. 9 is a diagram showing another example of the phosphor sheet attaching method according to the embodiment of the present invention.
  • FIG. 9 shows a pasting method in which a plurality of LED chips 1 are collectively covered with a phosphor sheet 2 and then the phosphor sheet 2 is cut and individualized.
  • the phosphor sheet laminate 20, which is a laminate of the base material 19 and the phosphor sheet 2 is not separated into a plurality of pieces on the package substrate 21.
  • the LED chip 1 and the phosphor sheet 2 are positioned so as to face each other at once (state F1).
  • the plurality of LED chips 1 are mounted in advance on the package substrate 21 by connecting the gold bumps 8 and the package electrodes 22 as in the case shown in FIG. Thereafter, the phosphor sheet 2 (not separated into individual pieces) of the phosphor sheet laminate 20 is subjected to at least light emitting surfaces (for example, upper and side surfaces) of the plurality of LED chips 1 on the package substrate 21 by thermocompression bonding or the like. (State F2). Although not specifically shown in FIG. 9, the phosphor sheet 2 attached to the plurality of LED chips 1 is then cut and individualized individually for each of the plurality of LED chips 1.
  • Examples of the method for attaching the phosphor sheet 2 to the LED chip 1 in the method for producing the LED chip with the phosphor sheet include the method shown in FIG. 8 and the method shown in FIG. 9 described above, and any method is used. Also good.
  • the affixing of the phosphor sheet 2 to the LED chip 1 is performed by pressing the base material 19 in a state of softening and flowing.
  • the sticking temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher, from the viewpoint of enhancing adhesiveness.
  • the heat-fusible resin used for the phosphor sheet 2 has a property that the viscosity is temporarily lowered by heating, and is further cured by heating. Therefore, the temperature of the attaching step is preferably 150 ° C. or less from the viewpoint of maintaining adhesiveness, and further, 120 ° C.
  • the viewpoint of maintaining the shape of the phosphor sheet 2 at a certain level or more is more preferable. Further, in order to prevent the remaining of the air pool, it is preferable to perform the pasting under a reduced pressure of 0.01 MPa or less.
  • Examples of the manufacturing apparatus for performing such affixing include vacuum affixing machines such as a vacuum diaphragm laminator, a vacuum roll laminator, a vacuum hydraulic press, a vacuum servo press, a vacuum electric press, and a TOM molding machine.
  • a vacuum diaphragm muraminator is preferable because the number that can be processed at one time is large, and pressure can be applied without deviation from directly above.
  • the LED package manufacturing method is not limited to these examples.
  • FIG. 10 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • a temporary fixing step of temporarily fixing the LED chip 1 on the pedestal 24 via the double-sided adhesive tape 23 is performed (state G1).
  • the lamination process which positions and laminates
  • a laminate 37 that is a laminate of the LED chip 1, the phosphor sheet 2, and the base material 19 on the pedestal 24 (see state G1) is obtained.
  • an adhesion process for adhering the LED chip 1 and the phosphor sheet 2 of the laminate 37 is performed (state G3).
  • the laminate 37 is placed in the lower chamber 26 of the vacuum diaphragm muraminator 28.
  • the vacuum diaphragm muraminator 28 depressurizes the upper chamber 25 and the lower chamber 26 by exhausting from the exhaust port 29 b while heating the laminate 37.
  • the vacuum diaphragm muraminator 28 performs heating under reduced pressure until the base material 19 of the laminate 37 flows, and then expands the diaphragm 27 by sucking air into the upper chamber 25 through the air inlet 29a.
  • the diaphragm 27 presses the phosphor sheet 2 against the LED chip 1 through the base material 19 and affixes the phosphor sheet 2 so as to follow the light emitting surface of the LED chip 1.
  • a cutting step is performed in which the adhesive between the LED chip 1 and the phosphor sheet 2 is cut into pieces (state G4).
  • the vacuum diaphragm muraminator 28 returns the upper chamber 25 and the lower chamber 26 to atmospheric pressure.
  • the laminate 37 is taken out from the vacuum diaphragm laminator 28, and after being allowed to cool, the substrate 19 (see state G3) is peeled off.
  • the phosphor sheet 2 is cut in a state where the light emitting surface of the LED chip 1 is covered by cutting the cut portion 30 between the LED chips 1 on the pedestal 24 together with the double-sided adhesive tape 23 with a dicing cutter or the like. It becomes.
  • an individual LED chip 31 with a phosphor sheet is manufactured.
  • the LED package 32 is manufactured (state G6).
  • the LED package 32 is provided with an overcoat layer made of a transparent resin, a lens, or the like as necessary.
  • FIG. 11 is a diagram showing another example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
  • a mounting process is performed in which the LED chip 1 is bonded to the package electrode 22 on the package substrate 21 via the gold bumps 8 (state H1).
  • the lamination process which positions and laminates
  • a laminate 38 that is a laminate of the LED chip 1, the phosphor sheet 2, and the base material 19 on the package substrate 21 is obtained.
  • an adhesion process for adhering the LED chip 1 and the phosphor sheet 2 of the laminate 38 is performed (state H3).
  • the laminate 38 is placed in the lower chamber 26 of the vacuum diaphragm muraminator 28.
  • the vacuum diaphragm muraminator 28 depressurizes the upper chamber 25 and the lower chamber 26 by exhausting from the exhaust port 29b while heating the laminate 38.
  • the vacuum diaphragm muraminator 28 performs heating under reduced pressure until the base material 19 of the laminate 38 flows, and then expands the diaphragm 27 by sucking air into the upper chamber 25 through the air inlet 29a.
  • the diaphragm 27 presses the phosphor sheet 2 against the LED chip 1 through the base material 19 and affixes the phosphor sheet 2 so as to follow the light emitting surface of the LED chip 1.
  • a cutting process is performed in which the joined product of the package substrate 21, the LED chip 1, and the phosphor sheet 2 is cut into individual pieces (state H4).
  • the vacuum diaphragm muraminator 28 returns the upper chamber 25 and the lower chamber 26 to atmospheric pressure.
  • the laminate 38 is taken out from the vacuum diaphragm laminator 28, and after standing to cool, the substrate 19 (see state H3) is peeled off.
  • the phosphor sheet 2 is cut into pieces together with the package substrate 21 in a state where the light emitting surface of the LED chip 1 is covered by cutting the cut portions 30 between the LED chips 1 in the package substrate 21.
  • the LED package 32 is manufactured through the above steps (state H5). Although not particularly shown in FIG. 11, the LED package 32 is provided with an overcoat layer made of a transparent resin, a lens, or the like as necessary.
  • the light emitting device is an application example of the phosphor composition, the phosphor sheet, or the phosphor formed article described above.
  • this light-emitting device includes a phosphor formed product containing the above-described phosphor composition or a cured product thereof, and an LED chip (light emission) whose emitted light is color-converted by the phosphor composition contained in the phosphor formed product. And an LED package having a body.
  • the backlight unit according to the embodiment of the present invention is an application example of this light emitting device.
  • the backlight unit includes an LED package having a cured product of the phosphor composition described above, or an LED package having the phosphor sheet described above or a cured product thereof.
  • the backlight unit configured as described above can be used for displays, lighting, interiors, signs, signboards, and the like, but is particularly suitable for display and lighting applications.
  • a display (for example, a liquid crystal display) according to an embodiment of the present invention is an application example of this backlight unit.
  • the display includes an LED package having a cured product of the above-described phosphor composition, or an LED package having the above-described phosphor sheet or a cured product thereof.
  • ⁇ Base material> As the base material, “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 ⁇ m), which is a polyethylene terephthalate (polyethylene terephthalate film) that has been subjected to a release treatment, was used.
  • YAG phosphor type 1 (YAG1) as an example of the inorganic phosphor is “YAG81003” manufactured by Nemoto Lumi Materials.
  • Type 1 ( ⁇ 1) of ⁇ -sialon phosphor as an example of the inorganic phosphor is “GR-SW529Y” manufactured by Denka Co., Ltd.
  • the peak wavelength of the ⁇ -type sialon phosphor ( ⁇ 1) is 529 nm, and the average particle size (D50) is 16 ⁇ m.
  • Type 2 ( ⁇ 2) of the ⁇ -type sialon phosphor is “GR-MW540H” manufactured by Denka Co., Ltd.
  • the peak wavelength of the ⁇ -type sialon phosphor ( ⁇ 2) is 544 nm, and the average particle size (D50) is 20 ⁇ m.
  • Type 3 ( ⁇ 3) of the ⁇ -type sialon phosphor is “GR-SW532D” manufactured by Denka Co., Ltd.
  • the peak wavelength of the ⁇ -type sialon phosphor ( ⁇ 3) is 538 nm, and the average particle size (D50) is 16 ⁇ m.
  • the KSF phosphor type 1 (KSF1) as an example of the inorganic phosphor is a KSF phosphor sample A manufactured by Nemoto Lumi Material Co., Ltd.
  • the average particle diameter (D50) of this KSF phosphor (KSF1) is 50 ⁇ m.
  • Type 2 (KSF2) of KSF phosphor is KSF phosphor sample B manufactured by Nemoto Lumi Material Co., Ltd.
  • the average particle diameter (D50) of this KSF phosphor (KSF2) is 30 ⁇ m.
  • the absorption spectrum and fluorescence spectrum were measured in a 4 ⁇ 10 ⁇ 6 mol / L dichloromethane solution using a U-3200 type spectrophotometer and an F-2500 type spectrophotometer (both manufactured by Hitachi, Ltd.), respectively. And measured.
  • reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g) as a white solid.
  • the main resin component is (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 0.45 (HO 1/2 ) 0.03 (average composition) is there. This corresponds to the component (A) described above.
  • the hardness adjusting agent is ViMe 2 SiO (MePhSiO) 17.5 SiMe 2 Vi (average composition). This corresponds to the component (B) described above.
  • the crosslinker is (HMe 2 SiO) 2 SiPh 2 . This corresponds to the component (C) described above.
  • the reaction inhibitor is 1-ethynylhexanol.
  • the catalyst is a platinum catalyst, and a platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) having a platinum content of 5% by weight is used as the platinum catalyst.
  • the matrix resin used for the production of the phosphor composition was a silicone resin type 1 (Si1).
  • the silicone resin (Si1) used for the preparation of the phosphor composition was prepared as a matrix resin by blending the above silicone components.
  • the resin main component is 16.7 parts by weight
  • the hardness adjusting agent is 16.7 parts by weight
  • the crosslinking agent is 66.7 parts by weight
  • the reaction inhibitor is 0.025 parts by weight.
  • Parts and the platinum catalyst is 0.03 parts by weight.
  • epoxy resin type 1 (EP1) specifically, “CELVENUS W0910 (A liquid, B liquid)” (manufactured by Daicel Corporation) was used.
  • the prepared phosphor composition is a package frame (manufactured by Enomoto Co., Ltd.) on which an LED chip (“GM2QT450G” manufactured by Showa Denko KK, average wavelength: 453.4 nm) is mounted.
  • An LED package was manufactured by pouring into a frame “TOP LED BASE” using a dispenser (“MPP-1” manufactured by Musashino Engineering Co., Ltd.) and curing at 80 ° C. for 1 hour and 150 ° C. for 2 hours.
  • LED package manufacturing method-2 In LED package manufacturing method-2 in the example, the produced phosphor sheet of 5 cm square was cut by a cutting device (GCUT manufactured by UHT) to produce 100 phosphor sheets of 1 mm square pieces. Using a die bonding apparatus (manufactured by Toray Engineering), the phosphor layer cut into 1 mm square was vacuum-adsorbed with a collet and peeled from the substrate. This was aligned and affixed to the surface of the light emitting element of the LED package in which the flip chip type blue LED light emitting element was mounted and the reflector was formed around the light emitting element.
  • GCUT manufactured by UHT
  • the phosphor layer cut into 1 mm square was vacuum-adsorbed with a collet and peeled from the substrate. This was aligned and affixed to the surface of the light emitting element of the LED package in which the flip chip type blue LED light emitting element was mounted and the reflector was formed around the light emitting element.
  • an adhesive was applied in advance on the flip chip type blue LED light emitting element, and a phosphor layer was attached via the adhesive.
  • a silicone resin (OE6630) was used as the adhesive.
  • the obtained light emitting device was connected to a direct current power source and turned on, and it was confirmed that the light emitting device was turned on.
  • the manufactured LED package is powered on by turning on the LED element, and using the total luminous flux measurement system (HM-3000, manufactured by Otsuka Electronics Co., Ltd.), the chromaticity (Cx, Cy) of the CIE1931 XYZ color system and The emission spectrum was measured. Further, the total luminous flux (lm) was measured, and the relative luminance when the total luminous flux in Comparative Example 1 described later was set to 100 was described in Table 1 described later (in the case of a phosphor sheet, Comparative Example 5 described later). The total luminous flux at 100 was taken as 100).
  • HM-3000 manufactured by Otsuka Electronics Co., Ltd.
  • B indicates that the total luminous flux retention is 86% or more and 90% or less, and “durability is good”.
  • C indicates that the total luminous flux retention is 81% or more and 85% or less, and “durability is not a problem in practice”.
  • D indicates that the total luminous flux retention is 80% or less and “durability is poor”.
  • Example 1 In Example 1, using a polyethylene container having a volume of 100 ml, 16.0 g of type 1 silicone resin (Si1) as a matrix resin, and 8.0 g of type 1 YAG phosphor (YAG1) as an inorganic phosphor, As the organic light emitting material, 1.24 ⁇ 10 ⁇ 3 g of the organic light emitting material (type 21) of Synthesis Example 1 was added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, the mixture was stirred and defoamed at 1000 rpm for 5 minutes to prepare a phosphor composition (type 1).
  • Si1 type 1 silicone resin
  • YAG1 type 1 YAG phosphor
  • Comparative Example 1 In Comparative Example 1, a phosphor composition (type 12) was prepared in the same manner as in Example 1 except that no organic light emitting material was added. Thereafter, using the phosphor composition (type 12), an LED package was produced in the same manner as in Example 1, and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 1, the durability was improved, but the color reproducibility was not improved.
  • Comparative Example 2 In Comparative Example 2, the same operation as in Example 1 was performed except that the organic light-emitting material (type 27) represented by the following general formula was used instead of the organic light-emitting material (type 21) of Synthesis Example 1.
  • a phosphor composition (type 13) was prepared. Thereafter, using the phosphor composition (type 13), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 2, neither color reproducibility nor durability was improved.
  • Comparative Example 3 a phosphor composition (Type 14) was prepared in the same manner as in Example 1 except that 20 g of Type 1 KSF phosphor (KSF1) was added instead of the organic light emitting material. Thereafter, using the phosphor composition (type 14), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 3, the durability was improved, but the color reproducibility was not improved.
  • Comparative Example 4 a phosphor composition (Type 15) was prepared in the same manner as in Comparative Example 2, except that an organic light-emitting material (Type 28) represented by the following general formula was used instead of the inorganic phosphor. Was made. Thereafter, using the phosphor composition (type 15), an LED package was produced in the same manner as in Comparative Example 2, and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 4, the color reproducibility was slightly improved, but the durability was not improved.
  • Example 2 to 10 a phosphor composition (type 2 to type 10) was prepared in the same manner as in Example 1 except that the inorganic phosphor and the organic light emitting material were appropriately changed as shown in Table 1 described later. Each was produced. Thereafter, using each of the phosphor compositions (type 2 to type 10), an LED package was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below. As shown in Table 1, from the evaluation results of Examples 2 to 10, it was found that the color reproducibility was improved with the phosphor composition according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
  • Example 11 In Example 11, a phosphor composition (type 11) was prepared in the same manner as in Example 1 except that the inorganic phosphor, the organic light emitting material, and the matrix resin were changed as shown in Table 1. Thereafter, using the phosphor composition (type 11), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1. As shown in Table 1, it was found from the evaluation results of Example 11 that the color reproducibility is improved with the phosphor composition according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
  • Example 12 In Example 12, using a polyethylene container having a volume of 100 ml, 16.0 g of type 1 silicone resin (Si1) as a matrix resin, and 8.0 g of type 1 YAG phosphor (YAG1) as an inorganic phosphor, As an organic light emitting material, 1.24 ⁇ 10 ⁇ 3 g of the organic light emitting material (type 21) of Synthesis Example 1 was added and mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming device to prepare a phosphor composition (type 1).
  • Si1 type 1 silicone resin
  • YAG1 type 1 YAG phosphor
  • Example 12 a phosphor composition (type 1) was formed on a release treatment surface of “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 ⁇ m) using a slit die coater. And heated and dried at 120 ° C. for 30 minutes to obtain an 80 ⁇ m, 100 mm square phosphor sheet (type 31). Using a phosphor sheet (type 31), an LED package was produced by the method described above, and chromaticity, total luminous flux, and total luminous flux maintenance factor were measured. The results of relative luminance, color reproducibility and durability are shown in Table 2 below. As shown in Table 2, there was no change in the relative luminance, but a result with good color reproducibility and good durability was obtained.
  • Comparative Example 5 In Comparative Example 5, a phosphor composition (type 12) was produced in the same manner as in Example 12 except that no organic light emitting material was added. Then, after producing a phosphor sheet (type 44) using the phosphor composition (type 12) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 44) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 5, the durability was improved, but the color reproducibility was not improved.
  • Comparative Example 6 a phosphor composition (type 13) was prepared in the same manner as in Example 12 except that an organic light emitting material (type 27) was used instead of the organic light emitting material (type 21). Then, after producing a phosphor sheet (type 45) using the phosphor composition (type 13) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 45) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 6, neither color reproducibility nor durability was improved.
  • Comparative Example 7 a phosphor composition (Type 14) was produced in the same manner as in Example 12 except that 20 g of Type 1 KSF phosphor (KSF1) was added instead of the organic light emitting material. Then, after producing a phosphor sheet (type 46) using the phosphor composition (type 14) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 46) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 7, the durability was improved, but the color reproducibility was not improved.
  • KSF1 Type 1 KSF phosphor
  • Comparative Example 8 In Comparative Example 8, a phosphor composition (Type 15) was prepared in the same manner as in Comparative Example 6, except that an organic light emitting material (Type 28) was used instead of the inorganic phosphor. Then, after producing a phosphor sheet (type 47) using the phosphor composition (type 15) in the same manner as in Comparative Example 6, an LED package is produced using the phosphor sheet (type 47) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 8, the color reproducibility was slightly improved, but the durability was not improved.
  • Example 13 to 21 In Examples 13 to 21, a phosphor composition (type 2 to type 10) was prepared in the same manner as in Example 12 except that the inorganic phosphor and the organic light emitting material were appropriately changed as shown in Table 2 below. Each was produced. Thereafter, a phosphor sheet (type 32 to type 40) was prepared in the same manner as in Example 12 using each phosphor composition (type 2 to type 10), and then phosphor sheet (type 32 to type 40). An LED package was fabricated using each of these and evaluated. The results are shown in Table 2 below. As shown in Table 2, from the evaluation results of Examples 13 to 21, it was found that the color reproducibility was improved with the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
  • Example 22 In Example 22, a phosphor composition (type 11) was produced in the same manner as in Example 12 except that the inorganic phosphor, the organic light emitting material, and the matrix resin were changed as shown in Table 2. Then, after producing a phosphor sheet (type 41) using the phosphor composition (type 11) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 41) and evaluated. Went. The results are shown in Table 2. As shown in Table 2, it was found from the evaluation results of Example 22 that the color reproducibility is improved if the phosphor sheet according to the embodiment of the present invention is used. Moreover, it turned out that durability is also favorable.
  • Example 23 In Example 23, as shown below, a phosphor composition (type 16) and an organic light emitting material composition (type 16) were prepared, and using these, a phosphor sheet (type) that was a two-layer phosphor sheet 42) was manufactured, and then an LED package was manufactured using a phosphor sheet (type 42) and evaluated.
  • Si1 type 1 silicone resin
  • ⁇ 3 type 3 ⁇ -sialon phosphor
  • the phosphor composition (type 16) was applied onto a release treatment surface of “Therapy” BX9 (produced by Toray Film Processing Co., Ltd., average film thickness 50 ⁇ m) as a base material. It was heated and dried at 0 ° C. for 30 minutes to obtain an 80 ⁇ m, 100 mm square phosphor layer.
  • An organic light emitting material composition (type 16) was applied on the obtained phosphor layer using a slit die coater. Then, it heated and dried at 120 degreeC for 30 minute (s), the organic light emitting material layer of 50 micrometers and a 100 mm square was formed, and the fluorescent substance sheet (type 42) was obtained.
  • Example 23 The evaluation results of Example 23 are shown in Table 2. As shown in Table 2, from the evaluation result of Example 23, it was found that the color reproducibility was improved if the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
  • Example 24 In Example 24, as shown below, a phosphor composition (type 17) and an organic light-emitting material composition (type 17) were prepared, and using these, a phosphor sheet (type) that is a two-layer phosphor sheet 43), and then an LED package was prepared using a phosphor sheet (type 43) and evaluated.
  • phosphor composition (type 17) Using a polyethylene container with a volume of 100 ml, add 15.0 g of type 1 silicone resin (Si1) as a matrix resin, 20 g of type 2 KSF phosphor (KSF2) as an inorganic phosphor, and 5 g of butyl carbitol. And mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming device, and then a phosphor composition (type 17) was produced.
  • Si1 type 1 silicone resin
  • KSF2 type 2 KSF phosphor
  • the phosphor composition (type 17) was applied onto a release treatment surface of “THERAPY” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 ⁇ m) as a base material. It was heated and dried at 0 ° C. for 30 minutes to obtain an 80 ⁇ m, 100 mm square phosphor layer.
  • An organic light emitting material composition (type 17) was applied onto the obtained phosphor layer using a slit die coater. Then, it heated and dried at 120 degreeC for 30 minute (s), the organic light emitting material layer of 50 micrometers and a 100 mm square was formed, and the fluorescent substance sheet (type 43) was obtained.
  • Example 24 The evaluation results of Example 24 are shown in Table 2. As shown in Table 2, from the evaluation results of Example 24, it was found that the color reproducibility was improved if the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
  • the phosphor composition according to the present invention, the phosphor sheet, and the formed article using them, the LED chip, the LED package, the light emitting device, the backlight unit, the display, and the manufacturing method of the LED package have high color reproduction.
  • a phosphor composition, a phosphor sheet, a phosphor formed product, an LED chip, an LED package, a light emitting device, a backlight unit, and a display that satisfy both the properties and the high durability.

Abstract

Provided are: a phosphor composition containing an organic compound represented by general formula (1), an inorganic phosphor, and a matrix resin; and a phosphor sheet. In the formula, R1, R2, Ar1 through Ar5, and L are selected from among hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, arylether, arylthioether, aryl, heteroaryl, heterocyclic, halogen, haloakyl, haloalkenyl, haloalkynyl, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, and siloxanyl groups, and a condensed ring and aliphatic ring formed between adjacent substituents. In the formula, M represents an m-valent metal, and is at least one species selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum.

Description

蛍光体組成物、蛍光体シート並びにそれらを用いた形成物、ＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニット、ディスプレイおよびＬＥＤパッケージの製造方法Phosphor composition, phosphor sheet and formed article using them, LED chip, LED package, light emitting device, backlight unit, display, and method for producing LED package
　本発明は、蛍光体組成物、蛍光体シート並びにそれらを用いた形成物、ＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニット、ディスプレイおよびＬＥＤパッケージの製造方法に関する。 The present invention relates to a phosphor composition, a phosphor sheet, and a formed article using them, an LED chip, an LED package, a light emitting device, a backlight unit, a display, and an LED package manufacturing method.
　色変換方式によるマルチカラー化技術は、液晶ディスプレイや有機ＥＬディスプレイ、照明などへの応用が盛んに検討されている。色変換とは、発光体からの発光をより長波長な光へと変換することであり、例えば青色発光を緑色発光や赤色発光へと変換することを表す。この色変換機能を有する組成物が蛍光体組成物であり、蛍光体組成物をフィルム化したものが蛍光体シートである。この蛍光体シートを例えば青色光源と組み合わせることにより、青色光源から、青色、緑色、赤色の３原色を取り出すこと、すなわち白色光を取り出すことが可能となる。このような青色光源と蛍光体シートとを組み合わせた白色光源をバックライトユニットとし、このバックライトユニットと、液晶駆動部分と、カラーフィルターとを組み合わせることで、フルカラーディスプレイの作製が可能になる。また、液晶駆動部分が無ければ、そのまま白色光源として用いることができ、例えばＬＥＤ照明などの白色光源として応用できる。 Multi-color technology based on color conversion is being actively studied for application to liquid crystal displays, organic EL displays, and lighting. Color conversion refers to conversion of light emitted from a light emitter into light having a longer wavelength, and represents, for example, conversion of blue light emission into green light emission or red light emission. The composition having this color conversion function is a phosphor composition, and the phosphor sheet is a phosphor sheet. By combining this phosphor sheet with, for example, a blue light source, it is possible to extract three primary colors of blue, green, and red from the blue light source, that is, to extract white light. A white light source combining such a blue light source and a phosphor sheet is used as a backlight unit, and a combination of this backlight unit, a liquid crystal driving portion, and a color filter makes it possible to produce a full color display. Moreover, if there is no liquid crystal drive part, it can be used as a white light source as it is, for example, it can be applied as a white light source such as LED lighting.
　液晶ディスプレイの課題として、色再現性の向上が挙げられる。色再現性の向上には、バックライトユニットの青、緑、赤の各発光スペクトルの半値幅を狭くし、青、緑、赤の各色の色純度を高めることが有効である。これを解決する手段として、無機半導体微粒子による量子ドットを蛍光体組成物の成分として用いる技術が提案されている（例えば、特許文献１参照）。これら量子ドットを用いる技術では、確かに緑色、赤色の発光スペクトルの半値幅が狭く、色再現性は向上するが、反面、量子ドットは熱、空気中の水分や酸素に弱く、耐久性が十分でなかった。 An improvement in color reproducibility is an issue with liquid crystal displays. In order to improve color reproducibility, it is effective to increase the color purity of each color of blue, green and red by narrowing the half width of each emission spectrum of blue, green and red of the backlight unit. As means for solving this problem, a technique using quantum dots made of inorganic semiconductor fine particles as a component of a phosphor composition has been proposed (for example, see Patent Document 1). With these quantum dot technologies, the half-value widths of the green and red emission spectra are certainly narrow and the color reproducibility is improved. On the other hand, the quantum dots are weak against heat, moisture and oxygen in the air, and have sufficient durability. It was not.
　また、量子ドットの代わりに有機物の発光材料を蛍光体組成物の成分として用いる技術も提案されている。有機発光材料を蛍光体組成物の成分として用いる技術の例としては、ピリジン－フタルイミド縮合体を用いたもの（例えば、特許文献２参照）、クマリン誘導体を用いたもの（例えば、特許文献３参照）、赤色発光材料についてはこれまでペリレン誘導体を用いたもの（例えば、特許文献４参照）、ローダミン誘導体を用いたもの（例えば、特許文献５参照）、ピロメテン誘導体を用いたもの（例えば、特許文献６～７参照）が開示されている。 Also, a technique has been proposed in which an organic light emitting material is used as a component of the phosphor composition instead of quantum dots. Examples of techniques using an organic light-emitting material as a component of a phosphor composition include those using a pyridine-phthalimide condensate (for example, see Patent Document 2) and those using a coumarin derivative (for example, see Patent Document 3). As for the red light emitting material, those using a perylene derivative so far (for example, see Patent Document 4), those using a rhodamine derivative (for example, see Patent Document 5), those using a pyromethene derivative (for example, Patent Document 6) To 7).
特開２０１２－２２０２８号公報JP 2012-22028 A 特開２００２－３４８５６８号公報JP 2002-348568 A 特開２００７－２７３４４０号公報JP 2007-273440 A 特開２００２－３１７１７５号公報JP 2002-317175 A 特開２００１－１６４２４５号公報JP 2001-164245 A 特開２０１１－２４１１６０号公報JP 2011-241160 A 特開２０１４－１３６７７１号公報Japanese Patent Application Laid-Open No. 2014-136771
　しかしながら、上述した従来の有機発光材料は、液晶ディスプレイ等に使用した場合、色再現性及び耐久性について未だ不十分であった。本発明は、上記課題に鑑みてなされたものであって、その目的は、液晶ディスプレイやＬＥＤ照明等に用いられる蛍光体組成物、蛍光体シートにおいて、高色再現性及び高耐久性を両立させることである。 However, the conventional organic light emitting materials described above are still insufficient in terms of color reproducibility and durability when used in liquid crystal displays and the like. This invention is made | formed in view of the said subject, The objective is to make high color reproducibility and high durability compatible in the fluorescent substance composition and fluorescent substance sheet which are used for a liquid crystal display, LED lighting, etc. That is.
　上述した課題を解決し、目的を達成するために、本発明に係る蛍光体組成物は、発光体からの発光光を該発光光よりも長波長の光へ変換する、一般式（１）で表される有機化合物および無機蛍光体と、前記有機化合物および前記無機蛍光体と混合して連続相を形成するマトリックス樹脂と、を含有することを特徴とする。 In order to solve the above-described problems and achieve the object, the phosphor composition according to the present invention converts the light emitted from the light emitter to light having a longer wavelength than the light emitted by the general formula (1). An organic compound and an inorganic phosphor that are represented, and a matrix resin that is mixed with the organic compound and the inorganic phosphor to form a continuous phase.
Figure JPOXMLDOC01-appb-C000007
 （Ｒ1、Ｒ2、Ａｒ1～Ａｒ5およびＬは同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、複素環基、ハロゲン、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ｍはｍ価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金から選ばれる少なくとも一種である。）
Figure JPOXMLDOC01-appb-C000007
 (R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from beryllium, magnesium, chromium, iron, nickel, copper, zinc, platinum It is also a kind.)
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ｍがホウ素であり、Ｌがフッ素または含フッ素アリール基であり、ｍ－１が２であることを特徴とする。 In the phosphor composition according to the present invention, in the above invention, in the general formula (1) representing the organic compound, M is boron, L is fluorine or a fluorine-containing aryl group, and m−1 is 2 is a feature.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ5が一般式（２）で表される基であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, Ar 5 in the general formula (1) representing the organic compound is a group represented by the general formula (2).
Figure JPOXMLDOC01-appb-C000008
 （ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基からなる群より選ばれる。ｋは１～３の整数である。ｋが２以上である場合、ｒはそれぞれ同じでも異なってもよい。）
Figure JPOXMLDOC01-appb-C000008
 (R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のフェニル基であることを特徴とする。 In the phosphor composition according to the present invention, in the above invention, Ar 1 to Ar 4 in the general formula (1) representing the organic compound may be the same or different, and may be substituted or unsubstituted. It is a phenyl group.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1～Ａｒ4のうち少なくとも一つが、一般式（３）で表される基であることを特徴とする。 In the phosphor composition according to the present invention, in the above invention, at least one of Ar 1 to Ar 4 in the general formula (1) representing the organic compound is a group represented by the general formula (3). It is characterized by being.
Figure JPOXMLDOC01-appb-C000009
 （Ｒ3はアルキル基、シクロアルキル基、アルコキシ基およびアルキルチオ基からなる群より選ばれる。ｎは１～３の整数である。ｎが２以上の場合、各Ｒ3は同じでも異なってもよい。）
Figure JPOXMLDOC01-appb-C000009
 (R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .)
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1とＡｒ2とが異なる構造の基である、または、Ａｒ3とＡｒ4とが異なる構造の基であることを特徴とする。 In the phosphor composition according to the present invention, in the above invention, Ar 1 and Ar 2 in the general formula (1) representing the organic compound are groups having different structures, or Ar 3 and Ar 4 And is a group having a different structure.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする。 In the phosphor composition according to the present invention, in the above invention, Ar 1 to Ar 4 in the general formula (1) representing the organic compound may be the same or different, and may be substituted or unsubstituted. It is an alkyl group.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is hydrogen.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物を表す一般式（１）における、Ｒ1およびＲ２のうち少なくとも一つが電子吸引基であることを特徴とする。 Moreover, the phosphor composition according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is an electron withdrawing group.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記有機化合物のＡｒ5を表す一般式（２）における、ｒが電子吸引基であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, r in the general formula (2) representing Ar 5 of the organic compound is an electron withdrawing group.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記無機蛍光体の発光スペクトルが５００～７００ｎｍの領域にピークを有することを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記無機蛍光体がβ型サイアロン蛍光体であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a β-type sialon phosphor.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記β型サイアロン蛍光体の発光スペクトルが５３５～５５０ｎｍの領域にピークを有することを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the emission spectrum of the β-type sialon phosphor has a peak in the region of 535 to 550 nm.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記β型サイアロン蛍光体の平均粒径が１６μｍ以上、１９μｍ以下であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the β-sialon phosphor has an average particle size of 16 μm or more and 19 μm or less.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記無機蛍光体がＫＳＦ蛍光体であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a KSF phosphor.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記ＫＳＦ蛍光体の平均粒径が１０μｍ以上、４０μｍ以下であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the KSF phosphor has an average particle size of 10 μm or more and 40 μm or less.
　また、本発明に係る蛍光体組成物は、上記の発明において、前記マトリックス樹脂がシリコーン樹脂であることを特徴とする。 The phosphor composition according to the present invention is characterized in that, in the above invention, the matrix resin is a silicone resin.
　また、本発明に係る蛍光体シートは、発光体からの発光光を該発光光よりも長波長の光へ変換する、一般式（１）で表される有機化合物および無機蛍光体と、少なくとも前記無機蛍光体と混合して連続相を形成するマトリックス樹脂と、を含有することを特徴とする。 In addition, the phosphor sheet according to the present invention includes an organic compound represented by the general formula (1) and an inorganic phosphor, which converts light emitted from a light emitter into light having a longer wavelength than the light emitted; And a matrix resin that forms a continuous phase by mixing with an inorganic phosphor.
Figure JPOXMLDOC01-appb-C000010
 （Ｒ1、Ｒ2、Ａｒ1～Ａｒ５およびＬは同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、複素環基、ハロゲン、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ｍはｍ価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金から選ばれる少なくとも一種である。）
Figure JPOXMLDOC01-appb-C000010
 (R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from beryllium, magnesium, chromium, iron, nickel, copper, zinc, platinum Both are also a kind.)
　また、本発明に係る蛍光体シートは、上記の発明において、前記無機蛍光体と前記マトリックス樹脂とを含有する蛍光体層と、一般式（１）で表される前記有機化合物を含有する有機発光材料層との積層構造を含むことを特徴とする。 In addition, the phosphor sheet according to the present invention is the above-described invention, wherein the phosphor layer includes the inorganic phosphor and the matrix resin, and the organic light emitting material includes the organic compound represented by the general formula (1). It includes a laminated structure with a material layer.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ｍがホウ素であり、Ｌがフッ素または含フッ素アリール基であり、ｍ－１が２であることを特徴とする。 In the phosphor sheet according to the present invention, in the above invention, in the general formula (1) representing the organic compound, M is boron, L is fluorine or a fluorine-containing aryl group, and m−1 is 2 It is characterized by being.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ5が一般式（２）で表される基であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, Ar 5 in the general formula (1) representing the organic compound is a group represented by the general formula (2).
Figure JPOXMLDOC01-appb-C000011
 （ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基からなる群より選ばれる。ｋは１～３の整数である。ｋが２以上である場合、ｒはそれぞれ同じでも異なってもよい。）
Figure JPOXMLDOC01-appb-C000011
 (R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のフェニル基であることを特徴とする。 In the phosphor sheet according to the present invention, in the above-described invention, in the general formula (1) representing the organic compound, Ar 1 to Ar 4 may be the same or different, and substituted or unsubstituted phenyl It is a group.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1～Ａｒ4のうち少なくとも一つが、一般式（３）で表される基であることを特徴とする。 In the phosphor sheet according to the present invention, in the above invention, at least one of Ar 1 to Ar 4 in the general formula (1) representing the organic compound is a group represented by the general formula (3). It is characterized by being.
Figure JPOXMLDOC01-appb-C000012
 （Ｒ3はアルキル基、シクロアルキル基、アルコキシ基およびアルキルチオ基からなる群より選ばれる。ｎは１～３の整数である。ｎが２以上の場合、各Ｒ3は同じでも異なってもよい。）
Figure JPOXMLDOC01-appb-C000012
 (R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .)
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1とＡｒ2とが異なる構造の基である、または、Ａｒ3とＡｒ4とが異なる構造の基であることを特徴とする。 In the phosphor sheet according to the present invention, in the above invention, Ar 1 and Ar 2 in the general formula (1) representing the organic compound are groups having different structures, or Ar 3 and Ar 4 Are groups having different structures.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする。 In the phosphor sheet according to the present invention, Ar 1 to Ar 4 in the general formula (1) representing the organic compound in the above invention may be the same or different from each other, and may be substituted or unsubstituted alkyl. It is a group.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is hydrogen.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物を表す一般式（１）における、Ｒ1およびＲ2のうち少なくとも一つが電子吸引基であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, at least one of R 1 and R 2 in the general formula (1) representing the organic compound is an electron withdrawing group.
　また、本発明に係る蛍光体シートは、上記の発明において、前記有機化合物のＡｒ5を表す一般式（２）における、ｒが電子吸引基であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, r in the general formula (2) representing Ar 5 of the organic compound is an electron withdrawing group.
　また、本発明に係る蛍光体シートは、上記の発明において、前記無機蛍光体の発光スペクトルが５００～７００ｎｍの領域にピークを有することを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
　また、本発明に係る蛍光体シートは、上記の発明において、前記無機蛍光体がβ型サイアロン蛍光体であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a β-type sialon phosphor.
　また、本発明に係る蛍光体シートは、上記の発明において、前記β型サイアロン蛍光体の発光スペクトルが５３５～５５０ｎｍの領域にピークを有することを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the emission spectrum of the β-sialon phosphor has a peak in the region of 535 to 550 nm.
　また、本発明に係る蛍光体シートは、上記の発明において、前記β型サイアロン蛍光体の平均粒径が１６μｍ以上、１９μｍ以下であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, the β-sialon phosphor has an average particle diameter of 16 μm or more and 19 μm or less.
　また、本発明に係る蛍光体シートは、上記の発明において、前記無機蛍光体がＫＳＦ蛍光体であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, the inorganic phosphor is a KSF phosphor.
　また、本発明に係る蛍光体シートは、上記の発明において、前記ＫＳＦ蛍光体の平均粒径が１０μｍ以上、４０μｍ以下であることを特徴とする。 Further, the phosphor sheet according to the present invention is characterized in that, in the above invention, the KSF phosphor has an average particle size of 10 μm or more and 40 μm or less.
　また、本発明に係る蛍光体シートは、上記の発明において、前記マトリックス樹脂がシリコーン樹脂であることを特徴とする。 The phosphor sheet according to the present invention is characterized in that, in the above invention, the matrix resin is a silicone resin.
　また、本発明に係る形成物は、上記の発明のいずれか一つに記載の蛍光体組成物またはその硬化物を含有することを特徴とする。 The formed product according to the present invention is characterized by containing the phosphor composition according to any one of the above inventions or a cured product thereof.
　また、本発明に係るＬＥＤチップは、上記の発明のいずれか一つに記載の蛍光体シートまたはその硬化物を発光面に備えることを特徴とする。 Further, an LED chip according to the present invention is characterized in that the phosphor sheet according to any one of the above inventions or a cured product thereof is provided on a light emitting surface.
　また、本発明に係るＬＥＤパッケージは、上記の発明のいずれか一つに記載の蛍光体組成物の硬化物を備えることを特徴とする。 Further, an LED package according to the present invention includes a cured product of the phosphor composition according to any one of the above-described inventions.
　また、本発明に係るＬＥＤパッケージは、上記の発明のいずれか一つに記載の蛍光体シートまたはその硬化物を備えることを特徴とする。 Further, an LED package according to the present invention includes the phosphor sheet according to any one of the above inventions or a cured product thereof.
　また、本発明に係るＬＥＤパッケージの製造方法は、上記の発明のいずれか一つに記載の蛍光体組成物を用いたＬＥＤパッケージの製造方法であって、ＬＥＤチップが設置されているパッケージフレームに前記蛍光体組成物を注入する注入工程と、前記注入工程の後、封止材で前記ＬＥＤチップを封止する封止工程と、を少なくとも含むことを特徴とする。 Moreover, the manufacturing method of the LED package which concerns on this invention is a manufacturing method of the LED package using the fluorescent substance composition as described in any one of said invention, Comprising: On the package frame in which the LED chip is installed It includes at least an injection step of injecting the phosphor composition and a sealing step of sealing the LED chip with a sealing material after the injection step.
　また、本発明に係るＬＥＤパッケージの製造方法は、上記の発明のいずれか一つに記載の蛍光体シートを用いたＬＥＤパッケージの製造方法であって、複数の区画に分割された状態にある前記蛍光体シートの一の区画を、一のＬＥＤチップの発光面に対向させる位置合わせ工程と、対向させた前記蛍光体シートの前記一の区画と前記一のＬＥＤチップの発光面とを、加熱圧着ツールにより加熱しながら加圧して接着する接着工程と、を少なくとも含むことを特徴とする。 Moreover, the manufacturing method of the LED package which concerns on this invention is a manufacturing method of the LED package using the fluorescent substance sheet as described in any one of said invention, Comprising: Said state in the state divided | segmented into several divisions An alignment step in which one section of the phosphor sheet faces the light emitting surface of one LED chip, and the one section of the phosphor sheet and the light emitting surface of the one LED chip opposed to each other are thermocompression bonded. And a bonding step of pressing and bonding while heating with a tool.
　また、本発明に係る発光装置は、上記の発明に記載の形成物と、前記形成物に含まれる蛍光体組成物によって発光光が色変換される発光体であるＬＥＤチップを有するＬＥＤパッケージと、を備えることを特徴とする。 Further, a light-emitting device according to the present invention includes an LED package having an LED chip that is a light-emitting body in which emitted light is color-converted by a phosphor composition included in the above-described invention, and a phosphor composition included in the formation; It is characterized by providing.
　また、本発明に係るバックライトユニットは、上記の発明のいずれか一つに記載のＬＥＤパッケージを含むことを特徴とする。 Further, a backlight unit according to the present invention includes the LED package according to any one of the above inventions.
　また、本発明に係るバックライトユニットは、上記の発明のいずれか一つに記載のＬＥＤパッケージを含むことを特徴とする。 Further, a backlight unit according to the present invention includes the LED package according to any one of the above inventions.
　本発明によれば、高色再現性及び高耐久性を双方とも満足する蛍光体組成物および蛍光体シートを提供することができるという効果を奏する。本発明に係る蛍光体組成物または蛍光体シートを備えるＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニット、およびディスプレイは、高色再現性及び高耐久性を両立させることができるという効果を奏する。 According to the present invention, it is possible to provide a phosphor composition and a phosphor sheet that satisfy both high color reproducibility and high durability. The LED chip, the LED package, the light emitting device, the backlight unit, and the display including the phosphor composition or the phosphor sheet according to the present invention have an effect that both high color reproducibility and high durability can be achieved.
図１は、本発明の実施の形態に係る蛍光体シートの一例を示す側面図である。FIG. 1 is a side view showing an example of a phosphor sheet according to an embodiment of the present invention. 図２は、本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの製造方法の一例を示す図である。FIG. 2 is a diagram showing an example of a method for manufacturing an LED package using the phosphor composition according to the embodiment of the present invention. 図３Ａは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの一例を示す図である。FIG. 3A is a diagram showing an example of an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. 図３Ｂは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの別例を示す図である。FIG. 3B is a diagram showing another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. 図３Ｃは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの更なる別例を示す図である。FIG. 3C is a diagram showing still another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. 図４Ａは、本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの一例を示す図である。FIG. 4A is a diagram showing an example of an LED package using the phosphor composition according to the embodiment of the present invention. 図４Ｂは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例１を示す図である。FIG. 4B is a diagram showing Example 1 of an LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｃは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例２を示す図である。FIG. 4C is a diagram showing an example 2 of the LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｄは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例３を示す図である。FIG. 4D is a diagram showing an example 3 of the LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｅは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例４を示す図である。FIG. 4E is a diagram showing Example 4 of an LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｆは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例５を示す図である。FIG. 4F is a diagram illustrating Example 5 of the LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｇは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例６を示す図である。FIG. 4G is a diagram showing Example 6 of an LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｈは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例７を示す図である。FIG. 4H is a diagram illustrating Example 7 of an LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｉは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例８を示す図である。FIG. 4I is a diagram showing Example 8 of an LED package using the phosphor sheet according to the embodiment of the present invention. 図４Ｊは、本発明の実施の形態に係る蛍光体組成物を使用した形成物を用いたＬＥＤパッケージの一例を示す図である。FIG. 4J is a diagram showing an example of an LED package using a formed article using the phosphor composition according to the embodiment of the present invention. 図５は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の一例を示す図である。FIG. 5 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention. 図６は、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの製造方法の一例を示す図である。FIG. 6 is a diagram illustrating an example of a method of manufacturing an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. 図７は、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの製造方法の別例を示す図である。FIG. 7 is a diagram showing another example of the method for manufacturing the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. 図８は、本発明の実施の形態に係る蛍光体シートの貼り付け方法の一例を示す図である。FIG. 8 is a diagram showing an example of a phosphor sheet attaching method according to the embodiment of the present invention. 図９は、本発明の実施の形態に係る蛍光体シートの貼り付け方法の別例を示す図である。FIG. 9 is a diagram showing another example of the phosphor sheet attaching method according to the embodiment of the present invention. 図１０は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の一例を示す図である。FIG. 10 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention. 図１１は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の別例を示す図である。FIG. 11 is a diagram showing another example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
　以下、本発明に係る蛍光体組成物、蛍光体シート並びにそれらを用いた形成物、ＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニットおよびＬＥＤパッケージの製造方法の好適な実施の形態を詳細に説明する。ただし、本発明は、以下の実施の形態に限定されるものではなく、目的や用途に応じて種々に変更して実施することができる。 Hereinafter, preferred embodiments of a phosphor composition, a phosphor sheet and a formed article using them, an LED chip, an LED package, a light emitting device, a backlight unit, and an LED package manufacturing method according to the present invention will be described in detail. To do. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application.
＜蛍光体組成物＞
　本発明の一つの実施形態である蛍光体組成物は、一般式（１）で表される有機化合物および無機蛍光体と、マトリックス樹脂とを含有する。本実施の形態において、この有機化合物は有機物の発光材料（すなわち有機発光材料）であり、これらの有機化合物および無機蛍光体は、各々、発光体から発光された光（発光光）をこの発光光よりも長波長の光へ変換するものである。また、蛍光体組成物に含有のマトリックス樹脂は、これらの有機化合物および無機蛍光体と混合して連続相を形成する樹脂である。 <Phosphor composition>
The phosphor composition which is one embodiment of the present invention contains an organic compound and an inorganic phosphor represented by the general formula (1), and a matrix resin. In this embodiment, the organic compound is an organic light-emitting material (that is, an organic light-emitting material), and these organic compound and inorganic phosphor respectively emit light (emitted light) emitted from the light emitter. The light is converted into light having a longer wavelength. The matrix resin contained in the phosphor composition is a resin that forms a continuous phase by mixing with these organic compounds and inorganic phosphors.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（一般式（１）で表される有機化合物）
　本実施の形態における有機化合物を表す一般式（１）において、Ｒ1、Ｒ2、Ａｒ1～Ａｒ5およびＬは、同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、複素環基、ハロゲン、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ｍは、ｍ価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金から選ばれる少なくとも一種である。上記の全ての基において、水素は重水素であってもよい。このことは、以下に説明する有機化合物またはその部分構造においても同様である。 (Organic compound represented by the general formula (1))
In the general formula (1) representing the organic compound in the present embodiment, R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group. Alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, Haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, condensed ring and aliphatic ring formed between adjacent substituents Chosen from. M represents an m-valent metal and is at least one selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum. In all of the above groups, hydrogen may be deuterium. The same applies to an organic compound or a partial structure thereof described below.
　また、以下の説明において、例えば炭素数６～４０の置換もしくは無置換のアリール基とは、アリール基に置換した置換基に含まれる炭素数も含めて全ての炭素数が６～４０となるアリール基である。炭素数を規定している他の置換基も、これと同様である。 In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl having 6 to 40 carbon atoms in total including the number of carbon atoms contained in the substituent substituted on the aryl group. It is a group. The same applies to other substituents that define the number of carbon atoms.
　また、上記の全ての基において、置換される場合における置換基としては、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基が好ましく、さらには、各置換基の説明において好ましいとする具体的な置換基が好ましい。また、これらの置換基は、さらに上述の置換基により置換されていてもよい。 Moreover, in all the above groups, the substituents in the case of substitution include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl Group and a phosphine oxide group are preferable, and specific substituents that are preferable in the description of each substituent are preferable. Moreover, these substituents may be further substituted with the above-mentioned substituents.
　「置換もしくは無置換の」という場合における「無置換」とは、水素原子または重水素原子が置換したことを意味する。以下に説明する有機化合物またはその部分構造において、「置換もしくは無置換の」という場合についても、上記と同様である。 In the case of “substituted or unsubstituted”, “unsubstituted” means that a hydrogen atom or a deuterium atom is substituted. The same applies to the case of “substituted or unsubstituted” in an organic compound or a partial structure thereof described below.
　また、上記の全ての基のうち、アルキル基とは、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基などの飽和脂肪族炭化水素基を示す。このアルキル基は、さらに置換基を有していても有していなくてもよい。置換されている場合の追加の置換基には特に制限は無く、例えば、アルキル基、アリール基、ヘテロアリール基等を挙げることができ、この点は、以下の記載にも共通する。また、アルキル基の炭素数は特に限定されないが、入手の容易性やコストの点から、好ましくは１以上、２０以下、より好ましくは１以上、８以下の範囲である。 Of all the groups mentioned above, the alkyl group is, for example, a saturated aliphatic group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. A hydrocarbon group is shown. This alkyl group may or may not further have a substituent. There is no restriction | limiting in particular in the additional substituent in the case of being substituted, For example, an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, This point is common also in the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.
　シクロアルキル基とは、例えば、シクロプロピル、シクロヘキシル、ノルボルニル、アダマンチルなどの飽和脂環式炭化水素基を示し、これは置換基を有していても有していなくてもよい。アルキル基部分の炭素数は特に限定されないが、好ましくは、３以上、２０以下の範囲である。 The cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is preferably in the range of 3 or more and 20 or less.
　アラルキル基とは、例えば、ベンジル基、フェニルエチル基などの脂肪族炭化水素を介した芳香族炭化水素基を示す。これらの脂肪族炭化水素と芳香族炭化水素は、いずれも無置換であってもよいし、置換基を有していてもよい。 The aralkyl group is an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. Any of these aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or may have a substituent.
　アルケニル基とは、例えば、ビニル基、アリル基、ブタジエニル基などの二重結合を含む不飽和脂肪族炭化水素基を示し、これは置換基を有していても有していなくてもよい。アルケニル基の炭素数は特に限定されないが、通常、２以上、２０以下の範囲である。 An alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent. Although carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.
　シクロアルケニル基とは、例えば、シクロペンテニル基、シクロペンタジエニル基、シクロヘキセニル基などの二重結合を含む不飽和脂環式炭化水素基を示し、これは置換基を有していても有していなくてもよい。 The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, which may have a substituent. You don't have to.
　アルキニル基とは、例えば、エチニル基などの三重結合を含む不飽和脂肪族炭化水素基を示し、これは置換基を有していても有していなくてもよい。アルキニル基の炭素数は特に限定されないが、通常、２以上、２０以下の範囲である。 The alkynyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. Although carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.
　アルコキシ基とは、例えば、メトキシ基、エトキシ基、プロポキシ基などのエーテル結合を介して脂肪族炭化水素基が結合した官能基を示し、この脂肪族炭化水素基は置換基を有していても有していなくてもよい。アルコキシ基の炭素数は特に限定されないが、好ましくは、１以上、２０以下の範囲である。 The alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent. It may not have. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.
　アルキルチオ基とは、アルコキシ基のエーテル結合の酸素原子が硫黄原子に置換されたものである。アルキルチオ基の炭化水素基は置換基を有していても有していなくてもよい。アルキルチオ基の炭素数は特に限定されないが、通常、１以上、２０以下の範囲である。 The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Usually, it is the range of 1-20.
　アリールエーテル基とは、例えば、フェノキシ基など、エーテル結合を介して芳香族炭化水素基が結合した官能基を示し、芳香族炭化水素基は置換基を有していても有していなくてもよい。アリールエーテル基の炭素数は特に限定されないが、好ましくは、６以上、４０以下の範囲である。 An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Good. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.
　アリールチオエーテル基とは、アリールエーテル基のエーテル結合の酸素原子が硫黄原子に置換されたものである。アリールチオエーテル基における芳香族炭化水素基は置換基を有していても有していなくてもよい。アリールチオエーテル基の炭素数は特に限定されないが、通常、６以上、４０以下の範囲である。 The aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the aryl thioether group may or may not have a substituent. The number of carbon atoms of the arylthioether group is not particularly limited, but is usually in the range of 6 or more and 40 or less.
　アリール基とは、例えば、フェニル基、ナフチル基、ビフェニル基、フルオレニル基、フェナントリル基、トリフェニレニル基、ターフェニル基などの芳香族炭化水素基を示す。アリール基は、置換基を有していても有していなくてもよい。アリール基の炭素数は特に限定されないが、好ましくは、６以上、４０以下の範囲である。 An aryl group refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group, or a terphenyl group. The aryl group may or may not have a substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.
　ヘテロアリール基とは、フラニル基、チオフェニル基、ピリジル基、キノリニル基、ピラジニル基、ピリミニジニル基、トリアジニル基、ナフチリジル基、ベンゾフラニル基、ベンゾチオフェニル基、インドリル基などの炭素以外の原子を一個または複数個環内に有する環状芳香族基を示し、これは無置換でも置換されていてもかまわない。ヘテロアリール基の炭素数は特に限定されないが、好ましくは、２以上、３０以下の範囲である。 A heteroaryl group is one or more atoms other than carbon such as furanyl, thiophenyl, pyridyl, quinolinyl, pyrazinyl, pyrimidinyl, triazinyl, naphthyridyl, benzofuranyl, benzothiophenyl, indolyl, etc. The cyclic aromatic group which has in an individual ring is shown, This may be unsubstituted or substituted. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 or more and 30 or less.
　複素環基とは、例えば、ピラン環、ピペリジン環、環状アミドなどの炭素以外の原子を環内に有する脂肪族環を示し、これは置換基を有していても有していなくてもよい。複素環基の炭素数は特に限定されないが、通常、２以上、２０以下の範囲である。 The heterocyclic group refers to an aliphatic ring having atoms other than carbon, such as a pyran ring, a piperidine ring, and a cyclic amide, in the ring, which may or may not have a substituent. . Although carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-20.
　カルボニル基、カルボキシル基、カルバモイル基は、置換基を有していても有していなくてもよい。ここで、置換基としては、例えばアルキル基、シクロアルキル基、アリール基、ヘテロアリール基などが挙げられ、これら置換基はさらに置換されてもよい。 The carbonyl group, carboxyl group, and carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.
　アミノ基とは、置換もしくは無置換のアミノ基である。アミノ基は、置換基を有していても有していなくてもよく、置換する場合の置換基としては、例えば、アリール基、ヘテロアリール基、直鎖アルキル基、分岐アルキル基などが挙げられる。アリール基、ヘテロアリール基としては、フェニル基、ナフチル基、ピリジル基、キノリニル基が好ましい。これら置換基はさらに置換されてもよい。炭素数は特に限定されないが、好ましくは、２以上、５０以下、より好ましくは、６以上、４０以下、特に好ましくは、６以上、３０以下の範囲である。 An amino group is a substituted or unsubstituted amino group. The amino group may or may not have a substituent. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group. . As the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted. Although carbon number is not specifically limited, Preferably it is 2 or more and 50 or less, More preferably, it is 6 or more and 40 or less, Especially preferably, it is the range of 6 or more and 30 or less.
　ハロゲンとは、フッ素、塩素、臭素またはヨウ素を示す。ハロアルキル基、ハロアルケニル基、ハロアルキニル基とは、例えばトリフルオロメチル基などの、前述のアルキル基、アルケニル基、アルキニル基の一部あるいは全部が、前述のハロゲンで置換されたものを示し、残りの部分は無置換でも置換されていてもよい。また、アルデヒド基、カルボニル基、エステル基、カルバモイル基には、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、複素環などで置換されたものも含まれ、さらに脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、複素環は、無置換でも置換されていてもよい。 Halogen means fluorine, chlorine, bromine or iodine. A haloalkyl group, a haloalkenyl group, or a haloalkynyl group is a group in which a part or all of the aforementioned alkyl group, alkenyl group, or alkynyl group such as a trifluoromethyl group is substituted with the aforementioned halogen, and the rest This part may be unsubstituted or substituted. In addition, the aldehyde group, carbonyl group, ester group, and carbamoyl group include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like. The alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
　シリル基とは、例えば、トリメチルシリル基などのケイ素原子への結合を有する官能基を示し、これは置換基を有していても有していなくてもよい。シリル基の炭素数は特に限定されないが、通常、３以上、２０以下の範囲である。また、ケイ素数は、通常、１以上、６以下である。 The silyl group refers to, for example, a functional group having a bond to a silicon atom such as a trimethylsilyl group, which may or may not have a substituent. Although carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20. The number of silicon is usually 1 or more and 6 or less.
　シロキサニル基とは、例えば、トリメチルシロキサニル基などのエーテル結合を介したケイ素化合物基を示す。ケイ素上の置換基は、さらに置換されてもよい。 Siloxanyl group refers to a silicon compound group via an ether bond such as trimethylsiloxanyl group. Substituents on silicon may be further substituted.
　上述したような一般式（１）で表される有機化合物は、高い蛍光量子収率を示し、かつ、発光スペクトルのピーク半値幅が小さいため、効率的な色変換と高い色純度の双方を達成することができる。 Since the organic compound represented by the general formula (1) as described above exhibits a high fluorescence quantum yield and has a small peak half-value width of the emission spectrum, it achieves both efficient color conversion and high color purity. can do.
　一般式（１）で表される有機化合物における金属錯体の中でも、Ｍがホウ素である錯体は蛍光量子収率が高い点で特に好ましい。さらに、Ｌがフッ素または含フッ素アリール基であり、ｍ－１が２であるフッ化ホウ素錯体が、材料の入手しやすさや、合成の容易さの点で特に好ましい。 Among the metal complexes in the organic compound represented by the general formula (1), a complex in which M is boron is particularly preferable because of high fluorescence quantum yield. Further, a boron fluoride complex in which L is fluorine or a fluorine-containing aryl group and m-1 is 2 is particularly preferable from the viewpoint of easy availability of materials and ease of synthesis.
　また、任意の隣接する２置換基（例えば一般式（１）のＲ1とＡｒ2）が互いに結合して、共役または非共役の縮合環を形成していてもよい。このような縮合環の構成元素としては、炭素以外にも窒素、酸素、硫黄、リンおよびケイ素から選ばれる元素を含んでいてもよい。また、縮合環がさらに別の環と縮合してもよい。 Further, any adjacent two substituents (for example, R 1 and Ar 2 in the general formula (1)) may be bonded to each other to form a conjugated or non-conjugated condensed ring. Such a constituent element of the condensed ring may contain an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon in addition to carbon. Further, the condensed ring may be further condensed with another ring.
　上述したような一般式（１）で表される有機化合物は、適切な置換基を適切な位置に導入することで、発光効率、色純度、熱的安定性、光安定性および分散性などのさまざまな特性および物性を調整することができる。 The organic compound represented by the general formula (1) as described above has a light emitting efficiency, a color purity, a thermal stability, a light stability, a dispersibility and the like by introducing an appropriate substituent at an appropriate position. Various properties and physical properties can be adjusted.
　例えば、一般式（１）で表される有機化合物の耐久性、すなわち、この有機化合物の発光強度の経時的な低下には、置換基Ａｒ5が大きく影響する。具体的には、Ａｒ5が水素である場合、この水素の反応性が高いため、この水素と空気中の水分や酸素とが容易に反応してしまう。このことは、Ａｒ5の分解を引き起こす。また、Ａｒ5が例えばアルキル基のような分子鎖の運動の自由度が大きい置換基である場合は、確かに反応性は低下するが、シート中で有機化合物同士が経時的に凝集し、結果的に濃度消光による発光強度の低下を招く。したがって、Ａｒ5は、剛直であり、かつ運動の自由度が小さく凝集を引き起こしにくい基であることが好ましく、具体的には、置換もしくは無置換のアリール基、または置換もしくは無置換のヘテロアリール基のいずれかであることが好ましい。 For example, the substituent Ar 5 greatly affects the durability of the organic compound represented by the general formula (1), that is, the decrease in the emission intensity of the organic compound over time. Specifically, when Ar 5 is hydrogen, the reactivity of this hydrogen is high, so that this hydrogen and moisture or oxygen in the air easily react. This causes the decomposition of Ar 5 . In addition, when Ar 5 is a substituent having a large degree of freedom of movement of a molecular chain such as an alkyl group, for example, the reactivity is certainly lowered, but the organic compounds aggregate in the sheet over time, and as a result In particular, the emission intensity is reduced due to concentration quenching. Therefore, Ar 5 is preferably a group that is rigid and has a low degree of freedom of movement and is unlikely to cause aggregation. Specifically, it is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It is preferable that it is either.
　より高い蛍光量子収率を与え、より熱分解しづらい点、また光安定性の観点から、Ａｒ5は、置換もしくは無置換のアリール基であることが好ましい。アリール基としては、発光波長を損なわないという観点から、フェニル基、ビフェニル基、ターフェニル基、ナフチル基、フルオレニル基、フェナントリル基、アントラセニル基が好ましい。 Ar 5 is preferably a substituted or unsubstituted aryl group from the viewpoint of giving a higher fluorescence quantum yield, being harder to thermally decompose, and from the viewpoint of light stability. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.
　さらに、上記有機化合物の光安定性を高めるためには、Ａｒ5とピロメテン骨格の炭素－炭素結合のねじれを適度に抑える必要がある。何故ならば、過度にねじれが大きいと、励起光に対する反応性が高まるなど、光安定性が低下するからである。このような観点から、Ａｒ5としては、置換もしくは無置換のフェニル基、置換もしくは無置換のビフェニル基、置換もしくは無置換のターフェニル基、置換もしくは無置換のナフチル基が好ましく、置換もしくは無置換のフェニル基、置換もしくは無置換のビフェニル基、置換もしくは無置換のターフェニル基であることがより好ましい。特に好ましくは、置換もしくは無置換のフェニル基である。 Furthermore, in order to enhance the light stability of the organic compound, it is necessary to moderately suppress the twist of the carbon-carbon bond of Ar 5 and the pyromethene skeleton. This is because, when the twist is excessively large, the light stability is lowered, for example, the reactivity to the excitation light is increased. From this point of view, Ar 5 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group. Of these, a phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group are more preferable. Particularly preferred is a substituted or unsubstituted phenyl group.
　また、Ａｒ5は、適度にかさ高い置換基であることが好ましい。Ａｒ5が、ある程度のかさ高さを有することにより、分子の凝集を防ぐことができる。この結果、上記有機化合物の発光効率や耐久性がより向上する。 Ar 5 is preferably a moderately bulky substituent. Since Ar 5 has a certain amount of bulkiness, aggregation of molecules can be prevented. As a result, the luminous efficiency and durability of the organic compound are further improved.
　このようなかさ高い置換基のさらに好ましい例としては、下記一般式（２）で表されるＡｒ5の構造が挙げられる。 A more preferred example of such a bulky substituent includes the structure of Ar 5 represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　すなわち、上記有機化合物を表す一般式（１）において、Ａｒ5は、一般式（２）で表される基であることが好ましい。このＡｒ5を表す一般式（２）において、ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基からなる群より選ばれる。ｋは１～３の整数である。ｋが２以上である場合、ｒは、それぞれ同じでも異なってもよい。 That is, in the general formula (1) representing the organic compound, Ar 5 is preferably a group represented by the general formula (2). In the general formula (2) representing Ar 5 , r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl Ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, Selected from the group consisting of phosphine oxide groups. k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
　これらの基のうち、例えば、オキシカルボニル基は、置換基を有していても有していなくてもよい。オキシカルボニル基の置換基としては、例えばアルキル基、シクロアルキル基、アリール基、ヘテロアリール基などが挙げられ、これら置換基はさらに置換されてもよい。 Of these groups, for example, an oxycarbonyl group may or may not have a substituent. Examples of the substituent for the oxycarbonyl group include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and the like, and these substituents may be further substituted.
　より高い蛍光量子収率を与えることができるという観点から、ｒは、置換もしくは無置換のアリール基であることが好ましい。このアリール基の中でも、特に、フェニル基、ナフチル基が好ましい例として挙げられる。ｒがアリール基である場合、一般式（２）のｋは、１もしくは２であることが好ましく、分子の凝集をより防ぐという観点から、ｋは、２であることがより好ましい。さらに、ｋが２以上である場合、ｒの少なくとも１つは、アルキル基で置換されていることが好ましい。この場合のアルキル基としては、熱的安定性の観点から、メチル基、エチル基およびｔｅｒｔ－ブチル基が特に好ましい例として挙げられる。 From the viewpoint that a higher fluorescence quantum yield can be provided, r is preferably a substituted or unsubstituted aryl group. Among these aryl groups, a phenyl group and a naphthyl group are particularly preferable examples. When r is an aryl group, k in the general formula (2) is preferably 1 or 2, and k is more preferably 2 from the viewpoint of further preventing aggregation of molecules. Furthermore, when k is 2 or more, it is preferable that at least one of r is substituted with an alkyl group. As the alkyl group in this case, a methyl group, an ethyl group, and a tert-butyl group are particularly preferable from the viewpoint of thermal stability.
　また、蛍光波長や吸収波長を制御したり、溶媒との相溶性を高めたりするという観点から、ｒは、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基またはハロゲンであることが好ましく、メチル基、エチル基、ｔｅｒｔ－ブチル基、メトキシ基がより好ましい。分散性の観点からは、ｔｅｒｔ－ブチル基、メトキシ基が特に好ましい。ｒがｔｅｒｔ－ブチル基またはメトキシ基であることは、分子同士の凝集による消光を防ぐことについてより有効である。 Further, from the viewpoint of controlling the fluorescence wavelength and absorption wavelength, and increasing the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen. , A methyl group, an ethyl group, a tert-butyl group, and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. When r is a tert-butyl group or a methoxy group, it is more effective for preventing quenching due to aggregation between molecules.
　Ａｒ1～Ａｒ4が全て水素の場合に比べ、Ａｒ1～Ａｒ4の少なくとも１つが置換もしくは無置換のアルキル基や置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基である場合の方が、より良い熱的安定性および光安定性を示す。 Compared to the case where Ar 1 to Ar 4 are all hydrogen, when at least one of Ar 1 to Ar 4 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group It shows better thermal stability and light stability.
　Ａｒ1～Ａｒ4の少なくとも１つが置換もしくは無置換のアリール基である場合、アリール基としては、フェニル基、ビフェニル基、ターフェニル基、ナフチル基が好ましく、さらに好ましくは、フェニル基、ビフェニル基である。特に好ましくは、フェニル基である。 When at least one of Ar 1 to Ar 4 is a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, more preferably a phenyl group or a biphenyl group. is there. Particularly preferred is a phenyl group.
　Ａｒ1～Ａｒ4の少なくとも１つが置換もしくは無置換のヘテロアリール基である場合、ヘテロアリール基としては、ピリジル基、キノリニル基、チオフェニル基が好ましく、さらに好ましくは、ピリジル基、キノリニル基である。特に好ましくは、ピリジル基である。 When at least one of Ar 1 to Ar 4 is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolinyl group, or a thiophenyl group, and more preferably a pyridyl group or a quinolinyl group. Particularly preferred is a pyridyl group.
　また、上記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4が全て、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であることが好ましい。これは、より良い熱的安定性および光安定性を示すからである。本実施の形態に係る蛍光体組成物などにおいて、上記有機化合物が、これと組み合わせられる無機蛍光体に比べて発光体からの発光光をより長波長の光へ変換する場合、一般式（１）に表されるＡｒ1～Ａｒ4は全て、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアリール基であることがより好ましく、フェニル基が特に好ましい。この場合、例えば、発光体からの発光光が青色光であれば、無機蛍光体は、この青色光を緑色光へ変換し、上記有機化合物は、この青色光を、この無機蛍光体の色変換よりも長波長の光、すなわち、赤色光へ変換する。 In the general formula (1) representing the organic compound, all of Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Is preferred. This is because it shows better thermal stability and light stability. In the phosphor composition and the like according to the present embodiment, when the organic compound converts light emitted from the light emitter into light having a longer wavelength than the inorganic phosphor combined therewith, the general formula (1) Ar 1 to Ar 4 may be the same or different from each other, more preferably a substituted or unsubstituted aryl group, and particularly preferably a phenyl group. In this case, for example, if the light emitted from the light emitter is blue light, the inorganic phosphor converts the blue light to green light, and the organic compound converts the blue light to the color of the inorganic phosphor. Longer wavelength light, that is, red light.
　さらに、上記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4のうち少なくとも１つは、一般式（３）で表される置換基であることが好ましい。これにより、高色純度と耐久性の両立ができる。 Furthermore, in the general formula (1) representing the organic compound, at least one of Ar 1 to Ar 4 is preferably a substituent represented by the general formula (3). Thereby, both high color purity and durability can be achieved.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（３）において、Ｒ3は、アルキル基、シクロアルキル基、アルコキシ基およびアルキルチオ基からなる群より選ばれる。ｎは、１～３の整数である。ｎが２以上の場合、各Ｒ3は、同じでも異なってもよい。 In the general formula (3), R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group. n is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different.
　一般式（３）で表されるアリール基において、Ｒ3が電子供与性基である場合、主に色純度に影響を与えることから、好ましい。電子供与性基としては、アルキル基、シクロアルキル基、アルコキシ基またはアルキルチオ基などが挙げられる。特に、炭素数１～８のアルキル基、炭素数１～８のシクロアルキル基、炭素数１～８のアルコキシ基または炭素数１～８のアルキルチオ基で置換されたアリール基が好ましい。Ｒ3が炭素数１～８のアルキル基または炭素数１～８のアルコキシ基である場合は、より高い色純度を得られることから、より好ましい。また、主に発光効率に影響を与えるアリール基としては、ｔ－ブチル基、アダマンチル基などのかさ高い置換基を有するアリール基が好ましい。 In the aryl group represented by the general formula (3), when R 3 is an electron donating group, it is preferable because it mainly affects the color purity. Examples of the electron donating group include an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group. In particular, an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkylthio group having 1 to 8 carbon atoms is preferable. R 3 is more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms because higher color purity can be obtained. Further, as the aryl group mainly affecting the luminous efficiency, an aryl group having a bulky substituent such as a t-butyl group or an adamantyl group is preferable.
　また、耐熱性と色純度の観点から、Ａｒ1とＡｒ4、Ａｒ2とＡｒ3は、それぞれ同じ構造のアリール基であることが好ましい。さらに、分散性の観点から、Ａｒ1～Ａｒ4のうち少なくとも１つは、一般式（３）で表される基であってＲ3が炭素数４以上のアルキル基またはアルコキシ基であることがより好ましい。中でも、ｔ－ブチル基、メトキシ基またはｔ－ブトキシ基であることが、Ａｒ1～Ａｒ4のうち少なくとも１つの例として、特に好ましく挙げられる。 Further, from the viewpoint of heat resistance and color purity, Ar 1 and Ar 4 , Ar 2 and Ar 3 are preferably aryl groups having the same structure. Further, from the viewpoint of dispersibility, at least one of Ar 1 to Ar 4 is a group represented by the general formula (3), and R 3 is an alkyl group or alkoxy group having 4 or more carbon atoms. More preferred. Among them, a t-butyl group, a methoxy group, or a t-butoxy group is particularly preferable as at least one example of Ar 1 to Ar 4 .
　一般式（３）において、ｎは、１～３の整数であることが好ましく、原料入手と合成の容易さの観点から、１または２であることがより好ましい。 In the general formula (3), n is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of availability of raw materials and ease of synthesis.
　一方、上記有機化合物を表す一般式（１）において、Ａｒ1≠Ａｒ2またはＡｒ3≠Ａｒ4であることは、膜中での分散性が向上し、高効率発光が得られるので、特に好ましい。ここで、「≠」は、異なる構造の基であることを示す。例えば、Ａｒ1≠Ａｒ2は、Ａｒ1とＡｒ2とが異なる構造の基であることを示す。Ａｒ3≠Ａｒ4は、Ａｒ3とＡｒ4とが異なる構造の基であることを示す。Ａｒ1≠Ａｒ2またはＡｒ3≠Ａｒ4であるとは、言い換えると、「Ａｒ1＝Ａｒ2かつＡｒ3＝Ａｒ4」ではないということである。すなわち、Ａｒ1～Ａｒ4の任意の組合せのうち、（１）Ａｒ1＝Ａｒ2＝Ａｒ3＝Ａｒ4であるもの、および（２）Ａｒ1＝Ａｒ2かつＡｒ3＝Ａｒ4であって、Ａｒ1≠Ａｒ3であるもの、が除かれることを表す。 On the other hand, in the general formula (1) representing the organic compound, Ar 1 ≠ Ar 2 or Ar 3 ≠ Ar 4 is particularly preferable because dispersibility in the film is improved and high efficiency light emission is obtained. . Here, “≠” indicates a group having a different structure. For example, Ar 1 ≠ Ar 2 indicates that Ar 1 and Ar 2 are groups having different structures. Ar 3 ≠ Ar 4 indicates that Ar 3 and Ar 4 are groups having different structures. In other words, Ar 1 ≠ Ar 2 or Ar 3 ≠ Ar 4 means that “Ar 1 = Ar 2 and Ar 3 = Ar 4 ” is not satisfied. That is, among arbitrary combinations of Ar 1 to Ar 4 , (1) Ar 1 = Ar 2 = Ar 3 = Ar 4 and (2) Ar 1 = Ar 2 and Ar 3 = Ar 4 , Ar 1 ≠ Ar 3 is excluded.
　一般式（３）で表されるアリール基により、一般式（１）で表される有機化合物の発光効率、色純度、耐熱性および耐光性などのさまざまな特性および物性に影響を与える。複数の性質を向上させるアリール基もあるが、全てにおいて十分な性能を示すアリール基は皆無である。特に、高発光効率と高色純度の両立が難しい。そのため、一般式（１）で表される有機化合物に対し複数種類のアリール基を導入できれば、発光特性や色純度などにバランスの取れた有機化合物を得ることが期待される。 The aryl group represented by the general formula (3) affects various properties and physical properties of the organic compound represented by the general formula (1) such as luminous efficiency, color purity, heat resistance and light resistance. Some aryl groups improve multiple properties, but none have sufficient performance in all. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, if a plurality of types of aryl groups can be introduced into the organic compound represented by the general formula (1), it is expected to obtain an organic compound balanced in light emission characteristics and color purity.
　Ａｒ1＝Ａｒ2＝Ａｒ3＝Ａｒ4である有機化合物は、一種類のアリール基しか有することができない。また、Ａｒ1＝Ａｒ2かつＡｒ3＝Ａｒ4であって、Ａｒ1≠Ａｒ3である有機化合物は、特定の物性を有するアリール基が片方のピロール環に偏ることとなる。この場合、発光効率と色純度との関係で後述するように各々のアリール基が有する物性を最大限に引き出すことが難しい。 An organic compound in which Ar 1 = Ar 2 = Ar 3 = Ar 4 can have only one kind of aryl group. Further, in an organic compound in which Ar 1 = Ar 2 and Ar 3 = Ar 4 and Ar 1 ≠ Ar 3 , an aryl group having specific physical properties is biased to one pyrrole ring. In this case, it is difficult to maximize the physical properties of each aryl group as will be described later in relation to the luminous efficiency and color purity.
　これに対し、本発明の実施の形態に係る有機化合物は、ある物性を有する置換基を左右のピロール環にバランスよく配置することが可能となるため、片方のピロール環に偏らせた場合と比べて、最大限にその物性を発揮させることが可能となる。 On the other hand, the organic compound according to the embodiment of the present invention can arrange substituents having certain physical properties in a balanced manner on the left and right pyrrole rings, compared with the case where it is biased to one pyrrole ring. Therefore, it is possible to maximize the physical properties.
　この効果は、発光効率と色純度とをバランスよく向上させる点において、特に優れている。色純度に影響を与えるアリール基は、両側のピロール環にそれぞれ１つ以上有していることが、共役系が拡張して高色純度の発光が得られる点で好ましい。しかし、Ａｒ1＝Ａｒ2かつＡｒ3＝Ａｒ4であって、Ａｒ1≠Ａｒ3である有機化合物は、例えば一方のピロール環に色純度に影響を与えるアリール基を導入した場合に、他方のピロール環に発光効率に影響を与えるアリール基を導入すると、色純度に影響を与えるアリール基が片側のピロール環に偏るため、共役系が十分に拡張せず、色純度が十分に向上しない。また、他方のピロール環に、同様に色純度に影響を与えるアリール基であって別の構造のものを導入すると、発光効率を向上させることができない。 This effect is particularly excellent in that the luminous efficiency and color purity are improved in a balanced manner. It is preferable that at least one aryl group that affects the color purity is present in each of the pyrrole rings on both sides, from the viewpoint that the conjugated system is expanded and light emission with high color purity is obtained. However, when Ar 1 = Ar 2 and Ar 3 = Ar 4 and Ar 1 ≠ Ar 3 , for example, when an aryl group that affects color purity is introduced into one pyrrole ring, the other When an aryl group that affects the luminous efficiency is introduced into the pyrrole ring, the aryl group that affects the color purity is biased to the pyrrole ring on one side, so that the conjugated system is not sufficiently expanded and the color purity is not sufficiently improved. In addition, if an aryl group having a different structure that similarly affects the color purity is introduced into the other pyrrole ring, the light emission efficiency cannot be improved.
　これに対し、本発明の実施の形態に係る有機化合物は、色純度に影響を与えるアリール基を両側のピロール環にそれぞれ１つ以上導入し、それ以外の位置に発光効率に影響を与えるアリール基を導入することができる。このため、本発明の実施の形態に係る有機化合物は、色純度および発光効率の両方の性質を最大限に向上させることができ、故に好ましい。なお、Ａｒ2およびＡｒ3の位置に色純度に影響を与えるアリール基を導入した場合が、最も共役系が拡張されるため、好ましい。 On the other hand, the organic compound according to the embodiment of the present invention introduces one or more aryl groups that affect the color purity into each of the pyrrole rings on both sides, and the aryl group that affects the luminous efficiency at other positions. Can be introduced. For this reason, the organic compound which concerns on embodiment of this invention can improve the property of both color purity and luminous efficiency to the maximum, and is therefore preferable. Note that it is preferable to introduce an aryl group that affects the color purity at the positions Ar 2 and Ar 3 because the conjugated system is most expanded.
　Ａｒ1～Ａｒ4の少なくとも１つが置換もしくは無置換のアルキル基である場合、アルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基といった炭素数１～６のアルキル基が好ましい。さらに、このアルキル基としては、熱的安定性に優れるという観点から、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基が好ましい。また、濃度消光を防ぎ、発光量子収率を向上させるという観点では、このアルキル基として、立体的にかさ高いｔｅｒｔ－ブチル基がより好ましい。一方、合成の容易さ、原料入手の容易さという観点から、このアルキル基として、メチル基も好ましく用いられる。 When at least one of Ar 1 to Ar 4 is a substituted or unsubstituted alkyl group, examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert group An alkyl group having 1 to 6 carbon atoms such as a butyl group, a pentyl group or a hexyl group is preferred. Further, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, this alkyl group is more preferably a sterically bulky tert-butyl group. On the other hand, from the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as the alkyl group.
　一方、上記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4が全て、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基である場合、バインダー樹脂や溶媒への溶解性が良好なため、好ましい。この場合、アルキル基としては、合成の容易さ、原料入手の容易さという観点から、メチル基が好ましい。例えば、本実施の形態に係る蛍光体組成物などにおいて、上記有機化合物が、これと組み合わせられる無機蛍光体に比べて発光体からの発光光をより短波長の光へ変換する場合、一般式（１）に表されるＡｒ1～Ａｒ4は全て、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であり、好ましくはメチル基である。具体的には、発光体からの発光光が青色光であれば、無機蛍光体は、この青色光を赤色光へ変換し、上記有機化合物は、この青色光を、この無機蛍光体の色変換よりも短波長の光、すなわち、緑色光へ変換する。 On the other hand, in the general formula (1) representing the organic compound, all of Ar 1 to Ar 4 may be the same or different, and when they are substituted or unsubstituted alkyl groups, they are soluble in a binder resin or a solvent. Is preferable. In this case, the alkyl group is preferably a methyl group from the viewpoints of ease of synthesis and availability of raw materials. For example, in the phosphor composition according to the present embodiment, when the organic compound converts light emitted from a light emitter into light having a shorter wavelength than an inorganic phosphor combined therewith, a general formula ( Ar 1 to Ar 4 represented by 1) may all be the same or different and each represents a substituted or unsubstituted alkyl group, preferably a methyl group. Specifically, if the light emitted from the light emitter is blue light, the inorganic phosphor converts the blue light into red light, and the organic compound converts the blue light into the color of the inorganic phosphor. Shorter wavelength light, that is, green light.
　このような有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも１つは、水素である。すなわち、Ｒ1およびＲ2は、水素、アルキル基、カルボニル基、オキシカルボニル基、アリール基のうちの何れかであることが好ましいが、熱的安定性の観点から、水素またはアルキル基であることが好ましい。特に、発光スペクトルにおいて狭い半値幅を得やすいという観点から、Ｒ1およびＲ2のうち少なくとも１つは、水素であることがより好ましい。 In the general formula (1) representing such an organic compound, at least one of R 1 and R 2 is hydrogen. That is, R 1 and R 2 are preferably any one of hydrogen, an alkyl group, a carbonyl group, an oxycarbonyl group, and an aryl group, but from the viewpoint of thermal stability, they are hydrogen or an alkyl group. Is preferred. In particular, from the viewpoint of easily obtaining a narrow half-value width in the emission spectrum, at least one of R 1 and R 2 is more preferably hydrogen.
　また、Ｌは、アルキル基、アリール基、ヘテロアリール基、フッ素、含フッ素アルキル基、含フッ素ヘテロアリール基または含フッ素アリール基であることが好ましい。特に、励起光に対して安定であって、より高い蛍光量子収率が得られることから、Ｌは、フッ素または含フッ素アリール基であることがより好ましい。さらに、Ｌは、合成の容易さから、フッ素であることがより一層好ましい。 Further, L is preferably an alkyl group, an aryl group, a heteroaryl group, fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group. In particular, L is more preferably a fluorine or fluorine-containing aryl group because it is stable against excitation light and a higher fluorescence quantum yield is obtained. Further, L is more preferably fluorine in view of ease of synthesis.
　ここで、含フッ素アリール基とは、フッ素を含むアリール基であり、例えば、フルオロフェニル基、トリフルオロメチルフェニル基およびペンタフルオロフェニル基などが挙げられる。含フッ素ヘテロアリール基とは、フッ素を含むヘテロアリール基であり、例えば、フルオロピリジル基、トリフルオロメチルピリジル基およびトリフルオロピリジル基などが挙げられる。含フッ素アルキル基とは、フッ素を含むアルキル基であり、例えば、トリフルオロメチル基やペンタフルオロエチル基などが挙げられる。 Here, the fluorine-containing aryl group is an aryl group containing fluorine, and examples thereof include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a heteroaryl group containing fluorine, and examples thereof include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group. The fluorine-containing alkyl group is an alkyl group containing fluorine, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.
　また、一般式（１）で表される有機化合物の別の態様として、Ｒ1、Ｒ2、Ａｒ1～Ａｒ5のうち少なくとも１つが電子吸引基であることが好ましい。特に、（１）Ｒ1、Ｒ2、Ａｒ1～Ａｒ4のうち少なくとも１つが電子吸引基であること、（２）Ａｒ5が電子吸引基であること、または（３）Ｒ1、Ｒ2、Ａｒ1～Ａｒ4のうち少なくとも１つが電子吸引基であり、かつ、Ａｒ5が電子吸引基であること、が好ましい。このように有機化合物のピロメテン骨格に電子吸引基を導入することで、ピロメテン骨格の電子密度を大幅に下げることができる。これにより、上記有機化合物の酸素に対する安定性がより向上し、この結果、上記有機化合物の耐久性をより向上させることができる。 As another embodiment of the organic compound represented by the general formula (1), it is preferable that at least one of R 1 , R 2 and Ar 1 to Ar 5 is an electron withdrawing group. In particular, (1) at least one of R 1 , R 2 and Ar 1 to Ar 4 is an electron withdrawing group, (2) Ar 5 is an electron withdrawing group, or (3) R 1 , R 2 , Ar 1 to Ar 4 are preferably electron withdrawing groups, and Ar 5 is preferably an electron withdrawing group. Thus, by introducing an electron withdrawing group into the pyromethene skeleton of the organic compound, the electron density of the pyromethene skeleton can be significantly reduced. Thereby, the stability with respect to oxygen of the organic compound is further improved, and as a result, the durability of the organic compound can be further improved.
　電子吸引基とは、電子受容性基とも呼称し、有機電子論において、誘起効果や共鳴効果により、置換した原子団から、電子を引き付ける原子団である。電子吸引基としては、ハメット則の置換基定数（σｐ（パラ））として、正の値をとるものが挙げられる。ハメット則の置換基定数（σｐ（パラ））は、化学便覧基礎編改訂５版（ＩＩ－３８０頁）から引用することができる。なお、フェニル基も、上記のような正の値をとる例もあるが、本発明において、電子吸引基にフェニル基は含まれない。 The electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory. Examples of the electron-withdrawing group include those that take a positive value as the Hammett's rule substituent constant (σp (para)). The Hammett's rule substituent constant (σp (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380). In addition, although a phenyl group also has the example which takes the above positive values, in this invention, a phenyl group is not contained in an electron withdrawing group.
　電子吸引基の例として、例えば、－Ｆ（σｐ：＋０．０６）、－Ｃｌ（σｐ：＋０．２３）、－Ｂｒ（σｐ：＋０．２３）、－Ｉ（σｐ：＋０．１８）、－ＣＯ2Ｒ12（σｐ：Ｒ12がエチル基の時＋０．４５）、－ＣＯＮＨ2（σｐ：＋０．３８）、－ＣＯＲ12（σｐ：Ｒ12がメチル基の時＋０．４９）、－ＣＦ3（σｐ：＋０．５０）、－ＳＯ2Ｒ12（σｐ：Ｒ12がメチル基の時＋０．６９）、－ＮＯ2（σｐ：＋０．８１）等が挙げられる。Ｒ12は、それぞれ独立に、水素原子、置換もしくは無置換の環形成炭素数６～３０の芳香族炭化水素基、置換もしくは無置換の環形成原子数５～３０の複素環基、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の炭素数１～３０のシクロアルキル基を表す。これら各基の具体例としては、上記と同様の例が挙げられる。 Examples of electron withdrawing groups include, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18),- CO 2 R 12 (σp: when R 12 is an ethyl group +0.45), —CONH 2 (σp: +0.38), —COR 12 (σp: when R 12 is a methyl group +0.49), —CF 3 (σp: +0.50), —SO 2 R 12 (+0.69 when σp: R 12 is a methyl group), —NO 2 (σp: +0.81), and the like. R 12 each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, substituted or unsubstituted A substituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms are represented. Specific examples of these groups include the same examples as described above.
　好ましい電子吸引基としては、フッ素、含フッ素アリール基、含フッ素ヘテロアリール基、含フッ素アルキル基、置換もしくは無置換のアシル基、置換もしくは無置換のエステル基、置換もしくは無置換のアミド基、置換もしくは無置換のスルホニル基またはシアノ基が挙げられる。何故なら、これらは、化学的に分解しにくいからである。 Preferred electron withdrawing groups include fluorine, fluorine-containing aryl groups, fluorine-containing heteroaryl groups, fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, substituted or unsubstituted amide groups, and substituted groups. Or an unsubstituted sulfonyl group or a cyano group is mentioned. This is because they are difficult to decompose chemically.
　より好ましい電子吸引基としては、含フッ素アルキル基、置換もしくは無置換のアシル基、置換もしくは無置換のエステル基またはシアノ基が挙げられる。何故なら、これらは、濃度消光を防ぎ、発光量子収率を向上させる効果につながるからである。特に好ましい電子吸引基は、置換もしくは無置換のエステル基である。 More preferred electron withdrawing groups include fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, and cyano groups. This is because these lead to effects of preventing concentration quenching and improving the emission quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.
　上記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも１つは、電子吸引基であることが好ましい。何故なら、発光効率および色純度を損なうことなく、一般式（１）で表される有機化合物の酸素に対する安定性を向上させることができ、この結果、上記有機化合物の耐久性を向上させることができるからである。 In the general formula (1) representing the organic compound, at least one of R 1 and R 2 is preferably an electron withdrawing group. This is because the stability of the organic compound represented by the general formula (1) to oxygen can be improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be improved. Because it can.
　また、上記有機化合物のＡｒ5を表す一般式（２）において、ｒは、電子吸引基であることがより好ましい。何故なら、発光効率および色純度を損なうことなく、一般式（１）で表される有機化合物の酸素に対する安定性がさらに向上し、この結果、上記有機化合物の耐久性を大幅に向上させることができるからである。 In the general formula (2) representing Ar 5 of the organic compound, r is more preferably an electron withdrawing group. This is because the stability of the organic compound represented by the general formula (1) to oxygen is further improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be greatly improved. Because it can.
　一般式（１）で表される有機化合物の好ましい例の一つとして、Ａｒ1～Ａｒ4が全て、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であって、さらに、Ａｒ5が一般式（２）で表される基である場合が挙げられる。この場合、Ａｒ5は、ｒが置換もしくは無置換のフェニル基として含まれる一般式（２）で表される基であることが特に好ましい。 As one of preferable examples of the organic compound represented by the general formula (1), Ar 1 to Ar 4 may all be the same or different and each is a substituted or unsubstituted alkyl group, and Ar The case where 5 is group represented by General formula (2) is mentioned. In this case, Ar 5 is particularly preferably a group represented by the general formula (2) in which r is included as a substituted or unsubstituted phenyl group.
　また、一般式（１）で表される有機化合物の好ましい例の別の一つとして、Ａｒ1～Ａｒ4が全て、それぞれ同じでも異なっていてもよく、上述の一般式（３）から選ばれるものであり、さらに、Ａｒ5が一般式（２）で表される基である場合が挙げられる。この場合、Ａｒ5は、ｒがｔｅｒｔ－ブチル基、メトキシ基として含まれる一般式（２）で表される基であることがより好ましく、ｒがメトキシ基として含まれる一般式（２）で表される基であることが特に好ましい。 As another preferred example of the organic compound represented by the general formula (1), all of Ar 1 to Ar 4 may be the same or different and are selected from the above general formula (3). And Ar 5 is a group represented by the general formula (2). Table In this case, Ar 5 is, r is tert- butyl group, at more preferably a group represented by the general formula to be included as a methoxy group (2), the general formula r is included as a methoxy group (2) It is particularly preferred that
　以下に、一般式（１）で表される有機化合物の一例を示すが、本実施の形態に係る有機化合物は、これらに限定されるものではない。 Hereinafter, examples of the organic compound represented by the general formula (1) are shown, but the organic compound according to the present embodiment is not limited to these.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
  
Figure JPOXMLDOC01-appb-C000021
  
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
  
Figure JPOXMLDOC01-appb-C000024
  
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
  
Figure JPOXMLDOC01-appb-C000026
  
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
  
Figure JPOXMLDOC01-appb-C000028
  
Figure JPOXMLDOC01-appb-C000029
  
Figure JPOXMLDOC01-appb-C000029
  
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　一般式（１）で表される有機化合物は、例えば特表平８－５０９４７１号公報や特開２０００－２０８２６２号公報に記載の方法で製造することができる。すなわち、ピロメテン化合物と金属塩とを塩基共存下で反応することにより、目的とするピロメテン系金属錯体が得られる。 The organic compound represented by the general formula (1) can be produced, for example, by the method described in JP-T-8-509471 and JP-A-2000-208262. That is, the target pyromethene metal complex is obtained by reacting the pyromethene compound and the metal salt in the presence of a base.
　また、ピロメテン－フッ化ホウ素錯体の合成については、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，ｖｏｌ．６４，Ｎｏ．２１，ｐｐ７８１３－７８１９（１９９９）、Ａｎｇｅｗ．Ｃｈｅｍ．，Ｉｎｔ．Ｅｄ．Ｅｎｇｌ．，ｖｏｌ．３６，ｐｐ１３３３－１３３５（１９９７）などに記載されている方法を参考にして、一般式（１）で表される有機化合物を製造することができる。例えば、下記一般式（４）で表される化合物と下記一般式（５）で表される化合物とをオキシ塩化リン存在下、１，２－ジクロロエタン中で加熱した後、下記一般式（６）で表される化合物をトリエチルアミン存在下、１，２－ジクロロエタン中で反応させ、これにより、一般式（１）で表される有機化合物を得る方法が挙げられる。しかし、本発明は、これに限定されるものではない。ここで、Ｒ101～Ｒ109は、上記のように説明した基と同様である。Ｊはハロゲンを表す。 For the synthesis of a pyromethene-boron fluoride complex, see J.A. Org. Chem. , Vol. 64, no. 21, pp 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, pp 1333-1335 (1997) and the like, the organic compound represented by the general formula (1) can be produced. For example, after heating a compound represented by the following general formula (4) and a compound represented by the following general formula (5) in 1,2-dichloroethane in the presence of phosphorus oxychloride, the following general formula (6) In the presence of triethylamine, 1,2-dichloroethane is reacted to obtain an organic compound represented by the general formula (1). However, the present invention is not limited to this. Here, R 101 to R 109 are the same as those described above. J represents halogen.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　さらに、アリール基やヘテロアリール基の導入の際は、ハロゲン化誘導体とボロン酸あるいはボロン酸エステル化誘導体とのカップリング反応を用いて炭素－炭素結合を生成する方法が挙げられるが、本発明は、これに限定されるものではない。同様に、アミノ基やカルバゾリル基の導入の際にも、例えば、パラジウムなどの金属触媒下でのハロゲン化誘導体とアミンあるいはカルバゾール誘導体とのカップリング反応を用いて炭素－窒素結合を生成する方法が挙げられるが、本発明は、これに限定されるものではない。 Furthermore, when introducing an aryl group or a heteroaryl group, a method of generating a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned. However, the present invention is not limited to this. Similarly, when introducing an amino group or a carbazolyl group, for example, there is a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium. However, the present invention is not limited to this.
　本発明の実施の形態に係る蛍光体組成物は、一般式（１）で表される有機化合物以外に、必要に応じてその他の化合物を適宜含有することができる。例えば、励起光から一般式（１）で表される有機化合物へのエネルギー移動効率を更に高めるために、ルブレンなどのアシストドーパントを含有してもよい。また、一般式（１）で表される有機化合物の発光色以外の発光色を加味したい場合は、所望の有機発光材料、例えば、クマリン系色素、ペリレン系色素、フタロシアニン系色素、スチルベン系色素、シアニン系色素、ポリフェニレン系色素、ローダミン系色素、ピリジン系色素、ピロメテン系色素、ポルフィリン色素、オキサジン系色素、ピラジン系色素などの化合物を添加することができる。その他、これらの有機発光材料以外でも、無機蛍光体、蛍光顔料、蛍光染料、量子ドットなどの公知の発光材料を組み合わせて添加することも可能である。 The phosphor composition according to the embodiment of the present invention can appropriately contain other compounds as required in addition to the organic compound represented by the general formula (1). For example, an assist dopant such as rubrene may be contained in order to further increase the energy transfer efficiency from the excitation light to the organic compound represented by the general formula (1). In addition, when it is desired to add a light emission color other than the light emission color of the organic compound represented by the general formula (1), a desired organic light emitting material such as a coumarin dye, a perylene dye, a phthalocyanine dye, a stilbene dye, Compounds such as cyanine dyes, polyphenylene dyes, rhodamine dyes, pyridine dyes, pyromethene dyes, porphyrin dyes, oxazine dyes and pyrazine dyes can be added. In addition to these organic light-emitting materials, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots can be added in combination.
　以下に、一般式（１）で表される有機化合物以外の有機発光材料の一例を示すが、本発明は、特にこれらに限定されるものではない。 Hereinafter, examples of organic light-emitting materials other than the organic compound represented by the general formula (1) are shown, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　本発明の実施の形態に係る蛍光体組成物における一般式（１）で表される有機化合物の含有量は、有機化合物のモル吸光係数、蛍光量子収率および励起波長における吸収強度、並びに作製するフィルムの厚みや透過率にもよるが、通常は蛍光体組成物全体の重量に対して、１０-5重量パーセント～１０重量パーセントであり、１０-4重量パーセント～５重量パーセントであることがさらに好ましく、１０-3重量パーセント～２重量パーセントであることが特に好ましい。 The content of the organic compound represented by the general formula (1) in the phosphor composition according to the embodiment of the present invention includes the molar absorption coefficient of the organic compound, the fluorescence quantum yield, the absorption intensity at the excitation wavelength, and the production. Depending on the thickness and transmittance of the film, it is usually 10 −5 weight percent to 10 weight percent, more preferably 10 −4 weight percent to 5 weight percent, based on the total weight of the phosphor composition. Preferably, it is 10 −3 weight percent to 2 weight percent.
（無機蛍光体）
　本発明の実施の形態における無機蛍光体は、上述した一般式（１）で表される有機化合物（有機発光材料）と組み合わせて用いられる無機物の蛍光体であり、発光体からの発光光を、この有機化合物とは異なる波長範囲の光へ変換する。本実施の形態における無機蛍光体として、特に、発光スペクトルが５００～７００ｎｍの領域にピークを有する無機蛍光体が好ましく用いられる。このような無機蛍光体は、４００～５００ｎｍの範囲の励起光によって励起され、５００～７００ｎｍの領域で発光する。 (Inorganic phosphor)
The inorganic phosphor in the embodiment of the present invention is an inorganic phosphor used in combination with the organic compound (organic light-emitting material) represented by the general formula (1) described above, and emits light emitted from the phosphor. The light is converted into light having a wavelength range different from that of the organic compound. As the inorganic phosphor in the present embodiment, an inorganic phosphor having a peak in the region where the emission spectrum is 500 to 700 nm is particularly preferably used. Such an inorganic phosphor is excited by excitation light in the range of 400 to 500 nm and emits light in the region of 500 to 700 nm.
　例えば、本実施の形態において、無機蛍光体には、緑色に発光する無機蛍光体、黄色に発光する無機蛍光体、赤色に発光する無機蛍光体が挙げられる。無機蛍光体の形状としては、特に制限はなく、球状、柱状など様々なものを用いることができる。また、無機蛍光体としては、最終的に所定の色を再現できるものであれば特に限定はなく、公知のものを用いることができる。 For example, in the present embodiment, examples of the inorganic phosphor include an inorganic phosphor that emits green light, an inorganic phosphor that emits yellow light, and an inorganic phosphor that emits red light. There is no restriction | limiting in particular as a shape of an inorganic fluorescent substance, Various things, such as spherical shape and a column shape, can be used. The inorganic phosphor is not particularly limited as long as it can finally reproduce a predetermined color, and a known phosphor can be used.
　上記のような無機蛍光体の例としては、ＹＡＧ系蛍光体、ＴＡＧ系蛍光体、シリケート蛍光体、ナイトライド系蛍光体、オキシナイトライド系蛍光体、窒化物、酸窒化物蛍光体、Ｍｎ4+付活フッ化物錯体蛍光体等が挙げられる。中でも、窒化物、酸窒化物蛍光体、Ｍｎ4+付活フッ化物錯体蛍光体が、上記無機蛍光体として好ましく用いられる。特に、β型サイアロン蛍光体、ＫＳＦ蛍光体が、上記無機蛍光体として好ましく用いられる。 Examples of the inorganic phosphor as described above include YAG phosphor, TAG phosphor, silicate phosphor, nitride phosphor, oxynitride phosphor, nitride, oxynitride phosphor, Mn 4 + Activated fluoride complex phosphor and the like. Among these, nitrides, oxynitride phosphors, and Mn 4+ activated fluoride complex phosphors are preferably used as the inorganic phosphors. In particular, a β-type sialon phosphor and a KSF phosphor are preferably used as the inorganic phosphor.
（β型サイアロン蛍光体）
　β型サイアロンは、β型窒化ケイ素の固溶体であり、β型窒化ケイ素結晶のケイ素（Ｓｉ）位置にアルミニウム（Ａｌ）が置換固溶し、窒素（Ｎ）位置に酸素（Ｏ）が置換固溶したものである。β型サイアロンの単位胞（単位格子）に２式量の原子があるので、β型サイアロンの一般式として、Ｓｉ6-ZＡｌzＯzＮ8-zが用いられる。ここで、組成ｚは、０～４．２であり、固溶範囲は非常に広く、また（Ｓｉ、Ａｌ）／（Ｎ、Ｏ）のモル比は、３／４を維持する必要がある。β型サイアロンの一般的な製法は、窒化ケイ素の他に、酸化ケイ素と窒化アルミニウムとを、あるいは酸化アルミニウムと窒化アルミニウムとを加えて、加熱する方法である。β型サイアロンは、結晶構造内に希土類などの発光元素（Ｅｕ、Ｓｒ、Ｍｎ、Ｃｅなど）を取り込むことで、紫外から青色の光で励起して５２０～５５０ｎｍの緑色発光を示すβ型サイアロン蛍光体となる。 (Β-type sialon phosphor)
β-type sialon is a solid solution of β-type silicon nitride. Aluminum (Al) is substituted and dissolved in silicon (Si) position of β-type silicon nitride crystal, and oxygen (O) is substituted and dissolved in nitrogen (N) position. It is a thing. Since there are two types of atoms in the unit cell (unit cell) of β-type sialon, Si 6-Z Al z O z N 8-z is used as a general formula of β-type sialon. Here, the composition z is 0 to 4.2, the solid solution range is very wide, and the molar ratio of (Si, Al) / (N, O) needs to be maintained at 3/4. A general method for producing β-sialon is a method of heating by adding silicon oxide and aluminum nitride, or adding aluminum oxide and aluminum nitride in addition to silicon nitride. β-Sialon is a β-Sialon fluorescence that emits green light of 520 to 550 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. Become a body.
　本発明において、β型サイアロン蛍光体は、発光スペクトルが５３５～５５０ｎｍの領域にピークを有するものが好ましく用いられる。このような発光スペクトルの波長範囲であれば、β型サイアロン蛍光体をＬＥＤパッケージに使用した場合、良好な発光特性が得られる。一方、β型サイアロン蛍光体の平均粒子径は、１μｍ以上が好ましく、１０μｍ以上がより好ましく、１６μｍ以上がさらに好ましい。また、β型サイアロン蛍光体の平均粒子径は、１００μｍ以下が好ましく、５０μｍ以下がより好ましく、１９μｍ以下がさらに好ましい。このような平均粒子径の範囲であれば、β型サイアロン蛍光体をＬＥＤパッケージに使用した場合、良好な発光特性が得られる。上記のようなβ型サイアロン蛍光体は、例えば、一般式（１）で表される有機化合物であって発光体からの青色発光を赤色発光に変換する有機発光材料と組み合わせて用いられる。 In the present invention, as the β-type sialon phosphor, those having an emission spectrum having a peak in the region of 535 to 550 nm are preferably used. Within such a wavelength range of the emission spectrum, good emission characteristics can be obtained when a β-type sialon phosphor is used in an LED package. On the other hand, the average particle size of the β-type sialon phosphor is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 16 μm or more. Further, the average particle diameter of the β-type sialon phosphor is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 19 μm or less. Within such an average particle size range, good light emission characteristics can be obtained when a β-type sialon phosphor is used in an LED package. The β-sialon phosphor as described above is used, for example, in combination with an organic light-emitting material that is an organic compound represented by the general formula (1) and converts blue light emission from a light emitter into red light emission.
（ＫＳＦ蛍光体）
　Ｍｎ賦活複フッ化物錯体蛍光体は、マンガン（Ｍｎ）を付活剤とし、アルカリ金属またはアルカリ土類金属のフッ化物錯体塩を母体結晶とする無機蛍光体である。この無機蛍光体は、その母体結晶を形成するフッ化物錯体の配位中心が４価金属（Ｓｉ、Ｔｉ、Ｚｒ、Ｈｆ、Ｇｅ、Ｓｎ）であることが好ましく、その周りに配位するフッ素原子の数は６であることが好ましい。この無機蛍光体は、Ａ2ＭＦ6：Ｍｎという一般式で表され、この一般式においてＫ2ＳｉＦ6：Ｍｎであるものが、ＫＳＦ蛍光体である。ここで、Ａは、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）およびセシウム（Ｃｓ）からなる群より選ばれ、かつＮａおよびＫのうち少なくとも１つを含む１種以上のアルカリ金属である。Ｍは、Ｓｉ、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ハフニウム（Ｈｆ）、ゲルマニウム（Ｇｅ）および錫（Ｓｎ）からなる群より選ばれる１種以上の４価元素である。 (KSF phosphor)
The Mn-activated double fluoride complex phosphor is an inorganic phosphor having manganese (Mn) as an activator and an alkali metal or alkaline earth metal fluoride complex salt as a base crystal. In this inorganic phosphor, the coordination center of the fluoride complex forming the host crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, Sn), and fluorine atoms coordinated around the center. The number of is preferably 6. This inorganic phosphor is represented by a general formula of A 2 MF 6 : Mn, and in this general formula, K 2 SiF 6 : Mn is a KSF phosphor. Here, A is one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and including at least one of Na and K These are alkali metals. M is one or more tetravalent elements selected from the group consisting of Si, titanium (Ti), zirconium (Zr), hafnium (Hf), germanium (Ge), and tin (Sn).
　本発明において、ＫＳＦ蛍光体の平均粒子径は、１μｍ以上が好ましく、２０μｍ以上であってもよいが、１０μｍ以上がより好ましい。また、ＫＳＦ蛍光体の平均粒子径は、１００μｍ以下が好ましく、７０μｍ以下がより好ましく、４０μｍ以下がさらに好ましい。このような平均粒子径の範囲であれば、ＫＳＦ蛍光体をＬＥＤパッケージに使用した場合、良好な発光特性が得られる。一方、ＫＳＦ蛍光体の形状としては、特に制限はなく、球状、柱状など様々なものを用いることができるが、粉砕されていないものが好ましく用いられる。上記のようなＫＳＦ蛍光体は、例えば、一般式（１）で表される有機化合物であって発光体からの青色発光を緑色発光に変換する有機発光材料と組み合わせて用いられる。 In the present invention, the average particle size of the KSF phosphor is preferably 1 μm or more, and may be 20 μm or more, but more preferably 10 μm or more. The average particle size of the KSF phosphor is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 40 μm or less. When the average particle size is within such a range, good light emission characteristics can be obtained when the KSF phosphor is used in an LED package. On the other hand, there is no restriction | limiting in particular as a shape of KSF fluorescent substance, Although various things, such as spherical shape and a column shape, can be used, The thing which is not grind | pulverized is used preferably. The KSF phosphor as described above is, for example, an organic compound represented by the general formula (1) and used in combination with an organic light emitting material that converts blue light emission from a light emitter to green light emission.
　ここでいう平均粒子径とは、メジアン径（Ｄ５０）のことであり、ＳＥＭ観察によって測定することができる。蛍光体層を観察して得られる２次元画像から、粒子の外縁と２点で交わる直線の当該２つの交点間の距離が最大になるものを算出し、それを平均粒子径と定義する。例えば、観測される２００個の粒子に対して測定を行い、粒径分布を求め、そこから得られる粒度分布において、小粒径側からの通過分積算５０％の粒子径をメジアン径（Ｄ５０）として求めることができる。蛍光体シートを搭載したＬＥＤ発光装置を対象とする場合は、機械研磨法、ミクロトーム法、ＣＰ法（Ｃｒｏｓｓ－ｓｅｃｔ（Ｉ）ｏｎ　Ｐｏｌ（Ｉ）ｓｈｅｒ）および集束イオンビーム（Ｆ（Ｉ）Ｂ）加工法のいずれかの方法で、蛍光体シートの断面が観測されるよう研磨を行った後、得られた断面をＳＥＭで観察して得られる２次元画像から平均粒子径を算出することができる。 Here, the average particle diameter is the median diameter (D50) and can be measured by SEM observation. From the two-dimensional image obtained by observing the phosphor layer, the one having the maximum distance between the two intersections of the straight line intersecting the outer edge of the particle at two points is calculated and defined as the average particle diameter. For example, measurement is performed on 200 particles observed to obtain a particle size distribution, and in the particle size distribution obtained therefrom, a particle size of 50% of the accumulated amount from the small particle size side is obtained as a median diameter (D50). Can be obtained as When targeting LED light-emitting devices equipped with phosphor sheets, mechanical polishing, microtome, CP (Cross-sect (I) on Pol (I) sher) and focused ion beam (F (I) B) After polishing so that the cross section of the phosphor sheet is observed by any of the processing methods, the average particle diameter can be calculated from a two-dimensional image obtained by observing the obtained cross section with an SEM. .
（マトリックス樹脂）
　マトリックス樹脂は、一般式（１）で表される有機化合物および上記無機蛍光体と混合して、あるいは、少なくとも上記無機蛍光体と混合して、連続相を形成する樹脂である。本実施の形態において、マトリックス樹脂は、成型加工性、透明性、耐熱性等に優れる材料であればよい。このようなマトリックス樹脂として、例えば、アクリル酸系、メタクリル酸系、ポリケイ皮酸ビニル系、環ゴム系等の反応性ビニル基を有する光硬化型レジスト材料、エポキシ樹脂、シリコーン樹脂（シリコーンゴム、シリコーンゲル等のオルガノポリシロキサン硬化物（架橋物）を含む）、ウレア樹脂、フッ素樹脂、ポリカーボネート樹脂、アクリル樹脂、ウレタン樹脂、メラミン樹脂、ポリビニル樹脂、ポリアミド樹脂、フェノール樹脂、ポリビニルアルコール樹脂、セルロース樹脂、脂肪族エステル樹脂、芳香族エステル樹脂、脂肪族ポリオレフィン樹脂、芳香族ポリオレフィン樹脂などの公知のものを用いることができる。また、マトリックス樹脂として、これらの共重合樹脂を用いても構わない。これらの樹脂を適宜設計することにより、本発明の実施の形態に係る蛍光体組成物および後述の蛍光体シートに有用なマトリックス樹脂が得られる。 (Matrix resin)
The matrix resin is a resin that forms a continuous phase by mixing with the organic compound represented by the general formula (1) and the inorganic phosphor, or at least by mixing with the inorganic phosphor. In the present embodiment, the matrix resin may be a material that is excellent in molding processability, transparency, heat resistance, and the like. Examples of such matrix resins include photocurable resist materials having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvinyl cinnamate, and ring rubber, epoxy resins, silicone resins (silicone rubber, silicone Organopolysiloxane cured product (cross-linked product) such as gel), urea resin, fluororesin, polycarbonate resin, acrylic resin, urethane resin, melamine resin, polyvinyl resin, polyamide resin, phenol resin, polyvinyl alcohol resin, cellulose resin, Known materials such as aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins, and aromatic polyolefin resins can be used. Further, these copolymer resins may be used as the matrix resin. By appropriately designing these resins, a matrix resin useful for the phosphor composition according to the embodiment of the present invention and the phosphor sheet described below can be obtained.
　また、マトリックス樹脂としては、上述した樹脂の中でも、フィルム化のプロセスが容易であることから、熱硬化性樹脂がさらに好ましい。さらに、透明性、耐熱性などの観点から、マトリックス樹脂として、エポキシ樹脂、シリコーン樹脂、アクリル樹脂またはこれらの混合物を好適に用いることができる。マトリックス樹脂に含有される熱硬化性樹脂は、１種類でもよいし、２種類以上の組み合わせであってもよい。マトリックス樹脂は、必要に応じて硬化剤を含有してもよい。例えば、エポキシ樹脂と硬化剤とを組み合わせることにより、マトリックス樹脂としてのエポキシ樹脂の硬化を促進して短時間で硬化させることができる。 Also, as the matrix resin, among the above-described resins, a thermosetting resin is more preferable because the film forming process is easy. Furthermore, from the viewpoints of transparency and heat resistance, an epoxy resin, a silicone resin, an acrylic resin, or a mixture thereof can be suitably used as the matrix resin. The thermosetting resin contained in the matrix resin may be one type or a combination of two or more types. The matrix resin may contain a curing agent as necessary. For example, by combining an epoxy resin and a curing agent, curing of the epoxy resin as the matrix resin can be accelerated and cured in a short time.
　本発明において、マトリックス樹脂は、耐熱性の観点から、シリコーン樹脂であることが最も好ましい。シリコーン樹脂の中でも、付加反応硬化型シリコーン組成物が、マトリックス樹脂として好ましい。付加反応硬化型シリコーン組成物は、常温または５０～２００℃の温度で、加熱、硬化し、透明性、耐熱性、接着性に優れる。付加反応硬化型シリコーン組成物は、ケイ素原子に結合したアルケニル基を有するシリコーンと、ケイ素原子に結合した水素原子を有するシリコーンと、触媒量の白金系触媒とを含有するものを使用することができる。 In the present invention, the matrix resin is most preferably a silicone resin from the viewpoint of heat resistance. Among silicone resins, addition reaction curable silicone compositions are preferred as the matrix resin. The addition reaction curable silicone composition is heated and cured at room temperature or 50 to 200 ° C., and is excellent in transparency, heat resistance, and adhesiveness. As the addition reaction curable silicone composition, a composition containing a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a catalytic amount of a platinum-based catalyst can be used. .
　本発明には、シロキサン結合を有し、かつアリール基が直結したケイ素原子を含有するシリコーン樹脂が好ましく用いられる。特に、シロキサン結合を有し、かつナフチル基が直結したケイ素原子を含有するシリコーン樹脂は、高屈折率と耐熱、耐光性とを両立できるため、本発明におけるマトリックス樹脂として好ましい。 In the present invention, a silicone resin containing a silicon atom having a siloxane bond and having an aryl group directly bonded thereto is preferably used. In particular, a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group is preferable as a matrix resin in the present invention because it can achieve both a high refractive index, heat resistance, and light resistance.
　シロキサン結合を有し、かつアリール基が直結したケイ素原子を含有するシリコーン樹脂としては、シロキサン結合を有し、かつフェニル基が直結したケイ素原子を含有するシリコーン樹脂、シロキサン結合を有し、かつメチル基とフェニル基がそれぞれ直結したケイ素原子を含有するシリコーン樹脂等が挙げられる。また、シロキサン結合を有し、かつナフチル基が直結したケイ素原子を含有するシリコーン樹脂としては、シロキサン結合を有し、かつメチル基とナフチル基がそれぞれ直結したケイ素原子を含有するシリコーン樹脂、シロキサン結合を有し、かつメチル基、フェニル基およびナフチル基がそれぞれ直結したケイ素原子を含有するシリコーン樹脂等が挙げられる。 The silicone resin having a siloxane bond and containing a silicon atom directly bonded to an aryl group includes a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a phenyl group, a siloxane bond, and a methyl resin. And a silicone resin containing a silicon atom in which a group and a phenyl group are directly connected. In addition, as a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group, a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a methyl group and a naphthyl group, and a siloxane bond And a silicone resin containing a silicon atom having a methyl group, a phenyl group and a naphthyl group directly bonded to each other.
　なお、メチル基とフェニル基がそれぞれ直結したケイ素原子を含有するシリコーン樹脂においては、１つのケイ素原子にメチル基とフェニル基とが直結している場合と、メチル基が直結したケイ素原子とフェニル基が直結したケイ素原子とをそれぞれ有する場合の両方が含まれる。このことは、メチル基、フェニル基およびナフチル基がそれぞれ直結したケイ素原子を含有するシリコーン樹脂についても同様である。 In addition, in a silicone resin containing a silicon atom in which a methyl group and a phenyl group are directly bonded, a case in which a methyl group and a phenyl group are directly bonded to one silicon atom, and a silicon atom and a phenyl group in which a methyl group is directly bonded And each having a silicon atom directly connected to each other. The same applies to a silicone resin containing a silicon atom in which a methyl group, a phenyl group, and a naphthyl group are directly connected.
　マトリックス樹脂としてのシリコーン樹脂について、より詳細に説明する。ケイ素原子に結合したアルケニル基を有するシリコーンと、ケイ素原子に結合した水素原子を有するシリコーンと、ヒドロシリル化反応用触媒として白金系触媒とを含む付加反応硬化型シリコーン組成物が、マトリックス樹脂（シリコーン樹脂）として好ましい。例えば、このシリコーン樹脂として、東レ・ダウコーニング（株）製封止材“ＯＥ６６３０”、“ＯＥ６６３６”などや信越化学工業株式会社製の“ＳＣＲ－１０１２”、“ＳＣＲ１０１６”などを用いることができる。特に、本発明の実施の形態に係る蛍光体組成物のマトリックス樹脂としては、後述する（Ａ）～（Ｄ）の組成を含む架橋性シリコーン組成物をヒドロシリル化反応してなる架橋物であることが特に好ましい。この架橋物は、６０℃～２５０℃で貯蔵弾性率が減少し、加熱によって高い接着力が得られるため、接着剤不要の蛍光体シート用のマトリックス樹脂として好ましく用いることができる。以下、この架橋物は、熱融着樹脂と適宜称される。 The silicone resin as the matrix resin will be described in more detail. An addition reaction curable silicone composition comprising a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a platinum-based catalyst as a hydrosilylation reaction catalyst is a matrix resin (silicone resin). ) Is preferred. For example, as the silicone resin, sealing materials “OE6630” and “OE6636” manufactured by Toray Dow Corning Co., Ltd., “SCR-1012” and “SCR1016” manufactured by Shin-Etsu Chemical Co., Ltd. can be used. In particular, the matrix resin of the phosphor composition according to the embodiment of the present invention is a cross-linked product obtained by hydrosilylation reaction of a cross-linkable silicone composition including the compositions (A) to (D) described later. Is particularly preferred. This crosslinked product can be preferably used as a matrix resin for a phosphor sheet that does not require an adhesive because the storage elastic modulus decreases at 60 ° C. to 250 ° C. and a high adhesive force is obtained by heating. Hereinafter, this crosslinked product is appropriately referred to as a heat-sealing resin.
　（Ａ）の組成（（Ａ）成分）は、（Ｒ1 2ＳｉＯ2/2）a（Ｒ1ＳｉＯ3/2）b（Ｒ2Ｏ1/2）cという平均単位式で表されるオルガノポリシロキサンである。この平均単位式において、Ｒ1は、フェニル基、炭素原子数１～６のアルキル基もしくはシクロアルキル基、または炭素原子数２～６のアルケニル基である。ただし、Ｒ1の６５～７５モル％はフェニル基であり、Ｒ1の１０～２０モル％はアルケニル基である。Ｒ2は、水素原子または炭素原子数１～６のアルキル基である。ａ、ｂ、およびｃは、０．５≦ａ≦０．６、０．４≦ｂ≦０．５、０≦ｃ≦０．１、かつａ＋ｂ＝１を満たす数である。 The composition of (A) (component (A)) is an organo represented by an average unit formula of (R 1 2 SiO 2/2 ) a (R 1 SiO 3/2 ) b (R 2 O 1/2 ) c Polysiloxane. In this average unit formula, 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. However, 65 to 75 mol% of R 1 is a phenyl group, 10-20 mol% of R 1 is an alkenyl group. R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a, b, and c are numbers satisfying 0.5 ≦ a ≦ 0.6, 0.4 ≦ b ≦ 0.5, 0 ≦ c ≦ 0.1, and a + b = 1.
　（Ｂ）の組成（（Ｂ）成分）は、Ｒ3 3ＳｉＯ（Ｒ3 2ＳｉＯ）ｍＳｉＲ3 3という一般式で表されるオルガノポリシロキサンである。この（Ｂ）成分は、（Ａ）成分の１００重量部に対して５～１５重量部のものである。また、この一般式において、Ｒ3は、フェニル基、炭素原子数１～６のアルキル基もしくはシクロアルキル基、または炭素原子数２～６のアルケニル基である。ただし、Ｒ3の４０～７０モル％はフェニル基であり、Ｒ3の少なくとも１個はアルケニル基である。ｍは、５～５０の整数である。 The composition (B) (component (B)) is an organopolysiloxane represented by the general formula R 3 3 SiO (R 3 2 SiO) m SiR 3 3 . The component (B) is 5 to 15 parts by weight based on 100 parts by weight of the component (A). In this general formula, 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. However, 40 to 70 mol% of R 3 is a phenyl group, at least one R 3 is an alkenyl group. m is an integer of 5 to 50.
　（Ｃ）の組成（（Ｃ）成分）は、（ＨＲ4 2ＳｉＯ）2ＳｉＲ4 2という一般式で表されるオルガノトリシロキサンである。この（Ｃ）成分は、（Ａ）成分中と（Ｂ）成分中とのアルケニル基の合計に対する当該（Ｃ）成分中のケイ素原子結合水素原子のモル比が０.５～２となる量のものである。また、この一般式において、Ｒ4は、フェニル基、または炭素原子数１～６のアルキル基もしくはシクロアルキル基である。ただし、Ｒ4の３０～７０モル％は、フェニル基である。 The composition of (C) (component (C)) is an organotrisiloxane represented by the general formula of (HR 4 2 SiO) 2 SiR 4 2 . The component (C) is an amount such that the molar ratio of silicon-bonded hydrogen atoms in the component (C) to the total of alkenyl groups in the component (A) and the component (B) is 0.5 to 2. Is. In this general formula, R 4 is a phenyl group, or an alkyl or cycloalkyl group having 1 to 6 carbon atoms. However, 30 to 70 mol% of R 4 is a phenyl group.
　（Ｄ）の組成（（Ｄ）成分）は、ヒドロシリル化反応用触媒である。この（Ｄ）成分は、（Ａ）成分中および（Ｂ）成分中のアルケニル基と（Ｃ）成分中のケイ素原子結合水素原子とのヒドロシリル化反応を促進するに十分な触媒量のものである。 (D) composition (component (D)) is a hydrosilylation catalyst. This component (D) has a catalytic amount sufficient to promote the hydrosilylation reaction between the alkenyl group in component (A) and component (B) and the silicon atom-bonded hydrogen atom in component (C). .
　（Ａ）成分の平均単位式において、ａ、ｂ、およびｃの値が上記条件を満たす場合、得られる架橋物の室温での十分な硬さが得られ、かつ高温での軟化が得られる。（Ｂ）成分の一般式において、フェニル基の含有量が上記範囲の下限未満である場合、得られる架橋物の高温での軟化が不十分である。一方、フェニル基の含有量が上記範囲の上限を超える場合、得られる架橋物の透明性が失われ、その機械的強度も低下する。また、（Ｂ）成分の一般式中、Ｒ3の少なくとも１個は、アルケニル基である。これは、（Ｂ）成分がアルケニル基を有さない場合、（Ｂ）成分が架橋反応に取り込まれず、この結果、得られる架橋物から（Ｂ）成分がブリードアウトするおそれがあるからである。また、（Ｂ）成分の一般式中、ｍは、上述したように、５～５０の範囲内の整数である。これは、得られる架橋物の機械的強度を維持しつつ取扱作業性を保持することを可能にするための範囲である。 In the average unit formula of the component (A), when the values of a, b, and c satisfy the above conditions, sufficient hardness of the resulting crosslinked product at room temperature can be obtained, and softening at high temperature can be obtained. In the general formula of the component (B), when the content of the phenyl group is less than the lower limit of the above range, the resulting crosslinked product is not sufficiently softened at a high temperature. On the other hand, when the content of the phenyl group exceeds the upper limit of the above range, the resulting crosslinked product loses its transparency and its mechanical strength also decreases. In the general formula of component (B), at least one R 3 is an alkenyl group. This is because when the component (B) does not have an alkenyl group, the component (B) is not taken into the crosslinking reaction, and as a result, the component (B) may bleed out from the resulting crosslinked product. In the general formula of component (B), m is an integer in the range of 5 to 50 as described above. This is a range for making it possible to maintain handling workability while maintaining the mechanical strength of the resulting crosslinked product.
　また、（Ｂ）成分の含有量は、上述したように、（Ａ）成分の１００重量部に対して５～１５重量部の範囲内となる量である。この含有量の範囲は、得られる架橋物の高温での十分な軟化を得るための範囲である。 Further, as described above, 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.
　（Ｃ）成分の一般式において、上述したように、Ｒ4は、フェニル基、または炭素原子数１～６のアルキル基もしくはシクロアルキル基である。Ｒ4のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘプチル基が例示される。Ｒ4のシクロアルキル基としては、シクロペンチル基、シクロヘプチル基が例示される。また、Ｒ4のうち、フェニル基の含有量は、上述したように、３０～７０モル％の範囲内である。これは、得られる架橋物の高温での十分な軟化が得られ、かつ透明性と機械的強度を保つことを可能にするための範囲である。 In the general formula of component (C), as described above, R 4 is a phenyl group, or an alkyl or cycloalkyl group having 1 to 6 carbon atoms. Examples of the 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. Examples of the cycloalkyl group represented by R 4 include a cyclopentyl group and a cycloheptyl group. Further, in R 4 , the phenyl group content is in the range of 30 to 70 mol% as described above. This is a range for obtaining sufficient softening at a high temperature of the obtained crosslinked product and maintaining transparency and mechanical strength.
　また、（Ｃ）成分の含有量は、上述したように、（Ａ）成分中および（Ｂ）成分中のアルケニル基の合計に対して、（Ｃ）成分中のケイ素原子結合水素原子のモル比が０.５～２の範囲内となる量である。この含有量の範囲は、得られる架橋物の室温での十分な硬さが得られるための範囲である。 Further, the content of the component (C) is, as described above, the molar ratio of silicon-bonded hydrogen atoms in the component (C) to the total of alkenyl groups in the component (A) and the component (B). Is an amount in the range of 0.5-2. The range of this content is a range for obtaining sufficient hardness at room temperature of the obtained crosslinked product.
　（Ｄ）成分は、（Ａ）成分中および（Ｂ）成分中のアルケニル基と（Ｃ）成分中のケイ素原子結合水素原子とのヒドロシリル化反応を促進するためのヒドロシリル化反応用触媒である。（Ｄ）成分としては、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示され、シリコーン組成物の硬化を著しく促進できることから、白金系触媒が好ましい。この白金系触媒としては、白金微粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金－アルケニルシロキサン錯体、白金－オレフィン錯体、白金－カルボニル錯体が例示され、特に、白金－アルケニルシロキサン錯体であることが好ましい。このアルケニルシロキサンとしては、１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン、１，３，５，７－テトラメチル－１，３，５，７－テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等で置換したアルケニルシロキサン、これらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンが例示される。特に、この白金－アルケニルシロキサン錯体の安定性が良好であることから、１，３－ジビニル－１，１，３，３－トテラメチルジシロキサンが好ましい。 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). Examples of the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the silicone composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable. Examples of the alkenyl siloxane 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. In particular, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good.
　また、この白金－アルケニルシロキサン錯体の安定性を向上させることができることから、この錯体に１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン、１，３－ジアリル－１，１，３，３－テトラメチルジシロキサン、１，３－ジビニル－１，３－ジメチル－１，３－ジフェニルジシロキサン、１，３－ジビニル－１，１，３，３－テトラフェニルジシロキサン、１，３，５，７－テトラメチル－１，３，５，７－テトラビニルシクロテトラシロキサン等のアルケニルシロキサンやジメチルシロキサンオリゴマー等のオルガノシロキサンオリゴマーを添加することが好ましく、特に、アルケニルシロキサンを添加することが好ましい。 Further, since the stability of this platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1 can be added to this complex. , 3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, , 3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and other alkenyl siloxanes, and dimethylsiloxane oligomers and other organosiloxane oligomers are preferably added. It is preferable.
　また、（Ｄ）成分の含有量は、（Ａ）成分中および（Ｂ）成分中のアルケニル基と（Ｃ）成分中のケイ素原子結合水素原子とのヒドロシリル化反応を促進するために十分な量であれば、特に限定されない。このような（Ｄ）成分の含有量は、シリコーン組成物に対して、（Ｄ）成分中の金属原子が質量単位で０.０１～５００ｐｐｍの範囲内となる量であることが好ましく、さらには、０.０１～１００ｐｐｍの範囲内となる量であることが好ましく、特には、０.０１～５０ｐｐｍの範囲内となる量であることが好ましい。これは、得られるシリコーン組成物が十分に架橋し、かつ着色等の問題を生じさせないことを可能にするための範囲である。 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). If it is, it will not be specifically limited. The content of such component (D) is preferably an amount such that the metal atom in component (D) is in the range of 0.01 to 500 ppm by mass with respect to the silicone composition, The amount is preferably in the range of 0.01 to 100 ppm, and particularly preferably in the range of 0.01 to 50 ppm. This is a range for allowing the obtained silicone composition to be sufficiently crosslinked and not to cause problems such as coloring.
　マトリックス樹脂としてのシリコーン樹脂（シリコーン組成物）は、少なくとも上記（Ａ）成分、（Ｂ）成分、（Ｃ）成分および（Ｄ）成分からなるが、その他任意の成分として、アルキンアルコール、エンイン化合物、反応抑制剤を含有してもよい。このアルキンアルコールとして、エチニルヘキサノール、２－メチル－３－ブチン－２－オール、３,５－ジメチル－１－ヘキシン－３－オール、２－フェニル－３－ブチン－２－オール等が挙げられる。このエンイン化合物として、３－メチル－３－ペンテン－１－イン、３，５－ジメチル－３－ヘキセン－１－イン等が挙げられる。この反応抑制剤として、１，３，５，７－テトラメチル－１，３，５，７－テトラビニルシクロテトラシロキサン、１，３，５，７－テトラメチル－１，３，５，７－テトラヘキセニルシクロテトラシロキサン、ベンゾトリアゾール等が挙げられる。また、この反応抑制剤の含有量は、特に限定されないが、シリコーン組成物の重量に対して１～５，０００ｐｐｍの範囲内であることが好ましい。このように反応抑制剤の含有量を調整することにより、得られる架橋物の貯蔵弾性率を調整することもできる。 The silicone resin (silicone composition) as the matrix resin is composed of at least the above component (A), component (B), component (C) and component (D), but as other optional components, alkyne alcohol, enyne compound, You may contain reaction inhibitor. Examples of the alkyne alcohol include ethynylhexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol. Examples of the enyne compound include 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne. As this reaction inhibitor, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7- Examples include tetrahexenylcyclotetrasiloxane and benzotriazole. The content of the reaction inhibitor is not particularly limited, but is preferably in the range of 1 to 5,000 ppm with respect to the weight of the silicone composition. Thus, the storage elastic modulus of the obtained crosslinked product can be adjusted by adjusting the content of the reaction inhibitor.
（溶媒）
　本発明の実施の形態に係る蛍光体組成物は、溶媒を含んでいてもよい。この溶媒は、流動状態の樹脂の粘度を調整できるものであれば、特に限定されない。例えば、トルエン、メチルエチルケトン、メチルイソブチルケトン、ヘキサン、アセトン、テルピネオール、テキサノール、メチルセルソルブ、ブチルカルビトール、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。 (solvent)
The phosphor composition according to the embodiment of the present invention may contain a solvent. The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a fluid state. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like can be mentioned.
（その他の成分）
　本発明の実施の形態に係る蛍光体組成物は、塗布膜安定化のための分散剤やレベリング剤、蛍光体シートとした場合のシート表面の改質剤としてシランカップリング剤等の接着補助剤等を含有していてもよい。 (Other ingredients)
The phosphor composition according to the embodiment of the present invention includes a dispersing agent and a leveling agent for stabilizing a coating film, and an adhesion assistant such as a silane coupling agent as a sheet surface modifier when a phosphor sheet is used. Etc. may be contained.
　また、本発明の実施の形態に係る蛍光体組成物は、微粒子を含有していてもよい。この微粒子の例としては、シリコーン微粒子やチタニア、シリカ、アルミナ、シリコーン、ジルコニア、セリア、窒化アルミニウム、炭化ケイ素、窒化ケイ素、チタン酸バリウムなどが挙げられる。入手しやすいという観点から、シリコーン微粒子、シリカ微粒子、アルミナ微粒子が、上記微粒子として好ましく用いられる。 Moreover, the phosphor composition according to the embodiment of the present invention may contain fine particles. Examples of the fine particles include silicone fine particles, titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate. From the viewpoint of easy availability, silicone fine particles, silica fine particles, and alumina fine particles are preferably used as the fine particles.
　また、本発明の実施の形態に係る蛍光体組成物は、１００℃における貯蔵弾性率（Ｇ’）を低下させるため、加熱粘着剤として、シラノール基含有メチルフェニル系シリコーンレジンを含有してもよい。このシラノール基含有メチルフェニル系シリコーンレジンの構造は、下記一般式（Ｅ）で表されるものであることが特に好ましい。
（Ｒ5ＳｉＯ3）d（ＰｈＳｉＯ3）e（Ｒ5ＯＨＳｉＯ2）f（ＰｈＯＨＳｉＯ2）g（Ｒ6ＳｉＯ2）h　　　　　・・・一般式（Ｅ） In addition, the phosphor composition according to the embodiment of the present invention may contain a silanol group-containing methylphenyl silicone resin as a heating adhesive in order to reduce the storage elastic modulus (G ′) at 100 ° C. . The structure of this silanol group-containing methylphenyl silicone resin is particularly preferably the one represented by the following general formula (E).
(R 5 SiO 3 ) d (PhSiO 3 ) e (R 5 OHSiO 2 ) f (PhOHSiO 2 ) g (R 6 SiO 2 ) h ... General formula (E)
　一般式（Ｅ）において、Ｒ5およびＲ6は、それぞれ炭素数１～６のアルキル基もしくはシクロアルキル基である。Ｐｈは、フェニル基である。ｄ、ｅ、ｆ、ｇおよびｈは、２０≦ｄ≦４０、２０≦ｅ≦４０、５≦ｆ≦１５、５≦ｇ≦１５、２０≦ｈ≦４０、かつｄ＋ｅ＋ｆ＋ｇ＋ｈ＝１００を満たす数である。 In the general formula (E), R 5 and R 6 are each an alkyl group or cycloalkyl group having 1 to 6 carbon atoms. Ph is a phenyl group. d, e, f, g, and h are numbers satisfying 20 ≦ d ≦ 40, 20 ≦ e ≦ 40, 5 ≦ f ≦ 15, 5 ≦ g ≦ 15, 20 ≦ h ≦ 40, and d + e + f + g + h = 100. .
＜蛍光体組成物の製造方法＞
　以下に、本発明の実施の形態に係る蛍光体組成物の製造方法の一例を説明する。この製造方法では、前述した、一般式（１）で表される有機化合物、無機蛍光体およびマトリックス樹脂、並びに必要に応じてシリコーン微粒子および溶剤等を所定量混合する。上記の成分を所定の組成になるよう混合した後、ホモジナイザー、自公転型攪拌機、３本ローラー、ボールミル、遊星式ボールミル、ビーズミル等の撹拌・混練機で均質に混合分散することで、蛍光体組成物が得られる。混合分散後、もしくは混合分散の過程で、真空もしくは減圧条件下で脱泡することも好ましく行われる。また、ある特定の成分を事前に混合することや、エージング等の処理をしても構わない。エバポレーターによって溶剤を除去して所望の固形分濃度にすることも可能である。 <Method for producing phosphor composition>
Below, an example of the manufacturing method of the phosphor composition which concerns on embodiment of this invention is demonstrated. In this production method, the organic compound represented by the general formula (1), the inorganic phosphor and the matrix resin, and the silicone fine particles and the solvent as required are mixed in a predetermined amount. After mixing the above components to a predetermined composition, the phosphor composition is uniformly mixed and dispersed with an agitator / kneader such as a homogenizer, a self-revolving stirrer, a 3-roller, a ball mill, a planetary ball mill, or a bead mill. A thing is obtained. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing. Further, a specific component may be mixed in advance or a process such as aging may be performed. It is also possible to remove the solvent with an evaporator to obtain a desired solid content concentration.
＜形成物＞
　本発明の実施の形態に係る形成物は、上述した蛍光体組成物またはその硬化物を含有する蛍光体形成物である。例えば、本発明の一つの実施形態である形成物は、上述した無機蛍光体および一般式（１）で表される有機化合物と、マトリックス樹脂またはその硬化物とを含有する。これらの無機蛍光体、一般式（１）で表される有機化合物およびマトリックス樹脂、ならびにその他に本発明の形成物に含まれていてもよい成分については、上述の蛍光体組成物におけるものと同様である。この形成物は、上述の蛍光体組成物や後述の蛍光体シートを成型して得ることができる。この形成物の製造では、必要に応じ、蛍光体組成物や蛍光体シートの成型工程においてマトリックス樹脂が硬化されていてもよい。 <Formation>
The formed product according to the embodiment of the present invention is a phosphor formed product containing the above-described phosphor composition or a cured product thereof. For example, a formed product according to one embodiment of the present invention contains the above-described inorganic phosphor and the organic compound represented by the general formula (1), and a matrix resin or a cured product thereof. These inorganic phosphors, the organic compound represented by the general formula (1), the matrix resin, and other components that may be contained in the formed product of the present invention are the same as those in the phosphor composition described above. It is. This formed product can be obtained by molding the above-described phosphor composition or a phosphor sheet described later. In the production of the formed product, the matrix resin may be cured in the molding process of the phosphor composition or the phosphor sheet, if necessary.
　本発明の形成物の形態としては、特に限定はなく、例えば、発光ダイオード形状に合わせたキャップ形状やシート形状等を挙げることができる。形成物をキャップ形状とするには、例えば、本発明の実施の形態に係る蛍光体組成物を、金型と加熱プレス機とを用いることにより、キャップ形状に成型すればよい。また、形成物をシート形状とするには、後述する蛍光体シートの製造方法を用いることができる。 The form of the formed product of the present invention is not particularly limited, and examples thereof include a cap shape and a sheet shape according to the light emitting diode shape. In order to make the formed product into a cap shape, for example, the phosphor composition according to the embodiment of the present invention may be formed into a cap shape by using a mold and a heat press. Moreover, in order to make a formation into a sheet shape, the manufacturing method of the fluorescent substance sheet mentioned later can be used.
　本発明の実施の形態に係る形成物は、リモートフォスファ用の形成物として用いることができる。リモートフォスファ技術とは、光源となる青色ＬＥＤから離れた位置に、蛍光体を練りこんだ３次元形状形成物を配置する技術である。リモートフォスファ技術では、蛍光体が青色ＬＥＤから離れているため、熱による蛍光体の劣化が少なく、光学特性が安定し製品バラツキをきわめて少なくすることが特徴である。本発明の実施の形態に係る形成物は、リモートフォスファ技術を用いたＬＥＤモジュール、例えば、トーチやスポットライト、クリップライト等のＬＥＤ照明に用いることができる。 The formation according to the embodiment of the present invention can be used as a formation for a remote phosphor. The remote phosphor technique is a technique in which a three-dimensional shape formed with a phosphor is kneaded at a position away from a blue LED serving as a light source. The remote phosphor technology is characterized in that since the phosphor is separated from the blue LED, there is little deterioration of the phosphor due to heat, the optical characteristics are stable, and the product variation is extremely small. The formed product according to the embodiment of the present invention can be used for an LED module using a remote phosphor technology, for example, an LED illumination such as a torch, a spotlight, and a clip light.
＜蛍光体シート＞
　本発明の実施の形態に係る蛍光体シートは、上述した蛍光体組成物をフィルム化したもの（シート形状に成型したもの）であり、一般式（１）で表される有機化合物と、無機蛍光体と、マトリックス樹脂またはその硬化物とを含有する。本実施の形態に係る蛍光シートおいて、これらの有機化合物および無機蛍光体は、各々、発光体からの発光光をこの発光光よりも長波長の光へ変換するものである。また、蛍光体シートに含有のマトリックス樹脂は、少なくとも上記無機蛍光体と混合して連続相を形成する樹脂である。これらの無機蛍光体、一般式（１）で表される有機化合物およびマトリックス樹脂、ならびにその他に本発明の蛍光体シートに含まれていてもよい成分については、上述の蛍光体組成物におけるものと同様である。また、蛍光体シートにおける有機発光材料（一般式（１）で表される有機化合物）と無機蛍光体との色変換の関係についても、上述の蛍光体組成物におけるものと同様である。 <Phosphor sheet>
The phosphor sheet according to the embodiment of the present invention is a film obtained by forming the above-described phosphor composition into a film (molded into a sheet shape), an organic compound represented by the general formula (1), and inorganic fluorescence. And a matrix resin or a cured product thereof. In the phosphor sheet according to the present embodiment, these organic compounds and inorganic phosphors each convert light emitted from the light emitter into light having a longer wavelength than the light emitted. The matrix resin contained in the phosphor sheet is a resin that forms a continuous phase by mixing with at least the inorganic phosphor. These inorganic phosphors, the organic compound represented by the general formula (1), the matrix resin, and other components that may be contained in the phosphor sheet of the present invention are the same as those in the phosphor composition described above. It is the same. Further, the color conversion relationship between the organic light emitting material (organic compound represented by the general formula (1)) and the inorganic phosphor in the phosphor sheet is the same as that in the phosphor composition described above.
　本発明において、蛍光体シートの厚みは、特に制限はないが、１０～１０００μｍの範囲内であることが好ましい。蛍光体シートの厚みが１０μｍより小さいと、蛍光体粒子に起因する凹凸のため、蛍光体シートの均一なシート成型が難しい。蛍光体シートの厚みが１０００μｍを超えると、クラックが生じやすくなり、蛍光体シートのシート成型が難しい。蛍光体シートのより好ましい厚みは、３０～１００μｍである。一方、蛍光体シートの耐熱性を高めるという観点からは、蛍光体シートの厚みは、２００μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、５０μｍ以下であることがさらに好ましい。 In the present invention, the thickness of the phosphor sheet is not particularly limited, but is preferably in the range of 10 to 1000 μm. When the thickness of the phosphor sheet is smaller than 10 μm, it is difficult to form a uniform sheet of the phosphor sheet due to the unevenness caused by the phosphor particles. If the thickness of the phosphor sheet exceeds 1000 μm, cracks are likely to occur, and it is difficult to mold the phosphor sheet. A more preferable thickness of the phosphor sheet is 30 to 100 μm. On the other hand, from the viewpoint of enhancing the heat resistance of the phosphor sheet, the thickness of the phosphor sheet is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.
　また、本発明において、蛍光体シートは、保管性、運搬性および加工性の観点から、室温付近で弾性が高いことが好ましい。一方で、蛍光体シートは、ＬＥＤチップの形状に追従するように変形し、かつＬＥＤチップの光取出し面に密着させるという観点から、一定の温度条件下で弾性が低くなり、柔軟性、密着性、流動性を発現することが好ましい。このような蛍光体シートの粘弾性挙動としては、以下の条件（ｉ）～（ｉｉｉ）を満たすことが望ましい。 In the present invention, the phosphor sheet preferably has high elasticity near room temperature from the viewpoints of storage properties, transportability, and processability. On the other hand, the phosphor sheet is deformed so as to follow the shape of the LED chip and is in close contact with the light extraction surface of the LED chip. It is preferable to exhibit fluidity. As the viscoelastic behavior of such a phosphor sheet, it is desirable to satisfy the following conditions (i) to (iii).
　条件（ｉ）は、「温度２５℃において、蛍光体シートの貯蔵弾性率Ｇ’が１．０×１０4Ｐａ≦Ｇ’≦１．０×１０6Ｐａであり、かつ蛍光体シートの損失正接（ｔａｎδ）がｔａｎδ＜１である」というものである。条件（ｉｉ）は、「温度１００℃において、貯蔵弾性率Ｇ’が１．０×１０2Ｐａ≦Ｇ’＜１．０×１０4Ｐａであり、かつ蛍光体シートの損失正接がｔａｎδ≧１である」というものである。条件（ｉｉｉ）は、「温度２００℃において、貯蔵弾性率Ｇ’が１．０×１０4Ｐａ≦Ｇ’≦１．０×１０6Ｐａであり、かつ蛍光体シートの損失正接がｔａｎδ＜１である」というものである。 Condition (i) is: “At 25 ° C., the storage elastic modulus G ′ of the phosphor sheet is 1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa and the loss tangent of the phosphor sheet (Tan δ) is tan δ <1 ”. Condition (ii) is: “At a temperature of 100 ° C., the storage elastic modulus G ′ is 1.0 × 10 2 Pa ≦ G ′ <1.0 × 10 4 Pa, and the loss tangent of the phosphor sheet is tan δ ≧ 1. Is. Condition (iii) is: “At a temperature of 200 ° C., the storage elastic modulus G ′ is 1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa, and the loss tangent of the phosphor sheet is tan δ <1. Is.
　ここでいう蛍光体シートの貯蔵弾性率Ｇ’とは、レオメーターにより蛍光体シートの動的粘弾性測定（温度依存性）を行った場合の貯蔵弾性率である。動的粘弾性測定（温度依存性）とは、材料に対してある正弦周波数で剪断歪みを加えたときに、定常状態に達した場合に現れる剪断応力を、剪断歪みと位相の一致する応力成分（弾性的成分）と、剪断歪みと位相が９０°遅れた応力成分（粘性的成分）とに分解して、材料の動的な力学特性を解析する手法である。動的粘弾性測定（温度依存性）は、一般的な粘度・粘弾性測定装置を用いて行うことができる。本発明において、蛍光体シートの貯蔵弾性率Ｇ’は、以下の条件にて動的粘弾性測定（温度依存性）を行った場合の値とする。 Here, the storage elastic modulus G ′ of the phosphor sheet is a storage elastic modulus when the dynamic viscoelasticity measurement (temperature dependence) of the phosphor sheet is performed with a rheometer. Dynamic viscoelasticity measurement (temperature dependence) is a stress component whose phase matches the shear stress that appears when a steady state is reached when shear strain is applied to a material at a certain sine frequency. This is a technique for analyzing the dynamic mechanical properties of a material by breaking it down into (elastic component) and a stress component (viscous component) whose phase is delayed by 90 °. Dynamic viscoelasticity measurement (temperature dependence) can be performed using a general viscosity / viscoelasticity measuring apparatus. In the present invention, the storage elastic modulus G ′ of the phosphor sheet is a value when dynamic viscoelasticity measurement (temperature dependence) is performed under the following conditions.
　動的粘弾性測定（温度依存性）の条件として、測定装置は、粘度・粘弾性測定装置ＨＡＡＫＥ　ＭＡＲＳIII（Ｔｈｅｒｍｏ　Ｆｉｓｈｅｒ　ＳＣＩＥＮＴＩＦＩＣ製）である。測定条件は、ＯＳＣ温度依存測定である。ジオメトリーは、平行円板型（２０ｍｍ）である。測定時間は、１９８０秒である。角周波数は、１Ｈｚである。角速度は、６．２８３２ｒａｄ／秒である。温度範囲は、２５～２００℃（低温温度制御機能あり）である。昇温速度は、０．０８３３３℃／秒である。サンプル形状は、円形（直径１８ｍｍ）である。 As a condition for dynamic viscoelasticity measurement (temperature dependence), the measuring device is a viscosity / viscoelasticity measuring device HAAKE MARSIII (manufactured by Thermo Fisher SCIENTIFIC). The measurement condition is OSC temperature-dependent measurement. The geometry is a parallel disk type (20 mm). The measurement time is 1980 seconds. The angular frequency is 1 Hz. The angular velocity is 6.2832 rad / sec. The temperature range is 25 to 200 ° C. (with low temperature temperature control function). The heating rate is 0.08333 ° C./second. The sample shape is circular (diameter 18 mm).
　ここで、蛍光体シートの剪断歪みに位相が一致する応力成分をこの剪断歪みで除したものが、蛍光体シートの貯蔵弾性率Ｇ’である。この貯蔵弾性率Ｇ’は、各温度における動的な歪みに対する材料の弾性を表すものであるので、蛍光体シートの硬さ、すなわち加工性に密接に関連している。一方、蛍光体シートの剪断歪みと位相が９０°遅れた応力成分をこの剪断歪みで除したものが、蛍光体シートの損失弾性率Ｇ”である。この損失弾性率Ｇ”は、材料の粘性を表すものであるので、蛍光体シートの流動性、すなわち密着性に密接に関連している。 Here, the storage elastic modulus G ′ of the phosphor sheet is obtained by dividing the stress component whose phase is coincident with the shear strain of the phosphor sheet by the shear strain. Since the storage elastic modulus G ′ represents the elasticity of the material against dynamic strain at each temperature, it is closely related to the hardness of the phosphor sheet, that is, processability. On the other hand, the loss elastic modulus G ″ of the phosphor sheet is obtained by dividing the stress component whose phase is delayed by 90 ° from the shear strain of the phosphor sheet by the shear strain. This loss elastic modulus G ″ is the viscosity of the material. Therefore, it is closely related to the fluidity of the phosphor sheet, that is, the adhesion.
　また、損失弾性率Ｇ”を貯蔵弾性率Ｇ’で除したものが、蛍光体シートの損失正接（ｔａｎδ）である。このｔａｎδは、材料が置かれている状態を示す指標となる。例えば、ｔａｎδが１未満であれば、弾性が支配的であり、蛍光体シートは、固体の状態である。一方、ｔａｎδが１以上であれば、粘性が支配的であり、蛍光体シートは、液体の状態である。 Further, the loss tangent (tan δ) of the phosphor sheet is obtained by dividing the loss elastic modulus G ″ by the storage elastic modulus G ′. This tan δ is an index indicating the state in which the material is placed. If tan δ is less than 1, the elasticity is dominant and the phosphor sheet is in a solid state, whereas if tan δ is 1 or more, the viscosity is dominant and the phosphor sheet is liquid. State.
　本発明において、蛍光体シートは、上述の条件（ｉ）「２５℃において１．０×１０4Ｐａ≦Ｇ’≦１．０×１０6Ｐａであり、かつｔａｎδ＜１である」を満たすことにより、室温（２５℃）において十分に弾性的である。そのため、刃体による切断加工などの早い剪断応力に対しても、蛍光体シートが周囲の変形無しに切断され、この結果、蛍光体シートの高い寸法精度での加工性が得られる。蛍光体シートの２５℃における貯蔵弾性率Ｇ’は、ハンドリング時の割れ防止や加工性の観点から、より好ましくは、９．０×１０5Ｐａ以下である。蛍光体シートの室温におけるｔａｎδは、貼り付け温度の低温化の観点から、０．７以下であることがより好ましい。また、このｔａｎδの下限は、特に制限はないが、０．１以上であることが好ましく、０．２以上であることがより好ましく、０．２５以上であることがさらに好ましい。 In the present invention, the phosphor sheet satisfies the above-mentioned condition (i) “1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa and tan δ <1 at 25 ° C.” Therefore, it is sufficiently elastic at room temperature (25 ° C.). For this reason, the phosphor sheet is cut without deformation of the surroundings even with a fast shearing stress such as a cutting process with a blade, and as a result, the processability of the phosphor sheet with high dimensional accuracy can be obtained. The storage elastic modulus G ′ at 25 ° C. of the phosphor sheet is more preferably 9.0 × 10 5 Pa or less from the viewpoint of crack prevention during handling and workability. The tan δ at room temperature of the phosphor sheet is more preferably 0.7 or less from the viewpoint of lowering the attaching temperature. The lower limit of tan δ is not particularly limited, but is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.25 or more.
　また、蛍光体シートは、上述の条件（ｉｉ）「１００℃において１．０×１０2Ｐａ≦Ｇ’＜１．０×１０4Ｐａであり、かつｔａｎδ≧１である」を満たすことによって、１００℃において十分に粘性的であり、流動性が高い。そのため、この物性を備えた蛍光体シートを１００℃以上で加熱しながらＬＥＤチップへの貼り付けを行えば、ＬＥＤチップの発光面の形状に応じて蛍光体シートが素早く流動、変形して、これら蛍光体シートとＬＥＤチップとの高い密着性が得られる。これによって、ＬＥＤチップからの光取出し性が向上し、輝度が向上する。蛍光体シートの１００℃における貯蔵弾性率Ｇ’は、貼り付け温度の低温化の観点から、より好ましくは、９．０×１０3Ｐａ以下である。蛍光体シートの１００℃におけるｔａｎδは、密着性の観点から、１．６以上であることがより好ましい。また、このｔａｎδの上限は、特に制限はないが、４．０以下であることが好ましく、３．６以下であることがより好ましく、３．３以下であることがさらに好ましい。 Further, the phosphor sheet satisfies the above-mentioned condition (ii) “1.0 × 10 2 Pa ≦ G ′ <1.0 × 10 4 Pa and tan δ ≧ 1 at 100 ° C.” It is sufficiently viscous at 100 ° C. and has high fluidity. Therefore, if the phosphor sheet having this physical property is heated to 100 ° C. or higher and attached to the LED chip, the phosphor sheet quickly flows and deforms according to the shape of the light emitting surface of the LED chip. High adhesion between the phosphor sheet and the LED chip can be obtained. Thereby, the light extraction property from the LED chip is improved, and the luminance is improved. The storage elastic modulus G ′ at 100 ° C. of the phosphor sheet is more preferably 9.0 × 10 3 Pa or less from the viewpoint of lowering the bonding temperature. The tan δ at 100 ° C. of the phosphor sheet is more preferably 1.6 or more from the viewpoint of adhesion. The upper limit of tan δ is not particularly limited, but is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably 3.3 or less.
　さらに、蛍光体シートは、上述の条件（ｉｉｉ）「２００℃において１．０×１０4Ｐａ≦Ｇ’≦１．０×１０6Ｐａであり、かつｔａｎδ＜１である」を満たすことによって、最終的にＬＥＤチップを安定的に動作させることができる。何故ならば、ＬＥＤチップへ貼り付けた状態の蛍光体シートを２００℃以上で加熱すれば、この蛍光体シートの完全硬化が完了し、この蛍光体シートに含有の樹脂全体が一体化するので、ＬＥＤチップ点灯時の熱などの熱的要因の影響をこの蛍光体シートが受けなくなるためである。蛍光体シートの２００℃における貯蔵弾性率Ｇ’は、クラック防止の観点から、より好ましくは、９．０×１０5Ｐａ以下である。蛍光体シートの２００℃におけるｔａｎδは、熱安定性の観点から、０．０８以下であることがより好ましい。また、このｔａｎδの下限は、特に制限はないが、０．０１以上であることが好ましく、０．０２以上であることがより好ましく、０．０３以上であることがさらに好ましい。 Furthermore, the phosphor sheet satisfies the above-mentioned condition (iii) “1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa and tan δ <1 at 200 ° C.” Finally, the LED chip can be stably operated. Because, if the phosphor sheet attached to the LED chip is heated at 200 ° C. or higher, complete curing of the phosphor sheet is completed, and the entire resin contained in the phosphor sheet is integrated. This is because the phosphor sheet is not affected by thermal factors such as heat when the LED chip is lit. The storage elastic modulus G ′ at 200 ° C. of the phosphor sheet is more preferably 9.0 × 10 5 Pa or less from the viewpoint of preventing cracks. The tan δ at 200 ° C. of the phosphor sheet is more preferably 0.08 or less from the viewpoint of thermal stability. The lower limit of tan δ is not particularly limited, but is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more.
　蛍光体シートとして上記の貯蔵弾性率Ｇ’が得られるのであれば、そこに含まれる樹脂は、未硬化状態のものであってもよい。また、蛍光体シートの取扱性および保存性等を考慮すると、蛍光体シートに含まれる樹脂は、その全体が一体化した完全硬化ではなく、ある程度硬化している状態であることが好ましい。一例としては、室温保存で１ヶ月以上の長期間、貯蔵弾性率Ｇ’が変化しない程度に、蛍光体シート含有の樹脂の硬化が進行していることが好ましい。 If the above storage elastic modulus G ′ is obtained as a phosphor sheet, the resin contained therein may be in an uncured state. In consideration of handling properties and storage stability of the phosphor sheet, the resin contained in the phosphor sheet is preferably in a state of being cured to some extent rather than being completely cured as a whole. As an example, it is preferable that the curing of the phosphor sheet-containing resin has progressed to such an extent that the storage elastic modulus G ′ does not change for a long period of time of one month or longer when stored at room temperature.
　図１は、本発明の実施の形態に係る蛍光体シートの一例を示す側面図である。図１に示すように、本発明の実施の形態に係る蛍光体シート２は、蛍光体層３４と有機発光材料層３５との積層構造を含むシート状の蛍光体である。蛍光体層３４は、本発明における無機蛍光体３６とマトリックス樹脂とを含有する層である。有機発光材料層３５は、一般式（１）で表される有機化合物を含有する層である。蛍光体シート２は、基材１４の上に、これらの蛍光体層３４と有機発光材料層３５とが形成されてなる。このような蛍光体シート２および基材１４は、基材１４の上に蛍光体層３４と有機発光材料層３５とが順次積層された状態にある積層構造の蛍光体シート積層体３３を構成する。基材１４の上に蛍光体層３４と有機発光材料層３５とを予め積層しておくことは、蛍光体シート２をＬＥＤパッケージに用いた場合に、これらの各層を別々に形成するよりも工程削減に繋がる。 FIG. 1 is a side view showing an example of a phosphor sheet according to an embodiment of the present invention. As shown in FIG. 1, the phosphor sheet 2 according to the embodiment of the present invention is a sheet-like phosphor including a laminated structure of a phosphor layer 34 and an organic light emitting material layer 35. The phosphor layer 34 is a layer containing the inorganic phosphor 36 and the matrix resin in the present invention. The organic light emitting material layer 35 is a layer containing an organic compound represented by the general formula (1). The phosphor sheet 2 is formed by forming the phosphor layer 34 and the organic light emitting material layer 35 on the base material 14. Such a phosphor sheet 2 and the substrate 14 constitute a phosphor sheet laminate 33 having a laminated structure in which the phosphor layer 34 and the organic light emitting material layer 35 are sequentially laminated on the substrate 14. . Preliminarily laminating the phosphor layer 34 and the organic light emitting material layer 35 on the substrate 14 is a process rather than forming each of these layers separately when the phosphor sheet 2 is used in an LED package. It leads to reduction.
　特に図１には示さないが、蛍光体シート２は、蛍光体層３４および有機発光材料層３５以外に、その他の層を備えた積層体であってもよい。例えば、その他の層として、バリア層などが挙げられる。 Although not particularly shown in FIG. 1, the phosphor sheet 2 may be a laminate including other layers in addition to the phosphor layer 34 and the organic light emitting material layer 35. For example, a barrier layer etc. are mentioned as another layer.
（蛍光体層）
　蛍光体層（例えば図１に示す蛍光体層３４等）は、無機蛍光体（粒子状の無機蛍光体３６等）とマトリックス樹脂とを含有する層であり、好ましくは、主として無機蛍光体とマトリックス樹脂とを混合した層である。無機蛍光体、マトリックス樹脂、ならびにその他に本発明の蛍光体層に含まれていてもよい成分については、上述の蛍光体組成物におけるものと同様である。 (Phosphor layer)
The phosphor layer (for example, the phosphor layer 34 shown in FIG. 1) is a layer containing an inorganic phosphor (particulate inorganic phosphor 36, etc.) and a matrix resin, and preferably mainly an inorganic phosphor and a matrix. It is a layer mixed with resin. The inorganic phosphor, the matrix resin, and other components that may be contained in the phosphor layer of the present invention are the same as those in the phosphor composition described above.
（有機発光材料層）
　有機発光材料層（例えば図１に示す有機発光材料層３５等）は、一般式（１）で表される有機化合物を含有する層であり、好ましくは、主として一般式（１）で表される有機化合物とマトリックス樹脂とを混合した層である。一般式（１）で表される有機化合物およびマトリックス樹脂については、上述の蛍光体組成物におけるものと同様である。有機発光材料層は、これらの有機化合物およびマトリックス樹脂以外に、塗布膜安定化のための分散剤やレベリング剤、有機発光材料層とした場合の表面の改質剤としてシランカップリング剤等の接着補助剤等を含有していてもよい。また、有機発光材料層は、微粒子を含有していてもよい。この微粒子の例としては、チタニア、シリカ、アルミナ、シリコーン、ジルコニア、セリア、窒化アルミニウム、炭化ケイ素、窒化ケイ素、チタン酸バリウムなどが挙げられる。これらのうち、入手しやすいという観点から、シリカ微粒子、アルミナ微粒子、シリコーン微粒子が好ましく用いられる。 (Organic light emitting material layer)
The organic light emitting material layer (for example, the organic light emitting material layer 35 shown in FIG. 1) is a layer containing an organic compound represented by the general formula (1), and is preferably represented mainly by the general formula (1). It is a layer in which an organic compound and a matrix resin are mixed. The organic compound and matrix resin represented by the general formula (1) are the same as those in the above-described phosphor composition. In addition to these organic compounds and matrix resins, the organic light-emitting material layer is a bonding agent such as a dispersing agent or leveling agent for stabilizing the coating film, and a silane coupling agent as a surface modifier when used as an organic light-emitting material layer. It may contain adjuvants and the like. The organic light emitting material layer may contain fine particles. Examples of the fine particles include titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate. Of these, silica fine particles, alumina fine particles, and silicone fine particles are preferably used from the viewpoint of easy availability.
（基材）
　基材（例えば図１に示す基材１４等）としては、特に制限無く公知の金属、フィルム、ガラス、セラミック、紙等を使用することができる。具体的には、基材として、アルミニウム（アルミニウム合金も含む）、亜鉛、銅、鉄などの金属板や箔、セルロースアセテート、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン、ポリエステル、ポリアミド、ポリイミド、ポリフェニレンサルファイド、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリビニルアセタール、アラミド、シリコーン、ポリオレフィン、熱可塑性フッ素樹脂、テトラフルオロエチレンとエチレンの共重合体（ＥＴＦＥ）などのプラスチックのフィルム、α－ポリオレフィン樹脂、ポリカプロラクトン樹脂、アクリル樹脂、シリコーン樹脂およびこれらとエチレンの共重合樹脂からなるプラスチックのフィルム、前記プラスチックがラミネートされた紙、または前記プラスチックによりコーティングされた紙、前記金属がラミネートまたは蒸着された紙、前記金属がラミネートまたは蒸着されたプラスチックフィルムなどが挙げられる。また、基材が金属板である場合、その表面にクロム系やニッケル系などのメッキ処理やセラミック処理が施されていてもよい。 (Base material)
As the substrate (for example, the substrate 14 shown in FIG. 1), a known metal, film, glass, ceramic, paper, or the like can be used without particular limitation. Specifically, as a base material, metal (including aluminum alloy), zinc, copper, iron, and other metal plates and foils, cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene , Polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, plastic film such as tetrafluoroethylene and ethylene copolymer (ETFE), α-polyolefin resin, polycaprolactone resin, acrylic resin, silicone Plastic film made of a resin and a copolymer resin of these with ethylene, paper laminated with the plastic, or coated with the plastic Paper was, said metal laminated or vapor-deposited paper, the metals and plastic film laminated or deposited. Moreover, when the base material is a metal plate, the surface thereof may be subjected to a plating treatment or ceramic treatment such as chromium or nickel.
　これらの中でも、蛍光体シート（例えば図１に示す蛍光体シート２等）の作製のし易さや蛍光体シートの個片化のし易さから、ガラスや樹脂フィルムが好ましく用いられる。特に、蛍光体シートをＬＥＤチップに貼りつける際の密着性の観点から、基材は、柔軟なフィルム状であることが好ましい。また、フィルム状の基材を取り扱う際に破断などの恐れがないように、強度が高いフィルムが好ましい。それらの要求特性や経済性の面で樹脂フィルムが好ましく、これらの中でも、経済性、取り扱い性の面でＰＥＴ、ポリフェニレンサルファイド、ポリプロピレンからなる群より選ばれるプラスチックフィルムが好ましい。また、蛍光体シートを乾燥させる場合や蛍光体シートをＬＥＤチップに貼り付ける際に２００℃以上の高温を必要とする場合は、耐熱性の面でポリイミドフィルムが好ましい。シートの剥離のし易さから、基材は、あらかじめ表面が離型処理されていてもよい。 Among these, glass and resin films are preferably used because of the ease of producing a phosphor sheet (for example, the phosphor sheet 2 shown in FIG. 1) and the ease of individualizing the phosphor sheet. In particular, from the viewpoint of adhesion when the phosphor sheet is attached to the LED chip, the substrate is preferably a flexible film. Moreover, a film with high strength is preferable so that there is no fear of breakage when handling a film-like substrate. Resin films are preferred in terms of their required characteristics and economy, and among these, plastic films selected from the group consisting of PET, polyphenylene sulfide, and polypropylene are preferred in terms of economy and handleability. Moreover, when drying a fluorescent substance sheet, or when attaching a fluorescent substance sheet to a LED chip, when a high temperature of 200 degreeC or more is required, a polyimide film is preferable at a heat resistant surface. The surface of the base material may be subjected to a mold release treatment in advance for ease of peeling of the sheet.
　基材の厚さは、特に制限はないが、下限としては２５μｍ以上が好ましく、３８μｍ以上がより好ましい。また、上限としては５０００μｍ以下が好ましく、３０００μｍ以下がより好ましい。 The thickness of the substrate is not particularly limited, but the lower limit is preferably 25 μm or more, and more preferably 38 μm or more. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.
（その他の層）
　蛍光体シートに含まれる上述したその他の層の一例として、バリア層が挙げられる。このバリア層としては、特に制限なく、蛍光体シートに対してガスバリア性を向上する場合などにおいて適宜用いられ、例えば、酸化ケイ素、酸化アルミニウム、酸化スズ、酸化インジウム、酸化イットリウム、酸化マグネシウムなど、またはこれらの混合物、またはこれらに他の元素を添加した金属酸化物薄膜、あるいはポリ塩化ビニリデン、アクリル系樹脂、シリコーン系樹脂、メラミン系樹脂、ウレタン系樹脂、フッ素系樹脂などの各種樹脂から成る膜を挙げることができる。また、水分に対してバリア機能を有する膜としては、例えば、ポリエチレン、ポリプロピレン、ナイロン、ポリ塩化ビニリデン、塩化ビニリデンと塩化ビニル、塩化ビニリデンとアクリロニトリルの共重合物、フッ素系樹脂などの各種樹脂から成る膜を挙げることができる。 (Other layers)
A barrier layer is mentioned as an example of the other layer mentioned above contained in a fluorescent substance sheet. The barrier layer is not particularly limited and is appropriately used in the case where the gas barrier property is improved with respect to the phosphor sheet. For example, silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or the like, or Mixtures of these, or metal oxide thin films with other elements added to them, or films made of various resins such as polyvinylidene chloride, acrylic resins, silicone resins, melamine resins, urethane resins, fluorine resins, etc. Can be mentioned. Examples of the film having a barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and acrylonitrile, and various resins such as fluorine resins. Mention may be made of membranes.
　また、蛍光体シートの要求される機能に応じて、反射防止機能、防眩機能、反射防止防眩機能、光拡散機能、ハードコート機能（耐摩擦機能）、帯電防止機能、防汚機能、電磁波シールド機能、赤外線カット機能、紫外線カット機能、偏光機能、調色機能を有した補助層を、上述したその他の層としてさらに設けてもよい。 Also, depending on the required functions of the phosphor sheet, antireflection function, antiglare function, antireflection antiglare function, light diffusion function, hard coat function (friction resistance function), antistatic function, antifouling function, electromagnetic wave An auxiliary layer having a shield function, an infrared cut function, an ultraviolet cut function, a polarization function, and a toning function may be further provided as the other layers described above.
＜蛍光体シートの製造方法－１＞
　以下に、本発明の実施の形態に係る蛍光体シートの製造方法の一例を説明する。本発明の実施の形態に係る蛍光体シートは、前述した蛍光体組成物から得ることができる。すなわち、この蛍光体シートの製造方法では、上述した方法で作製した蛍光体組成物を、基材上に塗布し、乾燥させ、加熱硬化させる。この結果、蛍光体シートを作製することができる。基材上への蛍光体組成物の塗布は、リバースロールコーター、ブレードコーター、スリットダイコーター、ダイレクトグラビアコーター、オフセットグラビアコーター、キスコーター、ナチュラルロールコーター、エアーナイフコーター、ロールブレードコーター、バリバーロールブレードコーター、トゥーストリームコーター、ロッドコーター、ワイヤーバーコーター、アプリケーター、ディップコーター、カーテンコーター、スピンコーター、ナイフコーター等により、行うことができる。蛍光体シートの膜厚均一性を得るためには、スリットダイコーターで塗布することが好ましい。 <Method for producing phosphor sheet-1>
Below, an example of the manufacturing method of the fluorescent substance sheet which concerns on embodiment of this invention is demonstrated. The phosphor sheet according to the embodiment of the present invention can be obtained from the phosphor composition described above. That is, in this phosphor sheet manufacturing method, the phosphor composition produced by the above-described method is applied onto a substrate, dried, and heat-cured. As a result, a phosphor sheet can be produced. The phosphor composition is coated on the substrate by reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade. A coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used. In order to obtain the film thickness uniformity of the phosphor sheet, it is preferably applied by a slit die coater.
　蛍光体シートの乾燥は、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置を用いて行うことができる。蛍光体シートの加熱には、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置が用いられる。この場合、加熱条件は、通常、４０℃～２５０℃で１分～５時間、好ましくは６０℃～２００℃で２分～４時間である。また、ステップキュア等の段階的に加熱硬化することも可能である。 The phosphor sheet can be dried using a general heating device such as a hot air dryer or an infrared dryer. For heating the phosphor sheet, a general heating device such as a hot air dryer or an infrared dryer is used. In this case, the heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
　蛍光体シートを作製した後、必要に応じて基材を変更することも可能である。この場合、簡易的な方法としてはホットプレートを用いて貼り替えを行なう方法や、真空ラミネーターやドライフィルムラミネーターを用いた方法などが挙げられる。 It is also possible to change the substrate as necessary after producing the phosphor sheet. In this case, examples of a simple method include a method of performing replacement using a hot plate and a method using a vacuum laminator or a dry film laminator.
＜蛍光体シートの製造方法－２＞
　以下に、本発明の実施の形態に係る蛍光体シートの製造方法の別例を説明する。この製造方法では、まず、蛍光体層形成用の塗布液として、無機蛍光体をマトリックス樹脂中に分散させた蛍光体組成物を作製する。この際、前述した無機蛍光体、マトリックス樹脂、シリコーン微粒子、溶剤等を所定量混合する。上記の成分を所定の組成になるよう混合した後、これらの混合物を、ホモジナイザー、自公転型攪拌機、３本ローラー、ボールミル、遊星式ボールミル、ビーズミル等の撹拌・混練機で均質に混合分散する。これにより、上記の蛍光体組成物が得られる。この混合分散後、もしくは、この混合分散の過程において、真空もしくは減圧条件下で脱泡することも好ましく行われる。 <Method for producing phosphor sheet-2>
Below, another example of the manufacturing method of the fluorescent substance sheet which concerns on embodiment of this invention is demonstrated. In this production method, first, a phosphor composition in which an inorganic phosphor is dispersed in a matrix resin is prepared as a coating solution for forming a phosphor layer. At this time, a predetermined amount of the aforementioned inorganic phosphor, matrix resin, silicone fine particles, solvent and the like are mixed. After mixing the above components so as to have a predetermined composition, these mixtures are homogeneously mixed and dispersed with a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a bead mill. Thereby, said fluorescent substance composition is obtained. Defoaming is preferably performed after this mixing and dispersion or in the process of mixing and dispersion under vacuum or reduced pressure conditions.
　つぎに、上述した方法で作製した蛍光体組成物を、基材上に塗布し、乾燥させ、加熱硬化させる。この結果、蛍光体層を作製することができる。基材上への蛍光体組成物の塗布は、リバースロールコーター、ブレードコーター、スリットダイコーター、ダイレクトグラビアコーター、オフセットグラビアコーター、キスコーター、ナチュラルロールコーター、エアーナイフコーター、ロールブレードコーター、バリバーロールブレードコーター、トゥーストリームコーター、ロッドコーター、ワイヤーバーコーター、アプリケーター、ディップコーター、カーテンコーター、スピンコーター、ナイフコーター等により、行うことができる。蛍光体層の膜厚均一性を得るためには、スリットダイコーターで塗布することが好ましい。 Next, the phosphor composition produced by the method described above is applied onto a substrate, dried, and heat-cured. As a result, a phosphor layer can be produced. The phosphor composition is coated on the substrate by reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade. A coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used. In order to obtain the film thickness uniformity of the phosphor layer, it is preferable to apply with a slit die coater.
　蛍光体層の乾燥は、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置を用いて行うことができる。蛍光体層の加熱には、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置が用いられる。この場合、加熱条件は、通常、４０℃～２５０℃で１分～５時間、好ましくは６０℃～２００℃で２分～４時間である。また、ステップキュア等の段階的に加熱硬化することも可能である。 The phosphor layer can be dried using a general heating device such as a hot air dryer or an infrared dryer. For heating the phosphor layer, a general heating device such as a hot air dryer or an infrared dryer is used. In this case, the heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
　つぎに、上記のように作製した蛍光体層上に有機発光材料層を形成する。例えば、有機発光材料を含む塗布液を、蛍光体層上に直接塗布した後、乾燥、加熱硬化処理を行うことによって、蛍光体層および有機発光材料層を有する蛍光体シートが得られる。詳細には、まず、有機発光材料層形成用の塗布液として、有機発光材料をマトリックス樹脂中に分散させた有機発光組成物を作製する。この際、前述した有機発光材料、マトリックス樹脂、溶剤等を所定量混合する。上記の成分を所定の組成になるよう混合した後、これらの混合物を、ホモジナイザー、自公転型攪拌機、３本ローラー、ボールミル、遊星式ボールミル、ビーズミル等の撹拌・混練機で均質に混合分散する。これにより、上記の有機発光組成物が得られる。この混合分散後、もしくは、この混合分散の過程において、真空もしくは減圧条件下で脱泡することも好ましく行われる。 Next, an organic light emitting material layer is formed on the phosphor layer produced as described above. For example, a phosphor sheet having a phosphor layer and an organic light emitting material layer can be obtained by directly applying a coating liquid containing an organic light emitting material on the phosphor layer, followed by drying and heat curing. Specifically, first, an organic light emitting composition in which an organic light emitting material is dispersed in a matrix resin is prepared as a coating liquid for forming an organic light emitting material layer. At this time, a predetermined amount of the aforementioned organic light emitting material, matrix resin, solvent and the like are mixed. After mixing the above components so as to have a predetermined composition, these mixtures are homogeneously mixed and dispersed with a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, or a bead mill. Thereby, said organic luminescent composition is obtained. Defoaming is preferably performed after this mixing and dispersion or in the process of mixing and dispersion under vacuum or reduced pressure conditions.
　蛍光体層上への有機発光材料の塗布は、リバースロールコーター、ブレードコーター、スリットダイコーター、ダイレクトグラビアコーター、オフセットグラビアコーター、キスコーター、ナチュラルロールコーター、エアーナイフコーター、ロールブレードコーター、バリバーロールブレードコーター、トゥーストリームコーター、ロッドコーター、ワイヤーバーコーター、アプリケーター、ディップコーター、カーテンコーター、スピンコーター、ナイフコーター等により、行うことができる。有機発光材料層の膜厚均一性を得るためには、スリットダイコーターで塗布することが好ましい。 Application of organic light emitting material on the phosphor layer is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade. A coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used. In order to obtain the film thickness uniformity of the organic light emitting material layer, it is preferably applied by a slit die coater.
　有機発光材料層の乾燥は、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置を用いて行うことができる。有機発光材料層の加熱には、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置が用いられる。この場合、加熱条件は、通常、４０℃～２５０℃で１分～５時間、好ましくは６０℃～２００℃で２分～４時間である。また、ステップキュア等の段階的に加熱硬化することも可能である。 The organic light emitting material layer can be dried 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 for heating the organic light emitting material layer. In this case, the heating conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.
＜蛍光体組成物の適用例＞
　本発明の実施の形態に係る蛍光体組成物は、好ましくは、ラテラル、バーティカル、フリップチップなどの一般的な構造のＬＥＤチップに好適に用いることができる。ＬＥＤチップは、発光効率を向上させるために、光学的な設計に基づいて、発光表面をテクスチャーなどに加工してもよい。なお、発光面とは、ＬＥＤチップからの光が取り出される面をいう。 <Application example of phosphor composition>
The phosphor composition according to the embodiment of the present invention can be preferably used for an LED chip having a general structure such as lateral, vertical, and flip chip. In order to improve the luminous efficiency, the LED chip may process the light emitting surface into a texture or the like based on an optical design. The light emitting surface is a surface from which light from the LED chip is extracted.
　このようなＬＥＤチップを金属配線し、その後、本発明の実施の形態に係る蛍光体組成物を用いて、このＬＥＤチップの封止を行うことにより、このＬＥＤチップをパッケージ化してＬＥＤパッケージとすることが可能である。このＬＥＤパッケージ内のＬＥＤチップは、その発光面を覆った状態の蛍光体組成物によって発光光が色変換される発光体である。そして、このＬＥＤパッケージは、このようなＬＥＤチップの発光面を含む全体を覆った状態にある蛍光体組成物の硬化物を備えている。その後、上記のように得られたＬＥＤパッケージをモジュールに組み込むことで、各種照明や液晶バックライト、ヘッドランプをはじめとする様々なＬＥＤ発光装置に上記ＬＥＤパッケージを好適に使用することができる。 Such an LED chip is metal-wired, and then the LED chip is sealed using the phosphor composition according to the embodiment of the present invention, whereby the LED chip is packaged into an LED package. It is possible. The LED chip in the LED package is a light emitting body whose emitted light is color-converted by the phosphor composition in a state of covering the light emitting surface. And this LED package is equipped with the hardened | cured material of the fluorescent substance composition in the state which covered the whole including the light emission surface of such an LED chip. After that, by incorporating the LED package obtained as described above into a module, the LED package can be suitably used for various LED light emitting devices such as various illuminations, liquid crystal backlights, and headlamps.
＜蛍光体組成物を用いたＬＥＤパッケージの製造方法＞
　本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの製造方法について説明する。図２は、本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの製造方法の一例を示す図である。ただし、本発明は、図２に示される製造方法には限定されない。本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの製造方法として、特に好適なものは、ＬＥＤチップが設置されているパッケージフレームに蛍光体組成物を注入する注入工程と、この注入工程の後、封止材でパッケージフレーム内のＬＥＤチップを封止する封止工程と、を少なくとも含む。 <Method for Manufacturing LED Package Using Phosphor Composition>
An LED package manufacturing method using the phosphor composition according to the embodiment of the present invention will be described. FIG. 2 is a diagram showing an example of a method for manufacturing an LED package using the phosphor composition according to the embodiment of the present invention. However, the present invention is not limited to the manufacturing method shown in FIG. As an LED package manufacturing method using the phosphor composition according to the embodiment of the present invention, a particularly preferable method is an injection step of injecting the phosphor composition into a package frame in which the LED chip is installed, After the injection step, at least a sealing step of sealing the LED chip in the package frame with a sealing material is included.
　詳細には、図２に示すように、まず、パッケージフレーム１２として、リフレクター５付きの実装基板７を用意する準備工程が行われる（状態Ａ１）。ついで、実装基板７の上にＬＥＤチップ１を実装して設置する実装工程が行われる（状態Ａ２）。 Specifically, as shown in FIG. 2, first, a preparation process for preparing the mounting substrate 7 with the reflector 5 as the package frame 12 is performed (state A1). Next, a mounting process for mounting and installing the LED chip 1 on the mounting substrate 7 is performed (state A2).
　つぎに、本発明の実施の形態に係る蛍光体組成物４を、ＬＥＤチップ１が設置されているパッケージフレーム１２の中に所望の量、注入する注入工程が行われる（状態Ａ３）。この蛍光体組成物４の注入方法として、射出成型、圧縮成型、注型成型、トランスファー成型、コーティング、ポッティング（ディスペンス）、印刷、転写等の方法が挙げられるが、これらに限定されない。特に好ましくは、ポッティング（ディスペンス）を用いることができる。この注入工程により、ＬＥＤチップ１の発光面を含む全体は、パッケージフレーム１２内において、蛍光体組成物４に覆われる。 Next, an injection step of injecting a desired amount of the phosphor composition 4 according to the embodiment of the present invention into the package frame 12 on which the LED chip 1 is installed is performed (state A3). Examples of the method for injecting the phosphor composition 4 include, but are not limited to, injection molding, compression molding, cast molding, transfer molding, coating, potting (dispensing), printing, and transfer. Particularly preferably, potting (dispensing) can be used. Through this injection step, the entire portion including the light emitting surface of the LED chip 1 is covered with the phosphor composition 4 in the package frame 12.
　蛍光体組成物４の注入後、この蛍光体組成物４を加熱硬化させる加熱硬化工程が行われる。これにより、パッケージフレーム１２の形状に合った形で、蛍光体組成物４の硬化物をＬＥＤチップ１上に設けることができる。この加熱硬化工程において、蛍光体組成物４の加熱硬化処理は、熱風乾燥機や赤外線乾燥機等の一般的な加熱装置を用いて行なうことができる。加熱硬化条件は、通常、４０℃～２５０℃で１分～５時間、好ましくは６０℃～２００℃で２分～４時間である。この場合、ステップキュア等の段階的に加熱硬化することも可能である。 After the injection of the phosphor composition 4, a heat curing step is performed in which the phosphor composition 4 is heat cured. Thereby, the hardened | cured material of the fluorescent substance composition 4 can be provided on the LED chip 1 in the form suitable for the shape of the package frame 12. FIG. In this heat curing step, the heat curing treatment of the phosphor composition 4 can be performed using a general heating device such as a hot air dryer or an infrared dryer. The heat curing conditions are usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. In this case, it is possible to perform heat curing stepwise such as step cure.
　その後、上記蛍光体組成物４の硬化物の上に、透明封止材６を注入し加熱硬化して、この硬化物中のＬＥＤチップ１を封止する封止工程が行われる（状態Ａ４）。この透明封止材６の注入方法および加熱硬化条件は、上述した蛍光体組成物４の注入方法および加熱硬化条件に準ずる。以上の工程により、ＬＥＤパッケージ１３が製造される。その後、ＬＥＤパッケージ１３には、必要に応じて、透明樹脂によるオーバーコート層やレンズ等を設けても構わない。 Then, the sealing process which inject | pours the transparent sealing material 6 on the hardened | cured material of the said phosphor composition 4, heat-hardens, and seals the LED chip 1 in this hardened | cured material is performed (state A4). . The injection method and heat curing conditions for the transparent sealing material 6 are based on the above-described injection method and heat cure conditions for the phosphor composition 4. The LED package 13 is manufactured through the above steps. Thereafter, the LED package 13 may be provided with an overcoat layer made of a transparent resin, a lens, or the like, if necessary.
＜蛍光体シート、蛍光体形成物の適用例＞
　本発明の実施の形態に係る蛍光体シートは、好ましくは、ラテラル、バーティカル、フィリップチップなどの一般的な構造のＬＥＤチップの発光面に貼り付けられる。これにより、ＬＥＤチップの表面に蛍光体シートが積層された蛍光体シート付きＬＥＤチップを形成することができる。蛍光体シートは、特に、発光面積が大きいバーティカル、フリップチップタイプのＬＥＤチップに好適に用いることができる。なお、発光面とは、ＬＥＤチップからの光が取り出される面をいう。 <Application examples of phosphor sheet and phosphor formed product>
The phosphor sheet according to the embodiment of the present invention is preferably attached to the light emitting surface of an LED chip having a general structure such as lateral, vertical, and Philip chip. Thereby, the LED chip with a phosphor sheet in which the phosphor sheet is laminated on the surface of the LED chip can be formed. The phosphor sheet can be suitably used particularly for vertical and flip chip type LED chips having a large light emitting area. The light emitting surface is a surface from which light from the LED chip is extracted.
　ここで、ＬＥＤチップからの発光面は、単一平面である場合と単一平面ではない場合とがある。単一平面の場合としては、主に上部発光面のみを有するＬＥＤチップが挙げられる。具体的には、バーティカルタイプのＬＥＤチップや、側面を反射層で覆い、上面からのみ光が取り出されるようにしたＬＥＤチップなどが例示される。一方、単一平面ではない場合としては、上部発光面および側部発光面を有するＬＥＤチップや曲面発光面を持つＬＥＤチップが挙げられる。 Here, the light emitting surface from the LED chip may be a single plane or not a single plane. In the case of a single plane, LED chips mainly having only an upper light emitting surface can be mentioned. Specifically, a vertical type LED chip, an LED chip whose side surface is covered with a reflective layer, and light is extracted only from the upper surface are exemplified. On the other hand, as a case where it is not a single plane, an LED chip having an upper light emitting surface and a side light emitting surface and an LED chip having a curved light emitting surface can be mentioned.
　ＬＥＤチップとしては、側部からの発光を利用でき明るくすることができることから、発光面が単一平面ではない場合が好ましい。特に、発光面積を大きくできること、およびチップ製造プロセスが容易なことから、上部発光面と側部発光面とを有するフリップチップタイプのＬＥＤチップが好ましい。また、ＬＥＤチップは、発光効率を向上させるために光学的な設計に基づいて、発光表面をテクスチャーなどに加工してもよい。 As the LED chip, it is preferable that the light emitting surface is not a single plane because the light emitted from the side can be used and brightened. In particular, a flip chip type LED chip having an upper light emitting surface and a side light emitting surface is preferable because the light emitting area can be increased and the chip manufacturing process is easy. In addition, the LED chip may process the light emitting surface into a texture or the like based on an optical design in order to improve the light emission efficiency.
　本発明の実施の形態に係る蛍光体シートは、直接ＬＥＤチップに貼付けせずに、透明樹脂などの接着剤を用いて貼付けを行なうことも可能である。一方で、ＬＥＤチップの発光面を蛍光体シートで被覆することは、ＬＥＤチップからの光を反射などによってロスすることなく、直接、色変換層である蛍光体シートへ入射させることができるため、好ましい。これにより、色バラツキが少なく高効率で均一な白色光を得ることができる。ここでいう色変換層とは、ＬＥＤチップから放出される光を吸収して波長を変換し、ＬＥＤチップの光と異なる波長の光を放出する層を表す。 The phosphor sheet according to the embodiment of the present invention can be pasted using an adhesive such as a transparent resin without being directly pasted on the LED chip. On the other hand, covering the light emitting surface of the LED chip with the phosphor sheet allows the light from the LED chip to be directly incident on the phosphor sheet that is the color conversion layer without losing light by reflection or the like. preferable. Thereby, uniform white light with little color variation and high efficiency can be obtained. The color conversion layer here refers to a layer that absorbs light emitted from the LED chip, converts the wavelength, and emits light having a wavelength different from that of the LED chip.
　これらの方法で得られた蛍光体シート付きＬＥＤチップは、金属配線や封止を行ってパッケージ化したＬＥＤパッケージとすることが可能である。その後、このＬＥＤパッケージをモジュールに組み込むことで、本発明の実施の形態に係る蛍光体シート、延いては、これを用いた蛍光体シート付きＬＥＤチップは、各種照明や液晶バックライト、ヘッドランプをはじめとする様々なＬＥＤ発光装置に好適に使用することができる。 The LED chip with a phosphor sheet obtained by these methods can be an LED package packaged by metal wiring or sealing. After that, by incorporating this LED package into the module, the phosphor sheet according to the embodiment of the present invention, that is, the LED chip with the phosphor sheet using this, can be used for various illuminations, liquid crystal backlights, and headlamps. It can use suitably for various LED light-emitting devices including the first.
　図３Ａ～図３Ｃは、本発明の実施の形態に係る蛍光体シート付きＬＥＤチップの好適な例を示す図である。図３Ａは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの一例を示す図である。図３Ａに例示する蛍光体シート付きＬＥＤチップ３１は、ＬＥＤチップ１の上面（発光面）に蛍光体シート２を貼り付けて設置したものである。図３Ｂは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの別例を示す図である。図３Ｂに例示する蛍光体シート付きＬＥＤチップ３１は、ＬＥＤチップ１の上面（上部発光面）だけでなく側面（側部発光面）にも、蛍光体シート２を貼り付けて設置したものである。このタイプの蛍光体シート付きＬＥＤチップ３１は、ＬＥＤチップ１の側面からの発光に対しても色変換できるため、好ましい。図３Ｃは、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの更なる別例を示す図である。図３Ｃに例示する蛍光体シート付きＬＥＤチップ３１は、下面に電極３を有するフリップチップタイプのＬＥＤチップ１を用いて、このＬＥＤチップ１の発光面である上面と側面とを蛍光体シート２によって被覆したものである。 FIG. 3A to FIG. 3C are views showing a suitable example of the LED chip with a phosphor sheet according to the embodiment of the present invention. FIG. 3A is a diagram showing an example of an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. The LED chip 31 with a phosphor sheet illustrated in FIG. 3A is obtained by attaching the phosphor sheet 2 to the upper surface (light emitting surface) of the LED chip 1. FIG. 3B is a diagram showing another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. The LED chip 31 with a phosphor sheet illustrated in FIG. 3B is obtained by attaching the phosphor sheet 2 to not only the upper surface (upper light emitting surface) but also the side surface (side light emitting surface) of the LED chip 1. . This type of LED chip 31 with a phosphor sheet is preferable because it can perform color conversion with respect to light emission from the side surface of the LED chip 1. FIG. 3C is a diagram showing still another example of the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. The LED chip 31 with a phosphor sheet illustrated in FIG. 3C uses a flip chip type LED chip 1 having an electrode 3 on the lower surface, and the phosphor sheet 2 has an upper surface and a side that are light emitting surfaces of the LED chip 1. It is coated.
　図４Ａ～図４Ｊは、本発明の実施の形態に係るＬＥＤパッケージの好適な例を示す図である。図４Ａは、本発明の実施の形態に係る蛍光体組成物を用いたＬＥＤパッケージの一例を示す図である。図４Ａに例示するＬＥＤパッケージ１３は、ＬＥＤチップ１を設置したリフレクター５付きの実装基板７に蛍光体組成物４を注入し、その後、このＬＥＤチップ１を透明封止材６によって封止したものである。このＬＥＤパッケージ１３は、蛍光体組成物４の硬化物を備えたものとしての好適な一例である。 FIG. 4A to FIG. 4J are views showing a suitable example of the LED package according to the embodiment of the present invention. FIG. 4A is a diagram showing an example of an LED package using the phosphor composition according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4A is obtained by injecting the phosphor composition 4 into the mounting substrate 7 with the reflector 5 on which the LED chip 1 is installed, and then sealing the LED chip 1 with the transparent sealing material 6. It is. This LED package 13 is a suitable example as a thing provided with the hardened | cured material of the phosphor composition 4. FIG.
　図４Ｂは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例１を示す図である。図４Ｂに例示するＬＥＤパッケージ１３は、リフレクター５付きの実装基板７に設置されたＬＥＤチップ１上に蛍光体シート２を貼り付け、その後、このＬＥＤチップ１を蛍光体シート２とともに透明封止材６によって封止したものである。図４Ｃは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例２を示す図である。図４Ｃに例示するＬＥＤパッケージ１３は、リフレクター５付きの実装基板７に設置されたＬＥＤチップ１に対して、その上面だけでなく側面にも蛍光体シート２を貼り付け、さらに、透明封止材６によるレンズも取り付けたものである。このタイプのＬＥＤパッケージ１３は、ＬＥＤチップ１の側面からの発光に対しても蛍光体シート２によって色変換できるため、好ましい。 FIG. 4B is a view showing Example 1 of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4B has a phosphor sheet 2 attached on the LED chip 1 installed on the mounting substrate 7 with the reflector 5, and then the LED chip 1 and the phosphor sheet 2 together with a transparent sealing material. 6 is sealed. FIG. 4C is a diagram showing an example 2 of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4C has the phosphor sheet 2 attached to the LED chip 1 placed on the mounting substrate 7 with the reflector 5 not only on the top surface but also on the side surface. A lens according to 6 is also attached. This type of LED package 13 is preferable because the phosphor sheet 2 can perform color conversion for light emitted from the side surface of the LED chip 1.
　図４Ｄは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例３を示す図である。図４Ｄに例示するＬＥＤパッケージ１３は、リフレクター５を用いず、透明封止材６のレンズ成型体により、ＬＥＤチップ１を蛍光体シート２とともに封止したものである。このこと以外は、図４Ｂに例示するＬＥＤパッケージ１３と同様である。図４Ｅは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例４を示す図である。図４Ｅに例示するＬＥＤパッケージ１３は、リフレクター５を用いないこと以外、図４Ｃに例示するＬＥＤパッケージ１３と同様のものである。 FIG. 4D is a view showing Example 3 of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4D is obtained by sealing the LED chip 1 together with the phosphor sheet 2 by using a lens molding of the transparent sealing material 6 without using the reflector 5. Except this, it is the same as the LED package 13 illustrated in FIG. 4B. FIG. 4E is a diagram showing Example 4 of an LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4E is the same as the LED package 13 illustrated in FIG. 4C except that the reflector 5 is not used.
　図４Ｆは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例５を示す図である。図４Ｆに例示するＬＥＤパッケージ１３は、下面に電極３および金バンプ８を有するフリップチップタイプのＬＥＤチップ１を用いて、このＬＥＤチップ１の発光面である上面と側面を蛍光体シート２によって被覆したものである。このこと以外は、図４Ｃに例示するＬＥＤパッケージ１３と同様である。なお、ＬＥＤチップ１の側面を蛍光体シート２で被覆する際、図４Ｆに示すように、蛍光体シート２が実装基板７の上面まで及ぶようにしてもよい。図４Ｇは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例６を示す図である。図４Ｇに例示するＬＥＤパッケージ１３は、リフレクター５を用いず、透明封止材６のレンズ成型体により、フリップチップタイプのＬＥＤチップ１（図４Ｆ参照）を蛍光体シート２とともに封止したものである。このこと以外は、図４Ｅに例示するＬＥＤパッケージ１３と同様である。 FIG. 4F is a view showing Example 5 of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4F uses a flip chip type LED chip 1 having electrodes 3 and gold bumps 8 on the lower surface, and the upper surface and side surfaces, which are the light emitting surfaces of the LED chip 1, are covered with the phosphor sheet 2. It is a thing. Except this, it is the same as the LED package 13 illustrated in FIG. 4C. When the side surface of the LED chip 1 is covered with the phosphor sheet 2, the phosphor sheet 2 may extend to the upper surface of the mounting substrate 7 as shown in FIG. 4F. FIG. 4G is a diagram showing Example 6 of an LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4G is obtained by sealing the flip chip type LED chip 1 (see FIG. 4F) together with the phosphor sheet 2 by using a lens molding of the transparent sealing material 6 without using the reflector 5. is there. Except this, it is the same as the LED package 13 illustrated in FIG. 4E.
　図４Ｈは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例７を示す図である。図４Ｈに例示するＬＥＤパッケージ１３は、ＬＥＤチップ１と蛍光体シート２とを透明接着剤９によって貼付けしたものである。このこと以外は、図４Ｂに例示するＬＥＤパッケージ１３と同様である。図４Ｉは、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの例８を示す図である。図４Ｉに例示するＬＥＤパッケージ１３は、あらかじめ用意した基材１０付きの蛍光体シート２を用いたものである。このタイプのＬＥＤパッケージ１３では、基材１０は、蛍光体シート２から剥離せずに用いられる。このこと以外は、図４Ｈに例示するＬＥＤパッケージ１３と同様である。基材１０の材質としては、ガラスが好ましい。図４Ｂ～図４Ｉに例示するＬＥＤパッケージ１３は、蛍光体シート２またはその硬化物を備えたものとしての好適な一例である。 FIG. 4H is a view showing Example 7 of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4H is obtained by pasting the LED chip 1 and the phosphor sheet 2 with the transparent adhesive 9. Except this, it is the same as the LED package 13 illustrated in FIG. 4B. FIG. 4I is a diagram showing Example 8 of an LED package using the phosphor sheet according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4I uses a phosphor sheet 2 with a base material 10 prepared in advance. In this type of LED package 13, the base material 10 is used without being peeled from the phosphor sheet 2. Except this, it is the same as the LED package 13 illustrated in FIG. 4H. As a material of the base material 10, glass is preferable. The LED package 13 illustrated in FIG. 4B to FIG. 4I is a preferred example as a phosphor sheet 2 or a cured product thereof.
　図４Ｊは、本発明の実施の形態に係る蛍光体組成物を使用した形成物を用いたＬＥＤパッケージの一例を示す図である。図４Ｊに例示するＬＥＤパッケージ１３は、フリップチップタイプのＬＥＤチップ１（図４Ｆ参照）を用いて、このＬＥＤチップ１の発光面である上面と側面を透明封止材６によって被覆し、さらに、蛍光体組成物を用いた形成物１１で、この透明封止材６を被覆したものである。このこと以外は、図４Ｇに例示するＬＥＤパッケージ１３と同様である。このＬＥＤパッケージ１３は、蛍光体組成物４またはその硬化物を含有する形成物１１（蛍光体形成物）を備えたものとしての好適な一例である。 FIG. 4J is a diagram showing an example of an LED package using a formed product using the phosphor composition according to the embodiment of the present invention. The LED package 13 illustrated in FIG. 4J uses a flip chip type LED chip 1 (see FIG. 4F), and covers the light emitting surface of the LED chip 1 with the transparent encapsulant 6, The transparent sealing material 6 is covered with a formed article 11 using a phosphor composition. Except this, it is the same as the LED package 13 illustrated in FIG. 4G. This LED package 13 is a suitable example as a thing provided with the formation 11 (phosphor formation) containing the phosphor composition 4 or its hardened | cured material.
　本発明を適用できるＬＥＤパッケージは、これらに限られない。例えば、図４Ｂに示すＬＥＤパッケージ１３において、透明封止材６が、図４Ｃに示すような形状であり、かつ、蛍光体シート２が、ＬＥＤチップ１の上面だけでなく側面にも貼り付けたものであっても構わない。このように、図４Ａ～図４Ｊに例示されたＬＥＤパッケージ１３の各パーツの構造を適宜組み合わせることが可能である。また、ＬＥＤパッケージ１３の各パーツは、これら以外の公知のパーツに置き換えたり、組み合わせたりしてもよい。 The LED package to which the present invention can be applied is not limited to these. For example, in the LED package 13 shown in FIG. 4B, the transparent sealing material 6 has a shape as shown in FIG. 4C, and the phosphor sheet 2 is attached not only to the top surface of the LED chip 1 but also to the side surface. It doesn't matter. As described above, the structure of each part of the LED package 13 illustrated in FIGS. 4A to 4J can be appropriately combined. Moreover, each part of the LED package 13 may be replaced with a known part other than these, or may be combined.
　ここで、透明封止材６は、成形加工性、透明性、耐熱性、接着性等に優れる材料であれば、エポキシ樹脂、シリコーン樹脂（シリコーンゴム、シリコーンゲル等のオルガノポリシロキサン硬化物（架橋物）を含む）、ウレア樹脂、フッ素樹脂、ポリカーボネート樹脂などの公知のものを用いることができる。また、透明接着剤９としては、上述した透明封止材６を用いることができる。 Here, as long as the transparent sealing material 6 is a material excellent in moldability, transparency, heat resistance, adhesiveness, etc., epoxy resin, silicone resin (organopolysiloxane cured product such as silicone rubber and silicone gel (crosslinked) And the like), known resins such as urea resins, fluororesins, and polycarbonate resins can be used. Moreover, as the transparent adhesive 9, the transparent sealing material 6 mentioned above can be used.
＜蛍光体シートを用いたＬＥＤパッケージの製造方法＞
　本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法について説明する。本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの代表的な製造方法では、ＬＥＤパッケージの製造に用いる蛍光体シート付きＬＥＤチップの製造方法が、主に２つある。１つは、蛍光体シートを個片に切断してから、個別のＬＥＤチップに、個片化した蛍光体シートを貼り付ける方法である。もう１つは、ＬＥＤチップを作り付けたウェハに対し、そのダイシング前に蛍光体シートを一括に貼り付けし、その後、このウェハのダイシングと蛍光体シートの切断とを一括して行う方法である。これら２つの方法の詳細は、後述する。本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法は、これら２つの方法に限定されない。 <Method of manufacturing LED package using phosphor sheet>
An LED package manufacturing method using the phosphor sheet according to the embodiment of the present invention will be described. In a typical method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention, there are mainly two methods for manufacturing an LED chip with a phosphor sheet used for manufacturing an LED package. One is a method of cutting the phosphor sheet into individual pieces and then attaching the separated phosphor sheets to individual LED chips. The other is a method in which a phosphor sheet is affixed to a wafer on which LED chips are formed before dicing, and then dicing of the wafer and cutting of the phosphor sheet are performed in a lump. Details of these two methods will be described later. The manufacturing method of the LED package using the phosphor sheet according to the embodiment of the present invention is not limited to these two methods.
　本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法として、特に好適なものは、蛍光体シートが複数の区画に分割されており、これら複数の区画に分割された状態にある前記蛍光体シートの一の区画を、一のＬＥＤチップの発光面に対向させる位置合わせ工程と、対向させた前記蛍光体シートの一の区画と前記一のＬＥＤチップの発光面とを、加熱圧着ツールにより加熱しながら加圧して接着する接着工程と、を少なくとも含む。 As a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention, a particularly preferable method is that the phosphor sheet is divided into a plurality of sections and is divided into the plurality of sections. An alignment step of causing one section of the phosphor sheet to face the light emitting surface of one LED chip, and heating one section of the phosphor sheet and the light emitting surface of the one LED chip opposed to each other An adhesion step of applying pressure while heating with a crimping tool.
　本発明の実施の形態に係る蛍光体シートは、直接ＬＥＤチップに貼付けせずに、透明樹脂などの接着剤を用いてＬＥＤチップに貼付けることも可能である。しかし、マトリックス樹脂として熱融着樹脂を含有する蛍光体シートを用いることが、接着剤なしでＬＥＤチップに蛍光体シートを容易に貼り付けることができるため、好ましい。 The phosphor sheet according to the embodiment of the present invention can be attached to the LED chip using an adhesive such as a transparent resin without being attached directly to the LED chip. However, it is preferable to use a phosphor sheet containing a heat fusion resin as the matrix resin because the phosphor sheet can be easily attached to the LED chip without an adhesive.
　接着工程において、蛍光体シートは、ＬＥＤチップに貼り付ける際、所望の温度で加熱しながら加圧することで圧着して貼り付ける。加熱温度は、６０℃以上、２５０℃以下が望ましく、より望ましくは、６０℃以上、１６０℃以下である。加熱温度を６０℃以上にすることで、室温と貼り付け温度での弾性率差を大きくするための樹脂設計が容易となる。また、加熱温度を２５０℃以下にすることで、基材および蛍光体シートの熱膨張、熱収縮を小さくすることができるので、貼り付けの精度を高めることができる。特に、蛍光体シートに予め孔開け加工を施して、ＬＥＤチップ上の所定部分と蛍光体シートとの位置合わせを行う場合などには、貼り付けの位置精度は重要である。貼り付けの精度を高めるためには、加熱温度を１６０℃以下にしてＬＥＤチップと蛍光体シートとを貼り付けることが、より好適である。 In the adhering step, the phosphor sheet is adhered by pressure bonding by applying pressure while heating at a desired temperature when adhering to the LED chip. The heating temperature is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 60 ° C. or higher and 160 ° C. or lower. By setting the heating temperature to 60 ° C. or higher, the resin design for increasing the difference in elastic modulus between the room temperature and the attaching temperature becomes easy. Moreover, since the thermal expansion and thermal shrinkage of the base material and the phosphor sheet can be reduced by setting the heating temperature to 250 ° C. or lower, the accuracy of pasting can be increased. In particular, when the phosphor sheet is previously perforated to align the predetermined portion on the LED chip with the phosphor sheet, the positional accuracy of the pasting is important. In order to increase the accuracy of attachment, it is more preferable to attach the LED chip and the phosphor sheet at a heating temperature of 160 ° C. or lower.
　蛍光体シートをＬＥＤチップ表面に貼り付ける方法としては、所望の温度で圧着できる装置であれば既存の任意の装置が利用でき、例えば、マウンターやフリップチップボンダーなどの加熱圧着ツールが利用できる。また、ウェハレベルのＬＥＤチップに一括して蛍光体シートを貼り付ける際には、真空ラミネーターや１００ｍｍ～２００ｍｍ角程度の加熱部分を有する加熱圧着ツールなどを用いて貼り付けることができる。いずれの場合も、所望の温度で蛍光体シートをＬＥＤチップに圧着して熱融着させてから、これらを室温まで放冷し、この蛍光体シートから基材を剥離する。本発明のような温度と弾性率との関係を持たせることで、熱融着後に室温まで放冷却した後の蛍光体シートは、ＬＥＤチップに強固に密着しつつ、基材から容易に剥離することが可能となる。 As a method for attaching the phosphor sheet to the LED chip surface, any existing apparatus can be used as long as it can be bonded at a desired temperature. For example, a thermocompression bonding tool such as a mounter or a flip chip bonder can be used. In addition, when the phosphor sheets are stuck together on the wafer level LED chips, they can be stuck using a vacuum laminator or a thermocompression bonding tool having a heating portion of about 100 mm to 200 mm square. In either case, the phosphor sheet is pressure-bonded to the LED chip at a desired temperature and thermally fused, and then allowed to cool to room temperature, and the substrate is peeled from the phosphor sheet. By giving the relationship between the temperature and the elastic modulus as in the present invention, the phosphor sheet after being allowed to cool to room temperature after heat fusion is easily peeled off from the substrate while firmly adhering to the LED chip. It becomes possible.
　蛍光体シートを切断加工する方法について説明する。蛍光体シートを切断加工する方法としては、蛍光体シートをＬＥＤチップへの貼り付け前に予め個片に切断し、個別のＬＥＤチップに、個片化した蛍光体シートを貼り付ける方法と、ウェハレベルのＬＥＤチップに蛍光体シートを貼り付けてからウェハのダイシングと同時に一括して蛍光体シートを切断する方法と、がある。蛍光体シートを貼りつけ前に予め切断する場合には、均一に形成された蛍光体シートを、レーザーによる加工、あるいは刃物による切削によって所定の形状に加工し、分割する。レーザーによる加工は、高エネルギーが付与されるので、蛍光体シート中の樹脂の焼け焦げや蛍光体の劣化を回避することが非常に難しいので、刃物による切削が望ましい。刃物での切削方法としては、単純な刃物を押し込んで蛍光体シートを切る方法と、回転刃によって蛍光体シートを切る方法とがあり、いずれも好適に使用できる。回転刃によって切断する装置としては、ダイサーと呼ばれる半導体基板（ウェハ）を個別のチップに切断（ダイシング）するのに用いる装置が好適に利用できる。ダイサーを用いれば、回転刃の厚みや条件設定により、蛍光体シートの分割ラインの幅を精密に制御できるため、単純な刃物の押し込みにより蛍光体シートを切断するよりも高い加工精度が得られる。 The method for cutting the phosphor sheet will be described. As a method of cutting the phosphor sheet, the phosphor sheet is cut into individual pieces before being attached to the LED chip, and the individual phosphor chips are attached to the individual LED chips, and the wafer. There is a method in which a phosphor sheet is attached to a level LED chip and then the phosphor sheet is cut simultaneously with wafer dicing. When the phosphor sheet is cut in advance before being attached, the uniformly formed phosphor sheet is processed into a predetermined shape by laser processing or cutting with a blade and divided. Since processing with a laser imparts high energy, it is very difficult to avoid scorching of the resin in the phosphor sheet and deterioration of the phosphor, so cutting with a blade is desirable. As a cutting method with a blade, there are a method of cutting a phosphor sheet by pushing a simple blade, and a method of cutting a phosphor sheet with a rotary blade, both of which can be suitably used. As an apparatus for cutting with a rotary blade, an apparatus used for cutting (dicing) a semiconductor substrate (wafer) called a dicer into individual chips can be suitably used. If the dicer is used, the width of the dividing line of the phosphor sheet can be precisely controlled by the thickness of the rotary blade and the condition setting, so that higher processing accuracy can be obtained than when the phosphor sheet is cut by pushing a simple blade.
　基材に積層された状態の蛍光体シートを切断する場合には、蛍光体シートは基材ごと個片化してもよいし、あるいは、蛍光体シートは個片化しつつ、基材は切断しなくても構わない。あるいは、基材は、貫通しない切り込みラインが入る、所謂、ハーフカットを施されてもよい。そのように個片化した蛍光体シートは、個別のＬＥＤチップの発光面上に熱融着される。 When cutting the phosphor sheet in a state of being laminated on the substrate, the phosphor sheet may be separated into the entire substrate, or the phosphor sheet is separated into pieces and the substrate is not cut. It doesn't matter. Alternatively, the substrate may be subjected to a so-called half cut in which a cut line that does not penetrate is entered. The phosphor sheet thus separated is heat-sealed on the light emitting surface of each individual LED chip.
　図５は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の一例を示す図である。このＬＥＤパッケージの製造方法は、蛍光体シートを基材ごと個片化する場合の、蛍光体シートの切断、ＬＥＤチップへの蛍光体シートの貼り付け、およびダイシング等の工程を含む。このＬＥＤパッケージの製造方法には、蛍光体シートを基材ごと個片に切断する工程、および該個片に切断された蛍光体シートを所望の温度で圧着してＬＥＤチップに貼り付ける工程が含まれる。 FIG. 5 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention. The LED package manufacturing method includes steps such as cutting the phosphor sheet, attaching the phosphor sheet to the LED chip, and dicing when the phosphor sheet is separated into individual substrates. This LED package manufacturing method includes a step of cutting the phosphor sheet into individual pieces together with a base material, and a step of pressing the phosphor sheet cut into the individual pieces at a desired temperature and attaching them to the LED chip. It is.
　例えば、図５に示すＬＥＤパッケ－ジの製造方法では、基材１４に積層された状態の蛍光体シート２を仮固定シート１５に固定する仮固定工程が行われる（状態Ｂ１）。図５に示すＬＥＤパッケ－ジの製造方法では、蛍光体シート２と基材１４は、いずれも個片化するので、取り扱いが容易なように仮固定シート１５に固定しておく。つぎに、蛍光体シート２と基材１４との双方を切断して蛍光体シート２を基材１４ごと個片化する切断工程が行われる（状態Ｂ２）。続いて、実装基板７に実装されたＬＥＤチップ１の上に、個片化された蛍光体シート２および基材１４の積層体（個片積層体）を位置合わせする位置合わせ工程が行われる（状態Ｂ３）。このＬＥＤチップ１は、ウェハのダイシング工程によって得られたものであり、パッケージフレーム１２を構成するリフレクター５付きの実装基板７に予め実装される。 For example, in the LED package manufacturing method shown in FIG. 5, a temporary fixing step of fixing the phosphor sheet 2 laminated on the base material 14 to the temporary fixing sheet 15 is performed (state B1). In the LED package manufacturing method shown in FIG. 5, since the phosphor sheet 2 and the base material 14 are both separated into pieces, they are fixed to the temporary fixing sheet 15 so as to be easy to handle. Next, the cutting process which cut | disconnects both the fluorescent substance sheet 2 and the base material 14, and separates the fluorescent substance sheet 2 with the base material 14 is performed (state B2). Subsequently, an alignment process is performed for aligning the laminated body (individual laminated body) of the phosphor sheet 2 and the base material 14 separated on the LED chip 1 mounted on the mounting substrate 7 ( State B3). This LED chip 1 is obtained by a wafer dicing process, and is mounted in advance on a mounting substrate 7 with a reflector 5 constituting a package frame 12.
　つぎに、上記の位置合わせ工程によってＬＥＤチップ１の発光面と蛍光体シート２とを対向させた状態にある蛍光体シート２および基材１４の個片積層体を、加熱圧着ツール１６を用いて、所望の温度で加熱しながら加圧してパッケージフレーム１２の実装基板７上のＬＥＤチップ１に接着（圧着）する接着工程が行われる（状態Ｂ４）。このとき、蛍光体シート２とＬＥＤチップ１との間に空気を噛み込まないように、接着工程は真空下あるいは減圧下で行うことが好ましい。この接着工程の後、パッケージフレーム１２内のＬＥＤチップ１と蛍光体シート２および基材１４の個片積層体とを室温まで放冷し、このＬＥＤチップ１に接着した状態の蛍光体シート２から基材１４を剥離する冷却工程が行われる（状態Ｂ５）。ここで、基材１４がガラス等の透明部材である場合、冷却工程では、蛍光体シート２から基材１４を剥離せず、そのままの状態にしてもよい（状態Ｂ６）。 Next, using the thermocompression bonding tool 16, the individual laminate of the phosphor sheet 2 and the base material 14 in a state where the light emitting surface of the LED chip 1 and the phosphor sheet 2 are opposed to each other by the above alignment process. Then, a bonding process is performed in which the pressure is applied while heating at a desired temperature to bond (crimp) the LED frame 1 on the mounting substrate 7 of the package frame 12 (state B4). At this time, it is preferable to perform the bonding step under vacuum or under reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip 1. After this bonding step, the LED chip 1 in the package frame 12, the phosphor sheet 2, and the individual laminate of the base material 14 are allowed to cool to room temperature, and from the phosphor sheet 2 in a state of being bonded to the LED chip 1. A cooling step for peeling the base material 14 is performed (state B5). Here, when the base material 14 is a transparent member such as glass, in the cooling step, the base material 14 may be left as it is without being peeled from the phosphor sheet 2 (state B6).
　一方、基材１４が連続したまま蛍光体シート２が個片化された場合には、この基材１４上の個片化された蛍光体シート２は、そのまま一括して、ダイシング前のウェハレベルのＬＥＤチップに熱融着されてもよい。図６は、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの製造方法の一例を示す図である。この蛍光体シート付きＬＥＤパッケージの製造方法は、基材１４が連続したまま蛍光体シート２が個片化される場合の、蛍光体シート２の切断、ウェハレベルのＬＥＤチップへの蛍光体シート２の貼り付け、およびダイシング等の工程を含む。この蛍光体シート付きＬＥＤパッケージの製造方法には、基材１４を個片化せずに蛍光体シート２を個片に切断する工程、および該個片に切断された蛍光体シート２を所望の温度で圧着してウェハレベルのＬＥＤチップに貼り付ける工程が含まれる。 On the other hand, when the phosphor sheet 2 is separated into individual pieces while the base material 14 is continuous, the individual phosphor sheets 2 on the base material 14 are collectively collected as they are at the wafer level before dicing. The LED chip may be heat-sealed. FIG. 6 is a diagram illustrating an example of a method of manufacturing an LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. In the manufacturing method of the LED package with the phosphor sheet, the phosphor sheet 2 is cut when the phosphor sheet 2 is separated into pieces while the base material 14 is continuous, and the phosphor sheet 2 to a wafer level LED chip. Steps such as pasting and dicing are included. In this method of manufacturing an LED package with a phosphor sheet, a step of cutting the phosphor sheet 2 into individual pieces without dividing the substrate 14 into individual pieces, and a phosphor sheet 2 cut into the individual pieces in a desired manner The process includes pressure bonding at a temperature and attaching the wafer level LED chip to the wafer level LED chip.
　例えば、図６に示す蛍光体シート付きＬＥＤパッケージの製造方法では、まず、基材１４に蛍光体シート２を積層する積層工程（状態Ｃ１）が予め行われた後、基材１４に積層された状態の蛍光体シート２を切断して個片化する切断工程が行われる（状態Ｃ２）。この切断工程で蛍光体シート２を個片化する際に、基材１４は個片化されない。図６に示す状態Ｃ２では、基材１４は全く切断されていないが、基材１４が連続している限りは、基材１４が部分的に切断されても構わない。 For example, in the method for manufacturing an LED package with a phosphor sheet shown in FIG. 6, first, a lamination process (state C1) for laminating the phosphor sheet 2 on the base material 14 is performed in advance, and then the base material 14 is laminated. A cutting process is performed in which the phosphor sheet 2 in a state is cut into pieces (state C2). When the phosphor sheet 2 is singulated in this cutting step, the base material 14 is not singulated. In the state C2 shown in FIG. 6, the base material 14 is not cut at all, but the base material 14 may be partially cut as long as the base material 14 is continuous.
　つぎに、個片化された蛍光体シート２を、ダイシング前のＬＥＤウェハ１７に対向させて、このＬＥＤウェハ１７のＬＥＤチップ（図示せず）と位置合わせする位置合わせ工程が行われる（状態Ｃ３）。ＬＥＤウェハ１７は、その表面に複数のＬＥＤチップが形成されたウェハである。ダイシング前のＬＥＤウェハ１７表面のＬＥＤチップが、ウェハレベルのＬＥＤチップである。続いて、これらの蛍光体シート２とダイシング前のＬＥＤウェハ１７とを、加熱圧着ツール１６を用いて、所望の温度で加熱しながら加圧して接着（圧着）する接着工程が行われる（状態Ｃ４）。このとき、蛍光体シート２とＬＥＤウェハ１７表面のＬＥＤチップとの間に空気を噛み込まないように、接着工程は真空下あるいは減圧下で行うことが好ましい。この接着工程により、蛍光体シート２（個片化されたもの）とＬＥＤウェハ１７表面のＬＥＤチップ（ウェハレベルのＬＥＤチップ）とが圧着される。 Next, an alignment step is performed in which the separated phosphor sheet 2 is opposed to the LED wafer 17 before dicing and aligned with an LED chip (not shown) of the LED wafer 17 (state C3). ). The LED wafer 17 is a wafer having a plurality of LED chips formed on the surface thereof. The LED chip on the surface of the LED wafer 17 before dicing is a wafer level LED chip. Subsequently, an adhesion process is performed in which these phosphor sheets 2 and the LED wafer 17 before dicing are pressed and bonded (crimped) while being heated at a desired temperature using the thermocompression bonding tool 16 (state C4). ). At this time, it is preferable to perform the bonding step under vacuum or under reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip on the surface of the LED wafer 17. By this bonding step, the phosphor sheet 2 (separated) and the LED chip (wafer level LED chip) on the surface of the LED wafer 17 are pressure-bonded.
　この接着工程の後、蛍光体シート２、ＬＥＤウェハ１７、および基材１４を室温まで放冷し、このＬＥＤウェハ１７に接着した状態の蛍光体シート２から基材１４を剥離する冷却工程が行われる（状態Ｃ５）。その後、ＬＥＤウェハ１７をダイシングしてＬＥＤチップに個片化するダイシング工程が行われる（状態Ｃ６）。この結果、個片化された蛍光体シート付きＬＥＤチップ１８が、所望数（例えば複数）得られる。 After this adhesion step, the phosphor sheet 2, the LED wafer 17 and the base material 14 are allowed to cool to room temperature, and a cooling step is performed in which the base material 14 is peeled off from the phosphor sheet 2 in a state of being adhered to the LED wafer 17. (State C5). Thereafter, a dicing process is performed in which the LED wafer 17 is diced into individual LED chips (state C6). As a result, a desired number (for example, a plurality) of LED chips 18 with phosphor sheets that are separated into individual pieces are obtained.
　ダイシング前のウェハレベルのＬＥＤチップに一括して蛍光体シート２を熱融着する場合には、貼り付け後にＬＥＤウェハ１７のダイシングと共に、蛍光体シート２を切断することもできる。図７は、本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップの製造方法の別例を示す図である。図７には、蛍光体シート２とＬＥＤウェハ１７とを貼り付け後に一括してダイシングする場合の工程の一例が示されている。この蛍光体シート付きＬＥＤパッケージの製造方法には、ダイシング前の複数のＬＥＤチップ（ウェハレベルのＬＥＤチップ）に蛍光体シート２を所望の温度で圧着して一括して貼り付ける工程、および蛍光体シート２とウェハレベルのＬＥＤチップとを一括してダイシングする工程が含まれる。 When the phosphor sheet 2 is heat-sealed collectively on the wafer level LED chips before dicing, the phosphor sheet 2 can be cut together with the dicing of the LED wafer 17 after being attached. FIG. 7 is a diagram showing another example of the method for manufacturing the LED chip with a phosphor sheet using the phosphor sheet according to the embodiment of the present invention. FIG. 7 shows an example of a process in the case where the phosphor sheet 2 and the LED wafer 17 are collectively diced after being bonded. In this method of manufacturing an LED package with a phosphor sheet, a phosphor sheet 2 is pressure-bonded to a plurality of LED chips (wafer level LED chips) before dicing and bonded together at a desired temperature, and phosphor A step of dicing the sheet 2 and the wafer level LED chips together is included.
　例えば、図７に示す蛍光体シート付きＬＥＤパッケージの製造方法では、まず、基材１４に蛍光体シート２を積層する積層工程が行われた後、蛍光体シート２を予め切断加工することなく、基材１４付きの蛍光体シート２をダイシング前のＬＥＤウェハ１７に対向させて、この蛍光体シート２とＬＥＤウェハ１７とを位置合わせする位置合わせ工程が行われる（状態Ｄ１）。これにより、蛍光体シート２とＬＥＤウェハ１７表面のＬＥＤチップ（図示せず）とが、位置合わせされる。 For example, in the manufacturing method of the LED package with a phosphor sheet shown in FIG. 7, first, after the lamination process of laminating the phosphor sheet 2 on the base material 14 is performed, the phosphor sheet 2 is not cut in advance, An alignment step is performed in which the phosphor sheet 2 with the base material 14 is opposed to the LED wafer 17 before dicing, and the phosphor sheet 2 and the LED wafer 17 are aligned (state D1). Thereby, the phosphor sheet 2 and the LED chip (not shown) on the surface of the LED wafer 17 are aligned.
　つぎに、これらの蛍光体シート２とダイシング前のＬＥＤウェハ１７とを、加熱圧着ツール１６により、所望の温度で加熱しながら加圧して接着（圧着）する接着工程が行われる（状態Ｄ２）。この場合、蛍光体シート２とＬＥＤウェハ１７表面のＬＥＤチップとの間に空気を噛み込まないように、接着工程は真空下あるいは減圧下で行うことが好ましい。この接着工程により、蛍光体シート２（基材１４付きの、個片化されていないもの）とＬＥＤウェハ１７表面のＬＥＤチップ（ウェハレベルのＬＥＤチップ）とが圧着される。 Next, an adhesion process is performed in which the phosphor sheet 2 and the LED wafer 17 before dicing are pressed and bonded (crimped) while being heated at a desired temperature by the thermocompression bonding tool 16 (state D2). In this case, it is preferable to perform the bonding step under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip on the surface of the LED wafer 17. By this bonding step, the phosphor sheet 2 (with the base material 14 and not separated) and the LED chip on the surface of the LED wafer 17 (wafer level LED chip) are pressure-bonded.
　この接着工程の後、蛍光体シート２、ＬＥＤウェハ１７、および基材１４を室温まで放冷し、このＬＥＤウェハ１７に接着した状態の蛍光体シート２から基材１４を剥離する冷却工程が行われる（状態Ｄ３）。その後、ＬＥＤウェハ１７をダイシングしてＬＥＤチップに個片化すると同時に、蛍光体シート２を切断して個片化するダイシング工程（切断工程）が行われる（状態Ｄ４）。この結果、個片化された蛍光体シート付きＬＥＤチップ１８が、所望数（例えば複数）得られる。 After this adhesion step, the phosphor sheet 2, the LED wafer 17 and the base material 14 are allowed to cool to room temperature, and a cooling step is performed in which the base material 14 is peeled off from the phosphor sheet 2 in a state of being adhered to the LED wafer 17. (State D3). Thereafter, the LED wafer 17 is diced to be separated into LED chips, and at the same time, a dicing process (cutting process) for cutting the phosphor sheet 2 into pieces is performed (state D4). As a result, a desired number (for example, a plurality) of LED chips 18 with phosphor sheets that are separated into individual pieces are obtained.
　一方、上述した接着工程の後、ＬＥＤウェハ１７に接着した状態の蛍光体シート２から基材１４を剥離せず、蛍光体シート２、ＬＥＤウェハ１７、および基材１４を室温まで放冷する冷却工程が行われてもよい（状態Ｄ５）。その後、ＬＥＤウェハ１７をダイシングしてＬＥＤチップに個片化すると同時に、蛍光体シート２を基材１４とともに切断して個片化するダイシング工程（切断工程）が行われる（状態Ｄ６）。この結果、基材付きの状態で個片化された蛍光体シート付きＬＥＤチップ１８が、所望数（例えば複数）得られる。このようにして得られた蛍光体シート付きＬＥＤチップ１８は、基材１４（状態Ｄ５参照）がガラス等の透明部材である場合、この基材１４を剥離せず、そのまま用いてもよい。また、基材１４は、ガラス以外のプラスチックフィルム等の不透明部材である場合、個片化された基材付きの蛍光体シート付きＬＥＤチップ１８を基板に実装した後、この蛍光体シート付きＬＥＤチップ１８から剥離してもよい。 On the other hand, after the above-described bonding step, the base material 14 is not peeled off from the phosphor sheet 2 adhered to the LED wafer 17, and the phosphor sheet 2, the LED wafer 17, and the base material 14 are allowed to cool to room temperature. A process may be performed (state D5). Thereafter, the LED wafer 17 is diced into individual LED chips, and at the same time, a dicing process (cutting process) is performed in which the phosphor sheet 2 is cut into individual pieces together with the base material 14 (state D6). As a result, a desired number (for example, a plurality) of LED chips 18 with a phosphor sheet that are separated into pieces with a substrate are obtained. When the base material 14 (see state D5) is a transparent member such as glass, the LED chip 18 with a phosphor sheet thus obtained may be used as it is without peeling off the base material 14. Further, when the base material 14 is an opaque member such as a plastic film other than glass, the LED chip 18 with a phosphor sheet with the base material separated is mounted on the substrate, and then the LED chip with the phosphor sheet is mounted. 18 may be peeled off.
　上述の図５～７に例示されるいずれの工程を採る製造方法においても、上面に電極があるＬＥＤチップに蛍光体シートを貼り付ける場合には、電極部分の蛍光体シートを除去するために、蛍光体シートの貼り付け前に予めその部分に孔開け加工をしておくことが望ましい。孔開け加工は、レーザー加工、金型パンチングなどの公知の方法が好適に使用できる。しかし、レーザー加工は、蛍光体シート中の樹脂の焼け焦げや蛍光体の劣化を引き起こすので、金型によるパンチング加工がより望ましい。蛍光体シートの孔開け加工としてパンチング加工を実施する場合、蛍光体シートをＬＥＤチップに貼り付けた後ではパンチング加工は不可能であるので、蛍光体シートには、貼り付け前にパンチング加工を施すことが必須となる。金型によるパンチング加工は、貼り付けるＬＥＤチップの電極形状などにより、任意の形状や大きさの孔を開けることができる。 In the manufacturing method employing any of the steps illustrated in FIGS. 5 to 7 described above, when the phosphor sheet is attached to the LED chip having the electrode on the upper surface, in order to remove the phosphor sheet in the electrode portion, It is desirable to make a hole in the portion in advance before attaching the phosphor sheet. A known method such as laser processing or die punching can be suitably used for the drilling. However, since laser processing causes scorching of the resin in the phosphor sheet and deterioration of the phosphor, punching with a mold is more desirable. When punching is performed as a punching process for the phosphor sheet, punching is not possible after the phosphor sheet is attached to the LED chip. Therefore, the phosphor sheet is punched before being applied. It is essential. Punching with a mold can open a hole of any shape or size depending on the electrode shape of the LED chip to be attached.
　孔の大きさや形状は、金型を設計すれば任意のものが形成できる。例えば、１ｍｍ角内外のＬＥＤチップ上の電極接合部分は、発光面の面積を小さくしないためには５００μｍ以下であることが望ましい。この場合、孔は、この電極接合部分の大きさに合わせて５００μｍ以下で形成される。また、ワイヤーボンディングなどを行う電極は、ある程度の大きさが必要であり、少なくとも５０μｍ程度の大きさとなる。この場合、孔は、この電極の大きさに合わせて５０μｍ程度で形成される。孔の大きさは、電極より大きすぎると、発光面が露出して光漏れが発生し、ＬＥＤパッケージの色特性が低下する。また、孔の大きさは、電極より小さすぎると、ワイヤーボンディング時にワイヤが触れて接合不良を起こす。従って、孔開け加工は、５０μｍ以上５００μｍ以下という小さい孔を±１０％以内の高精度で加工する必要がある。パンチング加工の精度を向上するためにも、蛍光体シートの２５℃での貯蔵弾性率Ｇ’は、１．０×１０4Ｐａ≦Ｇ’≦１．０×１０6Ｐａであり、かつｔａｎδ＜１であることが非常に重要となる。 Any size and shape of the hole can be formed by designing the mold. For example, the electrode joint portion on the LED chip inside and outside the 1 mm square is desirably 500 μm or less so as not to reduce the area of the light emitting surface. In this case, the hole is formed with a thickness of 500 μm or less in accordance with the size of the electrode joint portion. Moreover, the electrode for performing wire bonding or the like needs to have a certain size, and is at least about 50 μm. In this case, the hole is formed with a size of about 50 μm according to the size of the electrode. If the size of the hole is too large compared to the electrode, the light emitting surface is exposed, light leakage occurs, and the color characteristics of the LED package deteriorate. On the other hand, if the size of the hole is too small than the electrode, the wire touches at the time of wire bonding, resulting in poor bonding. Therefore, in the drilling process, it is necessary to process a small hole of 50 μm or more and 500 μm or less with high accuracy within ± 10%. In order to improve the punching accuracy, the storage elastic modulus G ′ of the phosphor sheet at 25 ° C. is 1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa and tan δ < 1 is very important.
　切断加工や孔開け加工を施した蛍光体シートを、ＬＥＤチップの所定部分に位置合わせして貼り付ける場合には、光学的な位置合わせ（アラインメント）機構を持つ、貼り付け装置が必要となる。このとき、蛍光体シートとＬＥＤチップとを近接させて位置合わせすることは、作業的に難しく、実用的には、蛍光体シートとＬＥＤチップとを軽く接触させた状態で位置合わせすることが、よく行われる。この位置合わせにおいて、蛍光体シートが粘着性を持っていると、この蛍光体シートをＬＥＤチップに接触させて動かすことは、非常に困難である。本発明の実施の形態に係る蛍光体シートであれば、室温で位置合わせを行えば粘着性がないので、蛍光体シートとＬＥＤチップとを軽く接触させた状態で位置合わせすることが容易である。 When a phosphor sheet that has been cut or perforated is aligned and adhered to a predetermined portion of the LED chip, an affixing device having an optical alignment mechanism is required. At this time, it is difficult to align the phosphor sheet and the LED chip in terms of work, and practically, it is possible to align the phosphor sheet and the LED chip in a lightly contacted state. Often done. In this alignment, if the phosphor sheet has adhesiveness, it is very difficult to move the phosphor sheet in contact with the LED chip. If the phosphor sheet according to the embodiment of the present invention is aligned at room temperature, it is not sticky, so that it is easy to align the phosphor sheet and the LED chip in a light contact state. .
　本発明の実施の形態に係る蛍光体シートを用いた蛍光体シート付きＬＥＤチップおよびＬＥＤパッケージの量産的な製造方法を説明する。まず、蛍光体シート付きＬＥＤチップの製造方法を説明する。図８は、本発明の実施の形態に係る蛍光体シートの貼り付け方法の一例を示す図である。図８には、個々のＬＥＤチップ毎に個片化した蛍光体シート積層体２０を用いて、ＬＥＤチップ１へ蛍光体シート２を一つずつ貼り付ける貼り付け方法が示されている。 DETAILED DESCRIPTION A mass production method for an LED chip with a phosphor sheet and an LED package using the phosphor sheet according to an embodiment of the present invention will be described. First, a method for manufacturing an LED chip with a phosphor sheet will be described. FIG. 8 is a diagram showing an example of a phosphor sheet attaching method according to the embodiment of the present invention. FIG. 8 shows a bonding method in which the phosphor sheets 2 are bonded to the LED chips 1 one by one using the phosphor sheet laminate 20 singulated for each LED chip.
　例えば、図８に示す蛍光体シートの貼り付け方法では、基材１９と蛍光体シート２との積層体である蛍光体シート積層体２０は、パッケージ基板２１に実装された複数のＬＥＤチップ１の各々個別に、切断して個片化される。これら複数のＬＥＤチップ１は、各々、その金バンプ８とパッケージ電極２２とを接続して、パッケージ基板２１に予め実装される。個片化された蛍光体シート積層体２０は、パッケージ基板２１上のＬＥＤチップ１と蛍光体シート２とを対向させるように位置決めされる（状態Ｅ１）。その後、この蛍光体シート積層体２０の蛍光体シート２（個片化されたもの）は、加熱圧着などにより、パッケージ基板２１上のＬＥＤチップ１の少なくとも発光面（例えば上面および側面）に順次貼り付けられる（状態Ｅ２）。 For example, in the phosphor sheet attaching method shown in FIG. 8, the phosphor sheet laminate 20, which is a laminate of the base material 19 and the phosphor sheet 2, has a plurality of LED chips 1 mounted on the package substrate 21. Each is individually cut into pieces. Each of the plurality of LED chips 1 is mounted in advance on the package substrate 21 by connecting the gold bump 8 and the package electrode 22. The separated phosphor sheet laminate 20 is positioned so that the LED chip 1 and the phosphor sheet 2 on the package substrate 21 face each other (state E1). Thereafter, the phosphor sheet 2 (separated) of the phosphor sheet laminate 20 is sequentially attached to at least the light emitting surface (for example, the upper surface and the side surface) of the LED chip 1 on the package substrate 21 by thermocompression bonding or the like. Attached (state E2).
　図９は、本発明の実施の形態に係る蛍光体シートの貼り付け方法の別例を示す図である。図９には、複数のＬＥＤチップ１に一括で蛍光体シート２を被覆した後、この蛍光体シート２をカットして個別化する貼り付け方法が示されている。例えば、図９に示す蛍光体シートの貼り付け方法では、基材１９と蛍光体シート２との積層体である蛍光体シート積層体２０は、個片化せずに、パッケージ基板２１上の複数のＬＥＤチップ１と蛍光体シート２とを一括して対向させるように位置決めされる（状態Ｆ１）。これら複数のＬＥＤチップ１は、図８に示した場合と同様に、金バンプ８とパッケージ電極２２とを接続してパッケージ基板２１に予め実装される。その後、この蛍光体シート積層体２０の蛍光体シート２（個片化されていないもの）は、加熱圧着などにより、パッケージ基板２１上の複数のＬＥＤチップ１の少なくとも発光面（例えば上面および側面）に一括して貼り付けられる（状態Ｆ２）。特に図９には示さないが、このように複数のＬＥＤチップ１に貼り付けられた蛍光体シート２は、その後、これら複数のＬＥＤチップ１の各々個別に、切断して個別化される。 FIG. 9 is a diagram showing another example of the phosphor sheet attaching method according to the embodiment of the present invention. FIG. 9 shows a pasting method in which a plurality of LED chips 1 are collectively covered with a phosphor sheet 2 and then the phosphor sheet 2 is cut and individualized. For example, in the phosphor sheet attaching method shown in FIG. 9, the phosphor sheet laminate 20, which is a laminate of the base material 19 and the phosphor sheet 2, is not separated into a plurality of pieces on the package substrate 21. The LED chip 1 and the phosphor sheet 2 are positioned so as to face each other at once (state F1). The plurality of LED chips 1 are mounted in advance on the package substrate 21 by connecting the gold bumps 8 and the package electrodes 22 as in the case shown in FIG. Thereafter, the phosphor sheet 2 (not separated into individual pieces) of the phosphor sheet laminate 20 is subjected to at least light emitting surfaces (for example, upper and side surfaces) of the plurality of LED chips 1 on the package substrate 21 by thermocompression bonding or the like. (State F2). Although not specifically shown in FIG. 9, the phosphor sheet 2 attached to the plurality of LED chips 1 is then cut and individualized individually for each of the plurality of LED chips 1.
　蛍光体シート付きＬＥＤチップの製造方法におけるＬＥＤチップ１への蛍光体シート２の貼り付け方法としては、上述した図８に示す方法および図９に示す方法が挙げられるが、いずれの方法を用いてもよい。 Examples of the method for attaching the phosphor sheet 2 to the LED chip 1 in the method for producing the LED chip with the phosphor sheet include the method shown in FIG. 8 and the method shown in FIG. 9 described above, and any method is used. Also good.
　ＬＥＤチップ１への蛍光体シート２の貼り付けは、基材１９が軟化流動する状態で押圧して行う。特に、蛍光体シート２として熱融着性の蛍光体シートを用いている場合は、接着性の強化の観点から、貼り付け温度は、６０℃以上が好ましく、８０℃以上がより好ましい。また、蛍光体シート２に用いる熱融着性樹脂は、加熱により一時的に粘度が下がり、さらに加熱を続けると熱硬化する性質を持っている。そのため、貼り付け工程の温度は、接着性を保持する観点から、１５０℃以下であることが好ましく、さらに、蛍光体シート２の粘度を一定以上に保ち、形状を保持するという観点から、１２０℃以下であることがより好ましい。また、空気溜まりの残存を防ぐために、０．０１ＭＰａ以下の減圧下で貼り付けを行うことが好ましい。 The affixing of the phosphor sheet 2 to the LED chip 1 is performed by pressing the base material 19 in a state of softening and flowing. In particular, when a heat-sealable phosphor sheet is used as the phosphor sheet 2, the sticking temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher, from the viewpoint of enhancing adhesiveness. Moreover, the heat-fusible resin used for the phosphor sheet 2 has a property that the viscosity is temporarily lowered by heating, and is further cured by heating. Therefore, the temperature of the attaching step is preferably 150 ° C. or less from the viewpoint of maintaining adhesiveness, and further, 120 ° C. from the viewpoint of maintaining the shape of the phosphor sheet 2 at a certain level or more. The following is more preferable. Further, in order to prevent the remaining of the air pool, it is preferable to perform the pasting under a reduced pressure of 0.01 MPa or less.
　このような貼り付けを行う製造装置としては、真空ダイアフラムラミネーター、真空ロールラミネーター、真空油圧プレス、真空サーボプレス、真空電動プレス、ＴＯＭ成形機などの真空貼り付け機などが例示される。中でも、一度に処理できる数が多く、また、真上から偏りなく加圧できることが可能であることから、真空ダイアフラムラミネーターが好ましい。 Examples of the manufacturing apparatus for performing such affixing include vacuum affixing machines such as a vacuum diaphragm laminator, a vacuum roll laminator, a vacuum hydraulic press, a vacuum servo press, a vacuum electric press, and a TOM molding machine. Among these, a vacuum diaphragm muraminator is preferable because the number that can be processed at one time is large, and pressure can be applied without deviation from directly above.
　つぎに、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法について、２つの方法を例示する。なお、ＬＥＤパッケージの製造方法は、これらの例に限定されない。 Next, two methods will be exemplified for the manufacturing method of the LED package using the phosphor sheet according to the embodiment of the present invention. The LED package manufacturing method is not limited to these examples.
　図１０は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の一例を示す図である。図１０に例示するＬＥＤパッケージの製造方法では、まず、台座２４上に両面粘着テープ２３を介してＬＥＤチップ１を仮固定する仮固定工程が行われる（状態Ｇ１）。続いて、蛍光体シート積層体２０を、蛍光体シート２がＬＥＤチップ１に接するように位置合わせして積層する積層工程が行われる（状態Ｇ２）。この積層工程により、台座２４（状態Ｇ１参照）上のＬＥＤチップ１と蛍光体シート２と基材１９との積層体である積層物３７が得られる。 FIG. 10 is a diagram showing an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention. In the LED package manufacturing method illustrated in FIG. 10, first, a temporary fixing step of temporarily fixing the LED chip 1 on the pedestal 24 via the double-sided adhesive tape 23 is performed (state G1). Then, the lamination process which positions and laminates | stacks the phosphor sheet laminated body 20 so that the phosphor sheet 2 may contact | connect the LED chip 1 is performed (state G2). By this lamination process, a laminate 37 that is a laminate of the LED chip 1, the phosphor sheet 2, and the base material 19 on the pedestal 24 (see state G1) is obtained.
　つぎに、積層物３７のＬＥＤチップ１と蛍光体シート２とを接着する接着工程が行われる（状態Ｇ３）。この接着工程において、積層物３７は、真空ダイアフラムラミネーター２８の下部チャンバー２６に入れる。その後、真空ダイアフラムラミネーター２８は、積層物３７を加熱しながら、排気口２９ｂからの排気により、上部チャンバー２５および下部チャンバー２６を減圧する。ついで、真空ダイアフラムラミネーター２８は、積層物３７の基材１９が流動するまで減圧加熱を行った後、上部チャンバー２５に吸気口２９ａを通じて大気を吸入することでダイアフラム２７を膨張させる。これにより、ダイアフラム２７は、この基材１９を通じて蛍光体シート２をＬＥＤチップ１に押圧し、この蛍光体シート２をＬＥＤチップ１の発光面に追従するように貼り付ける。 Next, an adhesion process for adhering the LED chip 1 and the phosphor sheet 2 of the laminate 37 is performed (state G3). In this bonding step, the laminate 37 is placed in the lower chamber 26 of the vacuum diaphragm muraminator 28. Thereafter, the vacuum diaphragm muraminator 28 depressurizes the upper chamber 25 and the lower chamber 26 by exhausting from the exhaust port 29 b while heating the laminate 37. Next, the vacuum diaphragm muraminator 28 performs heating under reduced pressure until the base material 19 of the laminate 37 flows, and then expands the diaphragm 27 by sucking air into the upper chamber 25 through the air inlet 29a. Thereby, the diaphragm 27 presses the phosphor sheet 2 against the LED chip 1 through the base material 19 and affixes the phosphor sheet 2 so as to follow the light emitting surface of the LED chip 1.
　ついで、ＬＥＤチップ１と蛍光体シート２との接着物を切断して個片化する切断工程が行われる（状態Ｇ４）。この切断工程において、真空ダイアフラムラミネーター２８は、上部チャンバー２５および下部チャンバー２６を大気圧に戻す。その後、積層物３７は、真空ダイアフラムラミネーター２８から取り出し、放冷後に、基材１９（状態Ｇ３参照）を剥離される。続いて、蛍光体シート２は、台座２４上の各ＬＥＤチップ１間の切断部分３０をダイシングカッターなどで両面粘着テープ２３ごと切断することにより、ＬＥＤチップ１の発光面を被覆した状態で個片化される。この結果、個片化した蛍光体シート付きＬＥＤチップ３１（状態Ｇ５参照）が作製される。 Next, a cutting step is performed in which the adhesive between the LED chip 1 and the phosphor sheet 2 is cut into pieces (state G4). In this cutting step, the vacuum diaphragm muraminator 28 returns the upper chamber 25 and the lower chamber 26 to atmospheric pressure. Thereafter, the laminate 37 is taken out from the vacuum diaphragm laminator 28, and after being allowed to cool, the substrate 19 (see state G3) is peeled off. Subsequently, the phosphor sheet 2 is cut in a state where the light emitting surface of the LED chip 1 is covered by cutting the cut portion 30 between the LED chips 1 on the pedestal 24 together with the double-sided adhesive tape 23 with a dicing cutter or the like. It becomes. As a result, an individual LED chip 31 with a phosphor sheet (see state G5) is manufactured.
　その後、蛍光体シート付きＬＥＤチップ３１をパッケージ基板２１に実装する実装工程が行われる（状態Ｇ５）。この実装工程において、蛍光体シート付きＬＥＤチップ３１は、パッケージ基板２１上のパッケージ電極２２に金バンプ８を介して接合される。以上の工程により、ＬＥＤパッケージ３２が製造される（状態Ｇ６）。特に図１０には示さないが、このＬＥＤパッケージ３２には、必要に応じて、透明樹脂によるオーバーコート層やレンズ等が設けられる。 Thereafter, a mounting process for mounting the LED chip 31 with the phosphor sheet on the package substrate 21 is performed (state G5). In this mounting process, the LED chip 31 with the phosphor sheet is bonded to the package electrode 22 on the package substrate 21 via the gold bumps 8. Through the above steps, the LED package 32 is manufactured (state G6). Although not particularly shown in FIG. 10, the LED package 32 is provided with an overcoat layer made of a transparent resin, a lens, or the like as necessary.
　図１１は、本発明の実施の形態に係る蛍光体シートを用いたＬＥＤパッケージの製造方法の別例を示す図である。図１１に例示するＬＥＤパッケージの製造方法では、まず、ＬＥＤチップ１をパッケージ基板２１上のパッケージ電極２２に金バンプ８を介して接合する実装工程が行われる（状態Ｈ１）。続いて、蛍光体シート積層体２０を、蛍光体シート２がＬＥＤチップ１に接するように位置合わせして積層する積層工程が行われる（状態Ｈ２）。この積層工程により、パッケージ基板２１上のＬＥＤチップ１と蛍光体シート２と基材１９との積層体である積層物３８が得られる。 FIG. 11 is a diagram showing another example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention. In the LED package manufacturing method illustrated in FIG. 11, first, a mounting process is performed in which the LED chip 1 is bonded to the package electrode 22 on the package substrate 21 via the gold bumps 8 (state H1). Then, the lamination process which positions and laminates | stacks the phosphor sheet laminated body 20 so that the phosphor sheet 2 may contact | connect the LED chip 1 is performed (state H2). By this lamination step, a laminate 38 that is a laminate of the LED chip 1, the phosphor sheet 2, and the base material 19 on the package substrate 21 is obtained.
　つぎに、積層物３８のＬＥＤチップ１と蛍光体シート２とを接着する接着工程が行われる（状態Ｈ３）。この接着工程において、積層物３８は、真空ダイアフラムラミネーター２８の下部チャンバー２６に入れる。その後、真空ダイアフラムラミネーター２８は、積層物３８を加熱しながら、排気口２９ｂからの排気により、上部チャンバー２５および下部チャンバー２６を減圧する。ついで、真空ダイアフラムラミネーター２８は、積層物３８の基材１９が流動するまで減圧加熱を行った後、上部チャンバー２５に吸気口２９ａを通じて大気を吸入することでダイアフラム２７を膨張させる。これにより、ダイアフラム２７は、この基材１９を通じて蛍光体シート２をＬＥＤチップ１に押圧し、この蛍光体シート２をＬＥＤチップ１の発光面に追従するように貼り付ける。 Next, an adhesion process for adhering the LED chip 1 and the phosphor sheet 2 of the laminate 38 is performed (state H3). In this bonding step, the laminate 38 is placed in the lower chamber 26 of the vacuum diaphragm muraminator 28. Thereafter, the vacuum diaphragm muraminator 28 depressurizes the upper chamber 25 and the lower chamber 26 by exhausting from the exhaust port 29b while heating the laminate 38. Next, the vacuum diaphragm muraminator 28 performs heating under reduced pressure until the base material 19 of the laminate 38 flows, and then expands the diaphragm 27 by sucking air into the upper chamber 25 through the air inlet 29a. Thereby, the diaphragm 27 presses the phosphor sheet 2 against the LED chip 1 through the base material 19 and affixes the phosphor sheet 2 so as to follow the light emitting surface of the LED chip 1.
　ついで、パッケージ基板２１とＬＥＤチップ１と蛍光体シート２との接合物を切断して個片化する切断工程が行われる（状態Ｈ４）。この切断工程において、真空ダイアフラムラミネーター２８は、上部チャンバー２５および下部チャンバー２６を大気圧に戻す。その後、積層物３８は、真空ダイアフラムラミネーター２８から取り出し、放冷後に、基材１９（状態Ｈ３参照）を剥離される。続いて、蛍光体シート２は、パッケージ基板２１における各ＬＥＤチップ１間の切断部分３０を切断することにより、ＬＥＤチップ１の発光面を被覆した状態でパッケージ基板２１とともに個片化される。以上の工程により、ＬＥＤパッケージ３２が製造される（状態Ｈ５）。特に図１１には示さないが、このＬＥＤパッケージ３２には、必要に応じて、透明樹脂によるオーバーコート層やレンズ等が設けられる。 Next, a cutting process is performed in which the joined product of the package substrate 21, the LED chip 1, and the phosphor sheet 2 is cut into individual pieces (state H4). In this cutting step, the vacuum diaphragm muraminator 28 returns the upper chamber 25 and the lower chamber 26 to atmospheric pressure. Thereafter, the laminate 38 is taken out from the vacuum diaphragm laminator 28, and after standing to cool, the substrate 19 (see state H3) is peeled off. Subsequently, the phosphor sheet 2 is cut into pieces together with the package substrate 21 in a state where the light emitting surface of the LED chip 1 is covered by cutting the cut portions 30 between the LED chips 1 in the package substrate 21. The LED package 32 is manufactured through the above steps (state H5). Although not particularly shown in FIG. 11, the LED package 32 is provided with an overcoat layer made of a transparent resin, a lens, or the like as necessary.
＜発光装置、バックライトユニット、ディスプレイ＞
　本発明の実施の形態に係る発光装置は、上述した蛍光体組成物、蛍光体シート、または蛍光体形成物の一適用例である。例えば、この発光装置は、上述した蛍光体組成物またはその硬化物を含有する蛍光体形成物と、この蛍光体形成物に含まれる蛍光体組成物によって発光光が色変換されるＬＥＤチップ（発光体）を有するＬＥＤパッケージと、を備える。本発明の実施の形態に係るバックライトユニットは、この発光装置の一応用例である。例えば、このバックライトユニットは、上述した蛍光体組成物の硬化物を有するＬＥＤパッケージ、あるいは、上述した蛍光体シートまたはその硬化物を有するＬＥＤパッケージを備える。このように構成されるバックライトユニットは、ディスプレイ、照明、インテリア、標識、看板、などの用途に使用できるが、特にディスプレイや照明用途に好適に用いられる。本発明の実施の形態に係るディスプレイ（例えば液晶ディスプレイ）は、このバックライトユニットの一適用例である。例えば、このディスプレイは、上述した蛍光体組成物の硬化物を有するＬＥＤパッケージ、あるいは、上述した蛍光体シートまたはその硬化物を有するＬＥＤパッケージを備える。 <Light emitting device, backlight unit, display>
The light emitting device according to the embodiment of the present invention is an application example of the phosphor composition, the phosphor sheet, or the phosphor formed article described above. For example, this light-emitting device includes a phosphor formed product containing the above-described phosphor composition or a cured product thereof, and an LED chip (light emission) whose emitted light is color-converted by the phosphor composition contained in the phosphor formed product. And an LED package having a body. The backlight unit according to the embodiment of the present invention is an application example of this light emitting device. For example, the backlight unit includes an LED package having a cured product of the phosphor composition described above, or an LED package having the phosphor sheet described above or a cured product thereof. The backlight unit configured as described above can be used for displays, lighting, interiors, signs, signboards, and the like, but is particularly suitable for display and lighting applications. A display (for example, a liquid crystal display) according to an embodiment of the present invention is an application example of this backlight unit. For example, the display includes an LED package having a cured product of the above-described phosphor composition, or an LED package having the above-described phosphor sheet or a cured product thereof.
　以下に、本発明を実施例により、具体的に説明する。ただし、本発明はこれらの例によって限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples.
＜基材＞
　基材は、離型処理済みポリエチレンテレフタレート（ポリエチレンテレフタレートフィルム）である“セラピール”ＢＸ９（東レフィルム加工（株）製、平均膜厚５０μｍ）を用いた。 <Base material>
As the base material, “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm), which is a polyethylene terephthalate (polyethylene terephthalate film) that has been subjected to a release treatment, was used.
＜無機蛍光体＞
　無機蛍光体の一例としてのＹＡＧ系蛍光体のタイプ１（ＹＡＧ１）は、（株）ネモト・ルミマテリアル社製“ＹＡＧ８１００３”である。無機蛍光体の一例としてのβ型サイアロン蛍光体のタイプ１（β１）は、デンカ（株）社製“ＧＲ－ＳＷ５２９Ｙ”である。このβ型サイアロン蛍光体（β１）のピーク波長は、５２９ｎｍであり、平均粒径（Ｄ５０）は、１６μｍである。β型サイアロン蛍光体のタイプ２（β２）は、デンカ（株）社製“ＧＲ－ＭＷ５４０Ｈ”である。このβ型サイアロン蛍光体（β２）のピーク波長は、５４４ｎｍであり、平均粒径（Ｄ５０）は、２０μｍである。β型サイアロン蛍光体のタイプ３（β３）は、デンカ（株）社製“ＧＲ－ＳＷ５３２Ｄ”である。このβ型サイアロン蛍光体（β３）のピーク波長は、５３８ｎｍであり、平均粒径（Ｄ５０）は、１６μｍである。無機蛍光体の一例としてのＫＳＦ蛍光体のタイプ１（ＫＳＦ１）は、（株）ネモト・ルミマテリアル社製のＫＳＦ蛍光体サンプルＡである。このＫＳＦ蛍光体（ＫＳＦ１）の平均粒径（Ｄ５０）は、５０μｍである。ＫＳＦ蛍光体のタイプ２（ＫＳＦ２）は、（株）ネモト・ルミマテリアル社製のＫＳＦ蛍光体サンプルＢである。このＫＳＦ蛍光体（ＫＳＦ２）の平均粒径（Ｄ５０）は、３０μｍである。 <Inorganic phosphor>
YAG phosphor type 1 (YAG1) as an example of the inorganic phosphor is “YAG81003” manufactured by Nemoto Lumi Materials. Type 1 (β1) of β-sialon phosphor as an example of the inorganic phosphor is “GR-SW529Y” manufactured by Denka Co., Ltd. The peak wavelength of the β-type sialon phosphor (β1) is 529 nm, and the average particle size (D50) is 16 μm. Type 2 (β2) of the β-type sialon phosphor is “GR-MW540H” manufactured by Denka Co., Ltd. The peak wavelength of the β-type sialon phosphor (β2) is 544 nm, and the average particle size (D50) is 20 μm. Type 3 (β3) of the β-type sialon phosphor is “GR-SW532D” manufactured by Denka Co., Ltd. The peak wavelength of the β-type sialon phosphor (β3) is 538 nm, and the average particle size (D50) is 16 μm. The KSF phosphor type 1 (KSF1) as an example of the inorganic phosphor is a KSF phosphor sample A manufactured by Nemoto Lumi Material Co., Ltd. The average particle diameter (D50) of this KSF phosphor (KSF1) is 50 μm. Type 2 (KSF2) of KSF phosphor is KSF phosphor sample B manufactured by Nemoto Lumi Material Co., Ltd. The average particle diameter (D50) of this KSF phosphor (KSF2) is 30 μm.
＜有機発光材料＞
　有機発光材料の合成例を以下に示す。1Ｈ－ＮＭＲは、超伝導ＦＴＮＭＲ　ＥＸ－２７０（日本電子（株）製）を用い、重クロロホルム溶液にて測定を行った。ＨＰＬＣは、高速液体クロマトグラフ　ＬＣ－１０（（株）島津製作所製）を用い、０．１ｇ／Ｌのクロロホルム溶液にて測定した。カラムの展開溶媒としては、０．１％リン酸水溶液とアセトニトリルとの混合溶液を用いた。吸収スペクトルおよび蛍光スペクトルは、それぞれ、Ｕ－３２００形分光光度計、Ｆ－２５００形蛍光分光光度計（ともに日立製作所（株）製）を用い、４×１０-6ｍｏｌ／Ｌのジクロロメタン溶液中にて測定を行った。 <Organic luminescent material>
Synthesis examples of organic light emitting materials are shown below. 1 H-NMR was measured in a deuterated chloroform solution using superconducting FTNMR EX-270 (manufactured by JEOL Ltd.). HPLC was measured with a 0.1 g / L chloroform solution using a high performance liquid chromatograph LC-10 (manufactured by Shimadzu Corporation). As a developing solvent for the column, a mixed solution of 0.1% phosphoric acid aqueous solution and acetonitrile was used. The absorption spectrum and fluorescence spectrum were measured in a 4 × 10 −6 mol / L dichloromethane solution using a U-3200 type spectrophotometer and an F-2500 type spectrophotometer (both manufactured by Hitachi, Ltd.), respectively. And measured.
（合成例１）
　以下に、合成例１の有機発光材料（タイプ２１）の合成方法について説明する。有機発光材料（タイプ２１）の合成方法では、４－ｔ－ブチルベンズアルデヒド１２．２ｇ、４－メトキシアセトフェノン１１．３ｇ、３Ｍ水酸化カリウム水溶液３２ｍｌとエタノール２０ｍｌの混合溶液を窒素気流下、室温で１２時間撹拌した。析出した固体をろ取し、冷エタノール５０ｍｌで２回洗浄した。真空乾燥した後、３－（４－ｔ－ブチルフェニル）－１－（４－メトキシフェニル）プロペノン１７ｇを得た。 (Synthesis Example 1)
Below, the synthesis | combining method of the organic luminescent material (type 21) of the synthesis example 1 is demonstrated. In the synthesis method of the organic light emitting material (type 21), 12.2 g of 4-t-butylbenzaldehyde, 11.3 g of 4-methoxyacetophenone, 32 ml of 3M potassium hydroxide aqueous solution and 20 ml of ethanol were mixed at room temperature under a nitrogen stream at room temperature. Stir for hours. The precipitated solid was collected by filtration and washed twice with 50 ml of cold ethanol. After vacuum drying, 17 g of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) propenone was obtained.
　つぎに、３－（４－ｔ－ブチルフェニル）－１－（４－メトキシフェニル）プロペノン１７ｇ、ジエチルアミン２１．２ｇ、ニトロメタン１７．７ｇとメタノール５８０ｍｌの混合溶液を窒素気流下、１４時間、加熱還流した。得られた溶液を、室温に冷却後、エバポレートした。シリカゲルカラムクロマトグラフィーにより精製し、真空乾燥した後、３－（４－ｔ－ブチルフェニル）－１－（４－メトキシフェニル）－４－ニトロブタン－１－オン１６ｇを得た。 Next, a mixed solution of 17 g of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) propenone, 21.2 g of diethylamine, 17.7 g of nitromethane and 580 ml of methanol was heated to reflux for 14 hours under a nitrogen stream. did. The resulting solution was cooled to room temperature and then evaporated. After purification by silica gel column chromatography and vacuum drying, 16 g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutan-1-one was obtained.
　つぎに、メタノール２３０ｍｌと濃硫酸４６ｍｌの混合溶液を窒素気流下、０℃で撹拌した。あらかじめ調整した３－（４－ｔ－ブチルフェニル）－１－（４－メトキシフェニル）－４－ニトロブタン－１－オン１．４２ｇ、メタノール４０ｍｌとテトラヒドロフラン８０ｍｌの混合溶液を窒素気流下、水酸化カリウム粉末１．１２ｇを加え、室温で１時間撹拌したものをゆっくり滴下し、室温でさらに１時間撹拌した。ついで、０℃まで冷却後、水５０ｍｌを加え、４Ｍ水酸化ナトリウム水溶液で中和し、ジクロロメタン５０ｍｌで抽出した。有機層を水３０ｍｌで２回洗浄し、硫酸ナトリウムで乾燥後、エバポレートし、粘調体を得た。 Next, a mixed solution of 230 ml of methanol and 46 ml of concentrated sulfuric acid was stirred at 0 ° C. under a nitrogen stream. A prepared solution of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutan-1-one (1.42 g), methanol (40 ml) and tetrahydrofuran (80 ml) was added in a nitrogen stream under potassium hydroxide. 1.12 g of powder was added, and the mixture stirred at room temperature for 1 hour was slowly added dropwise, and the mixture was further stirred at room temperature for 1 hour. Then, after cooling to 0 ° C., 50 ml of water was added, neutralized with 4M aqueous sodium hydroxide solution, and extracted with 50 ml of dichloromethane. The organic layer was washed twice with 30 ml of water, dried over sodium sulfate and evaporated to obtain a viscous product.
　つぎに、得られた粘調体、酢酸アンモニウム１．５４ｇと酢酸２０ｍｌの混合溶液を窒素気流下、１００℃で１時間、加熱還流した。ついで、室温に冷却後、氷水を加え、４Ｍ水酸化ナトリウム水溶液で中和し、ジクロロメタン５０ｍｌで抽出した。有機層を水３０ｍｌで２回洗浄し、硫酸ナトリウムで乾燥後、エバポレートした。エタノール２０ｍｌで洗浄し、真空乾燥した後、４－（４－ｔ－ブチルフェニル）－２－（４－メトキシフェニル）ピロール５５５ｍｇを得た。 Next, a mixed solution of the obtained viscous material, 1.54 g of ammonium acetate and 20 ml of acetic acid was heated to reflux at 100 ° C. for 1 hour under a nitrogen stream. Then, after cooling to room temperature, ice water was added, neutralized with 4M aqueous sodium hydroxide solution, and extracted with 50 ml of dichloromethane. The organic layer was washed twice with 30 ml of water, dried over sodium sulfate and evaporated. After washing with 20 ml of ethanol and vacuum drying, 555 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole was obtained.
　つぎに、２－ベンゾイル－３，５－ビス（４－ｔ－ブチルフェニル）ピロール３５７ｍｇ、４－（４－ｔ－ブチルフェニル）－２－（４－メトキシフェニル）ピロール２５０ｍｇ、オキシ塩化リン１３８ｍｇと１，２－ジクロロエタン１０ｍｌの混合溶液を窒素気流下、９時間、加熱還流した。ついで、室温に冷却後、ジイソプロピルエチルアミン８４７ｍｇ、三フッ化ホウ素ジエチルエーテル錯体９３１ｍｇを加え、３時間攪拌した。水２０ｍｌを注入し、ジクロロメタン３０ｍｌで抽出した。有機層を水２０ｍｌで２回洗浄し、硫酸マグネシウムで乾燥後、エバポレートした。シリカゲルカラムクロマトグラフィーにより精製し、真空乾燥した後、下記に示す有機発光材料（タイプ２１）を合成した。　
 
1Ｈ－ＮＭＲ（ＣＤＣｌ3（ｄ＝ｐｐｍ））：１．１８（ｓ，１８Ｈ）、１．３５（ｓ，９Ｈ）、３．８５（ｓ，３Ｈ）、６．３７－６．９９（ｍ，１７Ｈ）、７．４５（ｄ，２Ｈ）、７．８７（ｄ，４Ｈ）。
  Next, 357 mg of 2-benzoyl-3,5-bis (4-t-butylphenyl) pyrrole, 250 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 138 mg of phosphorus oxychloride, A mixed solution of 10 ml of 1,2-dichloroethane was heated to reflux for 9 hours under a nitrogen stream. Next, after cooling to room temperature, 847 mg of diisopropylethylamine and 931 mg of boron trifluoride diethyl ether complex were added and stirred for 3 hours. 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated. After purification by silica gel column chromatography and vacuum drying, an organic light emitting material (type 21) shown below was synthesized.

1 H-NMR (CDCl 3 (d = ppm)): 1.18 (s, 18H), 1.35 (s, 9H), 3.85 (s, 3H), 6.37-6.99 (m , 17H), 7.45 (d, 2H), 7.87 (d, 4H).
Figure JPOXMLDOC01-appb-C000043
  
Figure JPOXMLDOC01-appb-C000043
  
（合成例２）
　以下に、合成例２の有機発光材料（タイプ２２）の合成方法について説明する。有機発光材料（タイプ２２）の合成方法では、４－（４－ｔ－ブチルフェニル）－２－（４－メトキシフェニル）ピロール３００ｍｇ、２－メトキシベンゾイルクロリド２０１ｍｇとトルエン１０ｍｌの混合溶液を窒素気流下、１２０℃で６時間加熱した。ついで、室温に冷却後、エバポレートした。エタノール２０ｍｌで洗浄し、真空乾燥した後、２－（２－メトキシベンゾイル）－３－（４－ｔ－ブチルフェニル）－５－（４－メトキシフェニル）ピロール２６０ｍｇを得た。 (Synthesis Example 2)
Below, the synthesis | combining method of the organic luminescent material (type 22) of the synthesis example 2 is demonstrated. In the synthesis method of the organic light emitting material (type 22), a mixed solution of 300 mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was placed in a nitrogen stream. And heated at 120 ° C. for 6 hours. Subsequently, it was evaporated after cooling to room temperature. After washing with 20 ml of ethanol and vacuum drying, 260 mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.
　つぎに、２－（２－メトキシベンゾイル）－３－（４－ｔ－ブチルフェニル）－５－（４－メトキシフェニル）ピロール２６０ｍｇ、４－（４－ｔ－ブチルフェニル）－２－（４－メトキシフェニル）ピロール１８０ｍｇ、メタンスルホン酸無水物２０６ｍｇと脱気したトルエン１０ｍｌの混合溶液を窒素気流下、１２５℃で７時間加熱した。ついで、室温に冷却後、水２０ｍｌを注入し、ジクロロメタン３０ｍｌで抽出した。有機層を水２０ｍｌで２回洗浄し、エバポレートし、真空乾燥した。 Next, 260 mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 4- (4-tert-butylphenyl) -2- (4- A mixed solution of 180 mg of methoxyphenyl) pyrrole, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125 ° C. for 7 hours under a nitrogen stream. Then, after cooling to room temperature, 20 ml of water was poured and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated and dried in vacuo.
　つぎに、得られたピロメテン体とトルエン１０ｍｌの混合溶液を窒素気流下、ジイソプロピルエチルアミン３０５ｍｇ、三フッ化ホウ素ジエチルエーテル錯体６７０ｍｇを加え、室温で３時間攪拌した。ついで、水２０ｍｌを注入し、ジクロロメタン３０ｍｌで抽出した。有機層を水２０ｍｌで２回洗浄し、硫酸マグネシウムで乾燥後、エバポレートした。シリカゲルカラムクロマトグラフィーにより精製し、下記に示す有機発光材料（タイプ２２）を合成した。
 
1Ｈ－ＮＭＲ（ＣＤＣｌ3（ｄ＝ｐｐｍ））：１．１９（ｓ，１８Ｈ）、３．４２（ｓ，３Ｈ）、３．８５（ｓ，６Ｈ）、５．７２（ｄ，１Ｈ）、６．２０（ｔ，１Ｈ）、６．４２－６．９７（ｍ，１６Ｈ）、７．８９（ｄ，４Ｈ）。
  Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyromethene and 10 ml of toluene under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. Then, 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated. The organic light emitting material (type 22) shown below was synthesized by purification by silica gel column chromatography.

1 H-NMR (CDCl 3 (d = ppm)): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H).
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
（合成例３）
　以下に、合成例３の有機発光材料（タイプ２３）の合成方法について説明する。有機発光材料（タイプ２３）の合成方法では、１，２－ジクロロエタン３０ｍｌ中に、２－（２－メトキシベンゾイル）－３，５－ビス（４－ｔ－ブチルフェニル）ピロール５．０ｇ、２，４－ビス（４－ｔ－ブチルフェニル）ピロール３．３ｇ、オキシ塩化リン１．５ｇを入れ、加熱環流下、１２時間反応させた。ついで、室温に冷却した後、ジイソプロピルエチルアミン５．２ｇ、三フッ化ホウ素ジエチルエーテル錯体５．６ｇを加え、６時間撹拌した。５０ｍｌの水を加え、ジクロロメタンを投入後、有機層を抽出し、濃縮して、シリカゲルを用いたカラムクロマトグラフィーによる精製をした後、さらに昇華精製を行い、下記に示す有機発光材料（タイプ２３）を合成した。
 
1Ｈ－ＮＭＲ（ＣＤＣｌ3（ｄ＝ｐｐｍ））：１．０７（ｓ，９Ｈ）、２．１３（ｓ，６Ｈ）、２．３９（ｓ，６Ｈ）、６．４７（ｔ，４Ｈ）、６．６３（ｓ，８Ｈ）、６．７５（ｄ，２Ｈ）、７．２３（ｄ，４Ｈ）、７．８０（ｄ，４Ｈ）。
  (Synthesis Example 3)
Below, the synthesis | combining method of the organic luminescent material (type 23) of the synthesis example 3 is demonstrated. In the synthesis method of the organic light emitting material (type 23), 5.0 g of 2- (2-methoxybenzoyl) -3,5-bis (4-tert-butylphenyl) pyrrole in 30 ml of 1,2-dichloroethane, 2, 4-bis (4-t-butylphenyl) pyrrole (3.3 g) and phosphorus oxychloride (1.5 g) were added, and the mixture was reacted for 12 hours under heating and reflux. Then, after cooling to room temperature, 5.2 g of diisopropylethylamine and 5.6 g of boron trifluoride diethyl ether complex were added and stirred for 6 hours. 50 ml of water was added, dichloromethane was added, the organic layer was extracted, concentrated, purified by column chromatography using silica gel, further purified by sublimation, and the organic light emitting material shown below (type 23) Was synthesized.

1 H-NMR (CDCl 3 (d = ppm)): 1.07 (s, 9H), 2.13 (s, 6H), 2.39 (s, 6H), 6.47 (t, 4H), 6.63 (s, 8H), 6.75 (d, 2H), 7.23 (d, 4H), 7.80 (d, 4H).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
（合成例４）
　以下に、合成例４の有機発光材料（タイプ２４）の合成方法について説明する。有機発光材料（タイプ２４）の合成方法では、３，５－ジブロモベンズアルデヒド（３．０ｇ）、４－ｔ－ブチルフェニルボロン酸（５．３ｇ）、テトラキス（トリフェニルホスフィン）パラジウム（０）（０．４ｇ）、炭酸カリウム（２．０ｇ）をフラスコに入れ、窒素置換した。ここに、脱気したトルエン（３０ｍＬ）および脱気した水（１０ｍＬ）を加え、４時間還流した。反応溶液を室温まで冷却し、有機層を、分液した後に飽和食塩水で洗浄した。この有機層を硫酸マグネシウムで乾燥し、ろ過後、溶媒を留去した。得られた反応生成物をシリカゲルクロマトグラフィーにより精製し、３，５－ビス（４－ｔ－ブチルフェニル）ベンズアルデヒド（３．５ｇ）を白色固体として得た。 (Synthesis Example 4)
Below, the synthesis | combining method of the organic luminescent material (type 24) of the synthesis example 4 is demonstrated. In the synthesis method of the organic light emitting material (type 24), 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0 0.4 g) and potassium carbonate (2.0 g) were placed in a flask and purged with nitrogen. To this was added degassed toluene (30 mL) and degassed water (10 mL), and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g) as a white solid.
　つぎに、３，５－ビス（４－ｔ－ブチルフェニル）ベンズアルデヒド（１．５ｇ）と２，４－ジメチルピロール（０．７ｇ）を反応溶液に入れ、脱水ジクロロメタン（２００ｍＬ）およびトリフルオロ酢酸（１滴）を加えて、窒素雰囲気下、４時間撹拌した。ついで、２，３－ジクロロ－５，６－ジシアノ－１，４－ベンゾキノン（０．８５ｇ）の脱水ジクロロメタン溶液を加え、さらに１時間撹拌した。反応終了後、三弗化ホウ素ジエチルエーテル錯体（７．０ｍＬ）およびジイソプロピルエチルアミン（７．０ｍＬ）を加えて、４時間撹拌した後、さらに水（１００ｍＬ）を加えて撹拌し、有機層を分液した。この有機層を硫酸マグネシウムで乾燥し、ろ過後、溶媒を留去した。得られた反応生成物をシリカゲルクロマトグラフィーにより精製し、下記に示す有機発光材料（タイプ２４）を合成した。
 
1Ｈ－ＮＭＲ（ＣＤＣｌ3，ｐｐｍ）：７．９５（ｓ，１Ｈ）、７．６３－７．４８（ｍ，１０Ｈ）、６．００（ｓ，２Ｈ）、２．５８（ｓ，６Ｈ）、１．５０（ｓ，６Ｈ）、１．３７（ｓ，１８Ｈ）。
  Next, 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were added to the reaction solution, dehydrated dichloromethane (200 mL) and trifluoroacetic acid ( 1 drop) was added and stirred under a nitrogen atmosphere for 4 hours. Subsequently, a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added and further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was further added and stirred, and the organic layer was separated. did. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to synthesize the organic light-emitting material (type 24) shown below.

1 H-NMR (CDCl 3 , ppm): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s, 6H) 1.50 (s, 6H), 1.37 (s, 18H).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（合成例５）
　以下に、合成例５の有機発光材料（タイプ２５）の合成方法について説明する。有機発光材料（タイプ２５）の合成方法では、ピロール原料として、２，４－ジメチルピロールの代わりに２，４－ジメチルピロール－３－カルボン酸エチルを用いた以外は、合成例４と同様にして、有機発光材料（タイプ２５）を合成した。 (Synthesis Example 5)
Below, the synthesis | combining method of the organic luminescent material (type 25) of the synthesis example 5 is demonstrated. The organic light emitting material (type 25) was synthesized in the same manner as in Synthesis Example 4 except that ethyl 2,4-dimethylpyrrole-3-carboxylate was used as the pyrrole raw material instead of 2,4-dimethylpyrrole. An organic light emitting material (type 25) was synthesized.
Figure JPOXMLDOC01-appb-C000047
  
Figure JPOXMLDOC01-appb-C000047
  
（合成例６）
　以下に、合成例６の有機発光材料（タイプ２６）の合成方法について説明する。有機発光材料（タイプ２６）の合成方法では、ボロン酸原料として、４－ｔ－ブチルフェニルボロン酸の代わりに４－（メトキシカルボニル）フェニルボロン酸を用いた以外は、合成例５と同様にして、有機発光材料（タイプ２６）を合成した。 (Synthesis Example 6)
Below, the synthesis | combining method of the organic luminescent material (type 26) of the synthesis example 6 is demonstrated. In the synthesis method of the organic light emitting material (type 26), the same procedure as in Synthesis Example 5 was performed, except that 4- (methoxycarbonyl) phenylboronic acid was used as the boronic acid raw material instead of 4-t-butylphenylboronic acid. An organic light emitting material (type 26) was synthesized.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
＜マトリックス樹脂＞
　マトリックス樹脂として、シリコーン樹脂を用いる場合は、以下のものを使用した。シリコーン樹脂を配合するための成分において、樹脂主成分は、（ＭｅＶｉＳｉＯ2/2）0.25（Ｐｈ2ＳｉＯ2/2）0.3（ＰｈＳｉＯ3/2）0.45（ＨＯ1/2）0.03（平均組成）である。これは、上述した（Ａ）成分に該当する。硬度調整剤は、ＶｉＭｅ2ＳｉＯ（ＭｅＰｈＳｉＯ）17.5ＳｉＭｅ2Ｖｉ（平均組成）である。これは、上述した（Ｂ）成分に該当する。架橋剤は、（ＨＭｅ2ＳｉＯ）2ＳｉＰｈ2である。これは、上述した（Ｃ）成分に該当する。ただし、Ｍｅはメチル基を表し、Ｖｉはビニル基を表し、Ｐｈはフェニル基を表す。反応抑制剤は、１－エチニルヘキサノールである。触媒は白金触媒であり、白金触媒として、白金含有量が５重量％の白金錯体（１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン溶液）が用いられる。 <Matrix resin>
When a silicone resin was used as the matrix resin, the following was used. In the component for blending the silicone resin, the main resin component is (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 0.45 (HO 1/2 ) 0.03 (average composition) is there. This corresponds to the component (A) described above. The hardness adjusting agent is ViMe 2 SiO (MePhSiO) 17.5 SiMe 2 Vi (average composition). This corresponds to the component (B) described above. The crosslinker is (HMe 2 SiO) 2 SiPh 2 . This corresponds to the component (C) described above. However, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group. The reaction inhibitor is 1-ethynylhexanol. The catalyst is a platinum catalyst, and a platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) having a platinum content of 5% by weight is used as the platinum catalyst.
　蛍光体組成物の作製に用いるマトリックス樹脂は、シリコーン樹脂のタイプ１（Ｓｉ１）とした。蛍光体組成物の作製に用いたシリコーン樹脂（Ｓｉ１）は、上記のシリコーン成分を配合し、マトリックス樹脂として作製した。シリコーン樹脂（Ｓｉ１）において、樹脂主成分は１６．７重量部であり、硬度調整剤は１６．７重量部であり、架橋剤は６６．７重量部であり、反応抑制剤は０．０２５重量部であり、白金触媒は０．０３重量部である。また、マトリックス樹脂としてエポキシ樹脂を用いる場合は、エポキシ樹脂のタイプ１（ＥＰ１）、具体的には“ＣＥＬＶＥＮＵＳ　Ｗ０９１０（Ａ液、Ｂ液）”（（株）ダイセル社製）を使用した。 The matrix resin used for the production of the phosphor composition was a silicone resin type 1 (Si1). The silicone resin (Si1) used for the preparation of the phosphor composition was prepared as a matrix resin by blending the above silicone components. In the silicone resin (Si1), the resin main component is 16.7 parts by weight, the hardness adjusting agent is 16.7 parts by weight, the crosslinking agent is 66.7 parts by weight, and the reaction inhibitor is 0.025 parts by weight. Parts and the platinum catalyst is 0.03 parts by weight. When an epoxy resin is used as the matrix resin, epoxy resin type 1 (EP1), specifically, “CELVENUS W0910 (A liquid, B liquid)” (manufactured by Daicel Corporation) was used.
＜ＬＥＤパッケージの製造方法－１＞
　実施例におけるＬＥＤパッケージの製造方法－１では、作製した蛍光体組成物を、ＬＥＤチップ（昭和電工（株）製“ＧＭ２ＱＴ４５０Ｇ”、平均波長：４５３．４ｎｍ）が実装されたパッケージフレーム（エノモト社製フレーム“ＴＯＰ　ＬＥＤ　ＢＡＳＥ”）に、ディスペンサー（武蔵野エンジニアリング社製“ＭＰＰ－１”）を用いて流し込み、８０℃で１時間、１５０℃で２時間キュアすることによって、ＬＥＤパッケージを作製した。 <LED package manufacturing method-1>
In the LED package manufacturing method-1 in the examples, the prepared phosphor composition is a package frame (manufactured by Enomoto Co., Ltd.) on which an LED chip (“GM2QT450G” manufactured by Showa Denko KK, average wavelength: 453.4 nm) is mounted. An LED package was manufactured by pouring into a frame “TOP LED BASE” using a dispenser (“MPP-1” manufactured by Musashino Engineering Co., Ltd.) and curing at 80 ° C. for 1 hour and 150 ° C. for 2 hours.
＜ＬＥＤパッケージの製造方法－２＞
　実施例におけるＬＥＤパッケージの製造方法－２では、作製した５ｃｍ角の蛍光体シートをカッティング装置（ＵＨＴ社製ＧＣＵＴ）によりカットし、１ｍｍ角の個片の蛍光体シートを１００個、作成した。ダイボンディング装置（東レエンジニアリング製）を用いて、１ｍｍ角にカットした蛍光体層をコレットで真空吸着して基材から剥離した。これをフリップチップ型青色ＬＥＤ発光素子が実装され、かつ発光素子の周囲にリフレクターが形成されたＬＥＤパッケージの発光素子表面に位置合わせして貼り付けた。このとき、前記フリップチップ型青色ＬＥＤ発光素子上に予め接着剤を塗布し、接着剤を介して蛍光体層を貼り付けた。接着剤にはシリコーン樹脂（ＯＥ６６３０）を使用した。得られた発光装置を直流電源につないで点灯させ、点灯することを確認した。 <LED package manufacturing method-2>
In LED package manufacturing method-2 in the example, the produced phosphor sheet of 5 cm square was cut by a cutting device (GCUT manufactured by UHT) to produce 100 phosphor sheets of 1 mm square pieces. Using a die bonding apparatus (manufactured by Toray Engineering), the phosphor layer cut into 1 mm square was vacuum-adsorbed with a collet and peeled from the substrate. This was aligned and affixed to the surface of the light emitting element of the LED package in which the flip chip type blue LED light emitting element was mounted and the reflector was formed around the light emitting element. At this time, an adhesive was applied in advance on the flip chip type blue LED light emitting element, and a phosphor layer was attached via the adhesive. A silicone resin (OE6630) was used as the adhesive. The obtained light emitting device was connected to a direct current power source and turned on, and it was confirmed that the light emitting device was turned on.
＜色度、全光束測定＞
　作製したＬＥＤパッケージに１Ｗの電力を投入してＬＥＤ素子を点灯させ、全光束測定システム（ＨＭ－３０００、大塚電子社製）を用いて、ＣＩＥ１９３１　ＸＹＺ表色系の色度（Ｃｘ、Ｃｙ）および発光スペクトルを測定した。また、全光束（ｌｍ）を測定し、後述の比較例１における全光束を１００としたときの相対的な輝度を後述の表１に記載した（蛍光体シートの場合は、後述の比較例５における全光束を１００とした）。 <Chromaticity, total luminous flux measurement>
The manufactured LED package is powered on by turning on the LED element, and using the total luminous flux measurement system (HM-3000, manufactured by Otsuka Electronics Co., Ltd.), the chromaticity (Cx, Cy) of the CIE1931 XYZ color system and The emission spectrum was measured. Further, the total luminous flux (lm) was measured, and the relative luminance when the total luminous flux in Comparative Example 1 described later was set to 100 was described in Table 1 described later (in the case of a phosphor sheet, Comparative Example 5 described later). The total luminous flux at 100 was taken as 100).
＜色再現性の評価＞
　色度測定によって得られた発光スペクトルデータと、カラーフィルターの透過率のスペクトルデータとから、カラーフィルターにより色純度を向上させた場合の（ｕ’，ｖ’）色空間における色域を算出した。また、算出された（ｕ’，ｖ’）色空間における色域の面積は、ＢＴ．２０２０規格の色域面積を１００％とした場合の割合により評価した。この割合が高いほど色再現性が良好である。色再現性の評価結果として、「Ａ」は、上記の割合が９１％以上であり、「色再現性が非常に良好である」ことを示す。「Ｂ」は、上記の割合が８６％以上、９０％以下であり、「色再現性が良好である」ことを示す。「Ｃ」は、上記の割合が７５％以上、８５％以下であり、「色再現性が実用上問題ない」ことを示す。「Ｄ」は、上記の割合が７４％以下であり、「色再現性が良好ではない」ことを示す。 <Evaluation of color reproducibility>
The color gamut in the (u ′, v ′) color space when the color purity was improved by the color filter was calculated from the emission spectrum data obtained by the chromaticity measurement and the spectrum data of the transmittance of the color filter. The calculated area of the color gamut in the (u ′, v ′) color space is BT. Evaluation was based on the ratio when the color gamut area of the 2020 standard was 100%. The higher this ratio, the better the color reproducibility. As an evaluation result of color reproducibility, “A” indicates that the above ratio is 91% or more, and “color reproducibility is very good”. “B” indicates that the above ratio is 86% or more and 90% or less, and “color reproducibility is good”. “C” indicates that the above ratio is 75% or more and 85% or less, and “color reproducibility is not a problem in practice”. “D” indicates that the above ratio is 74% or less and “color reproducibility is not good”.
＜耐久性評価＞
　作製したＬＥＤパッケージに１Ｗの電力を投入してＬＥＤ素子を点灯させた状態で、温度８５℃、湿度８５％の条件下で放置し、３００時間経過後の全光束を測定した。下記式により全光束保持率を算出することで耐久性を評価した。全光束保持率が高いほど、耐久性に優れていることを示す。
 
全光束保持率（％）＝（３００時間経過後の全光束／試験開始直後の全光束）×１００）
耐久性の評価結果として、「Ａ」は、全光束保持率が９１％以上であり、「耐久性が非常に良好である」ことを示す。「Ｂ」は、全光束保持率が８６％以上、９０％以下であり、「耐久性が良好である」ことを示す。「Ｃ」は、全光束保持率が８１％以上、８５％以下であり、「耐久性が実用上問題ない」ことを示す。「Ｄ」は、全光束保持率が８０％以下であり、「耐久性が悪い」ことを示す。 <Durability evaluation>
In a state where 1 W of electric power was applied to the manufactured LED package and the LED element was turned on, the LED package was left under conditions of a temperature of 85 ° C. and a humidity of 85%, and the total luminous flux after 300 hours was measured. Durability was evaluated by calculating the total luminous flux retention rate according to the following formula. A higher total luminous flux retention indicates better durability.

Total luminous flux retention (%) = (total luminous flux after 300 hours / total luminous flux immediately after the start of the test) × 100)
As a result of evaluating durability, “A” indicates that the total luminous flux retention rate is 91% or more, and “durability is very good”. “B” indicates that the total luminous flux retention is 86% or more and 90% or less, and “durability is good”. “C” indicates that the total luminous flux retention is 81% or more and 85% or less, and “durability is not a problem in practice”. “D” indicates that the total luminous flux retention is 80% or less and “durability is poor”.
（実施例１）
　実施例１では、容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を１６．０ｇ、無機蛍光体としてタイプ１のＹＡＧ系蛍光体（ＹＡＧ１）を８．０ｇ、有機発光材料として合成例１の有機発光材料（タイプ２１）を１．２４×１０－３ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌、脱泡し、蛍光体組成物（タイプ１）を作製した。蛍光体組成物（タイプ１）を用いて、前述した方法でＬＥＤパッケージを作製し、色度、全光束、全光束維持率を測定した。相対輝度、色再現性および耐久性の結果は、後述の表１に示す。表１に示されるように、相対輝度に変化はなかったが、色再現性が良好で耐久性も良好な結果が得られた。 Example 1
In Example 1, using a polyethylene container having a volume of 100 ml, 16.0 g of type 1 silicone resin (Si1) as a matrix resin, and 8.0 g of type 1 YAG phosphor (YAG1) as an inorganic phosphor, As the organic light emitting material, 1.24 × 10 −3 g of the organic light emitting material (type 21) of Synthesis Example 1 was added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, the mixture was stirred and defoamed at 1000 rpm for 5 minutes to prepare a phosphor composition (type 1). Using the phosphor composition (type 1), an LED package was produced by the method described above, and chromaticity, total luminous flux, and total luminous flux maintenance factor were measured. The results of relative luminance, color reproducibility and durability are shown in Table 1 described later. As shown in Table 1, although there was no change in the relative luminance, a result with good color reproducibility and good durability was obtained.
（比較例１）
　比較例１では、有機発光材料を添加しないこと以外は、実施例１と同様の操作で蛍光体組成物（タイプ１２）を作製した。その後、蛍光体組成物（タイプ１２）を用いて、実施例１と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表１に示す。表１に示されるように、比較例１では、耐久性は向上するが、色再現性は改善されなかった。 (Comparative Example 1)
In Comparative Example 1, a phosphor composition (type 12) was prepared in the same manner as in Example 1 except that no organic light emitting material was added. Thereafter, using the phosphor composition (type 12), an LED package was produced in the same manner as in Example 1, and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 1, the durability was improved, but the color reproducibility was not improved.
（比較例２）
　比較例２では、合成例１の有機発光材料（タイプ２１）の代わりに、下記の一般式で表される有機発光材料（タイプ２７）を使用したこと以外は、実施例１と同様の操作で蛍光体組成物（タイプ１３）を作製した。その後、蛍光体組成物（タイプ１３）を用いて、実施例１と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表１に示す。表１に示されるように、比較例２では、色再現性も耐久性も改善されなかった。 (Comparative Example 2)
In Comparative Example 2, the same operation as in Example 1 was performed except that the organic light-emitting material (type 27) represented by the following general formula was used instead of the organic light-emitting material (type 21) of Synthesis Example 1. A phosphor composition (type 13) was prepared. Thereafter, using the phosphor composition (type 13), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 2, neither color reproducibility nor durability was improved.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
（比較例３）
　比較例３では、有機発光材料の代わりに、タイプ１のＫＳＦ蛍光体（ＫＳＦ１）を２０ｇ添加したこと以外は、実施例１と同様の操作で蛍光体組成物（タイプ１４）を作製した。その後、蛍光体組成物（タイプ１４）を用いて、実施例１と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表１に示す。表１に示されるように、比較例３では、耐久性は向上するが、色再現性は改善されなかった。 (Comparative Example 3)
In Comparative Example 3, a phosphor composition (Type 14) was prepared in the same manner as in Example 1 except that 20 g of Type 1 KSF phosphor (KSF1) was added instead of the organic light emitting material. Thereafter, using the phosphor composition (type 14), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 3, the durability was improved, but the color reproducibility was not improved.
（比較例４）
　比較例４では、無機蛍光体の代わりに、下記の一般式で表される有機発光材料（タイプ２８）を使用したこと以外は、比較例２と同様の操作で蛍光体組成物（タイプ１５）を作製した。その後、蛍光体組成物（タイプ１５）を用いて、比較例２と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表１に示す。表１に示されるように、比較例４では、色再現性は若干改善されるが、耐久性は改善されなかった。 (Comparative Example 4)
In Comparative Example 4, a phosphor composition (Type 15) was prepared in the same manner as in Comparative Example 2, except that an organic light-emitting material (Type 28) represented by the following general formula was used instead of the inorganic phosphor. Was made. Thereafter, using the phosphor composition (type 15), an LED package was produced in the same manner as in Comparative Example 2, and evaluated. The results are shown in Table 1 below. As shown in Table 1, in Comparative Example 4, the color reproducibility was slightly improved, but the durability was not improved.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
（実施例２～１０）
　実施例２～１０では、後述の表１に示すように無機蛍光体と有機発光材料とを適宜変更したこと以外は、実施例１と同様の操作で蛍光体組成物（タイプ２～タイプ１０）を各々作製した。その後、蛍光体組成物（タイプ２～タイプ１０）を各々用いて、実施例１と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表１に示す。表１に示されるように、これらの実施例２～１０の評価結果から、本発明の実施の形態に係る蛍光体組成物であれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 (Examples 2 to 10)
In Examples 2 to 10, a phosphor composition (type 2 to type 10) was prepared in the same manner as in Example 1 except that the inorganic phosphor and the organic light emitting material were appropriately changed as shown in Table 1 described later. Each was produced. Thereafter, using each of the phosphor compositions (type 2 to type 10), an LED package was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below. As shown in Table 1, from the evaluation results of Examples 2 to 10, it was found that the color reproducibility was improved with the phosphor composition according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
（実施例１１）
　実施例１１では、表１に示すように無機蛍光体、有機発光材料およびマトリックス樹脂を変更したこと以外は、実施例１と同様の操作で蛍光体組成物（タイプ１１）を作製した。その後、蛍光体組成物（タイプ１１）を用いて、実施例１と同様の操作でＬＥＤパッケージを作製し、評価を行った。その結果は、表１に示す。表１に示されるように、実施例１１の評価結果から、本発明の実施の形態に係る蛍光体組成物であれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 (Example 11)
In Example 11, a phosphor composition (type 11) was prepared in the same manner as in Example 1 except that the inorganic phosphor, the organic light emitting material, and the matrix resin were changed as shown in Table 1. Thereafter, using the phosphor composition (type 11), an LED package was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1. As shown in Table 1, it was found from the evaluation results of Example 11 that the color reproducibility is improved with the phosphor composition according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
（実施例１２）
　実施例１２では、容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を１６．０ｇ、無機蛍光体としてタイプ１のＹＡＧ系蛍光体（ＹＡＧ１）を８．０ｇ、有機発光材料として合成例１の有機発光材料（タイプ２１）を１．２４×１０-3ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌・脱泡し、蛍光体組成物（タイプ１）を作製した。 Example 12
In Example 12, using a polyethylene container having a volume of 100 ml, 16.0 g of type 1 silicone resin (Si1) as a matrix resin, and 8.0 g of type 1 YAG phosphor (YAG1) as an inorganic phosphor, As an organic light emitting material, 1.24 × 10 −3 g of the organic light emitting material (type 21) of Synthesis Example 1 was added and mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming device to prepare a phosphor composition (type 1).
　また、実施例１２では、スリットダイコーターを用いて、基材として“セラピール”ＢＸ９（東レフィルム加工（株）製、平均膜厚５０μｍ）の離型処理面上に蛍光体組成物（タイプ１）を塗布し、１２０℃で３０分間加熱、乾燥し、８０μｍ、１００ｍｍ角の蛍光体シート（タイプ３１）を得た。蛍光体シート（タイプ３１）を用いて、前述した方法でＬＥＤパッケージを作製し、色度、全光束、全光束維持率を測定した。相対輝度、色再現性および耐久性の結果は、後述の表２に示す。表２に示されるように、相対輝度に変化はなかったが、色再現性が良好で耐久性も良好な結果が得られた。 In Example 12, a phosphor composition (type 1) was formed on a release treatment surface of “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm) using a slit die coater. And heated and dried at 120 ° C. for 30 minutes to obtain an 80 μm, 100 mm square phosphor sheet (type 31). Using a phosphor sheet (type 31), an LED package was produced by the method described above, and chromaticity, total luminous flux, and total luminous flux maintenance factor were measured. The results of relative luminance, color reproducibility and durability are shown in Table 2 below. As shown in Table 2, there was no change in the relative luminance, but a result with good color reproducibility and good durability was obtained.
（比較例５）
　比較例５では、有機発光材料を添加しないこと以外は、実施例１２と同様の操作で蛍光体組成物（タイプ１２）を作製した。その後、蛍光体組成物（タイプ１２）を用いて実施例１２と同様の操作で蛍光体シート（タイプ４４）を作製した後、蛍光体シート（タイプ４４）を用いてＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表２に示す。表２に示されるように、比較例５では、耐久性は向上するが、色再現性は改善されなかった。 (Comparative Example 5)
In Comparative Example 5, a phosphor composition (type 12) was produced in the same manner as in Example 12 except that no organic light emitting material was added. Then, after producing a phosphor sheet (type 44) using the phosphor composition (type 12) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 44) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 5, the durability was improved, but the color reproducibility was not improved.
（比較例６）
　比較例６では、有機発光材料（タイプ２１）の代わりに、有機発光材料（タイプ２７）を使用したこと以外は、実施例１２と同様の操作で蛍光体組成物（タイプ１３）を作製した。その後、蛍光体組成物（タイプ１３）を用いて実施例１２と同様の操作で蛍光体シート（タイプ４５）を作製した後、蛍光体シート（タイプ４５）を用いてＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表２に示す。表２に示されるように、比較例６では、色再現性も耐久性も改善されなかった。 (Comparative Example 6)
In Comparative Example 6, a phosphor composition (type 13) was prepared in the same manner as in Example 12 except that an organic light emitting material (type 27) was used instead of the organic light emitting material (type 21). Then, after producing a phosphor sheet (type 45) using the phosphor composition (type 13) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 45) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 6, neither color reproducibility nor durability was improved.
（比較例７）
　比較例７では、有機発光材料の代わりに、タイプ１のＫＳＦ蛍光体（ＫＳＦ１）を２０ｇ添加したこと以外は、実施例１２と同様の操作で蛍光体組成物（タイプ１４）を作製した。その後、蛍光体組成物（タイプ１４）を用いて実施例１２と同様の操作で蛍光体シート（タイプ４６）を作製した後、蛍光体シート（タイプ４６）を用いてＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表２に示す。表２に示されるように、比較例７では、耐久性は向上するが、色再現性は改善されなかった。 (Comparative Example 7)
In Comparative Example 7, a phosphor composition (Type 14) was produced in the same manner as in Example 12 except that 20 g of Type 1 KSF phosphor (KSF1) was added instead of the organic light emitting material. Then, after producing a phosphor sheet (type 46) using the phosphor composition (type 14) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 46) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 7, the durability was improved, but the color reproducibility was not improved.
（比較例８）
　比較例８では、無機蛍光体の代わりに、有機発光材料（タイプ２８）を使用したこと以外は、比較例６と同様の操作で蛍光体組成物（タイプ１５）を作製した。その後、蛍光体組成物（タイプ１５）を用いて比較例６と同様の操作で蛍光体シート（タイプ４７）を作製した後、蛍光体シート（タイプ４７）を用いてＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表２に示す。表２に示されるように、比較例８では、色再現性は若干改善されるが、耐久性は改善されなかった。 (Comparative Example 8)
In Comparative Example 8, a phosphor composition (Type 15) was prepared in the same manner as in Comparative Example 6, except that an organic light emitting material (Type 28) was used instead of the inorganic phosphor. Then, after producing a phosphor sheet (type 47) using the phosphor composition (type 15) in the same manner as in Comparative Example 6, an LED package is produced using the phosphor sheet (type 47) and evaluated. Went. The results are shown in Table 2 below. As shown in Table 2, in Comparative Example 8, the color reproducibility was slightly improved, but the durability was not improved.
（実施例１３～２１）
　実施例１３～２１では、後述の表２に示すように無機蛍光体と有機発光材料とを適宜変更したこと以外は、実施例１２と同様の操作で蛍光体組成物（タイプ２～タイプ１０）を各々作製した。その後、蛍光体組成物（タイプ２～タイプ１０）を各々用いて実施例１２と同様の操作で蛍光体シート（タイプ３２～タイプ４０）を作製した後、蛍光体シート（タイプ３２～タイプ４０）を各々用いてＬＥＤパッケージを作製し、評価を行った。その結果は、後述の表２に示す。表２に示されるように、これらの実施例１３～２１の評価結果から、本発明の実施の形態に係る蛍光体シートであれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 (Examples 13 to 21)
In Examples 13 to 21, a phosphor composition (type 2 to type 10) was prepared in the same manner as in Example 12 except that the inorganic phosphor and the organic light emitting material were appropriately changed as shown in Table 2 below. Each was produced. Thereafter, a phosphor sheet (type 32 to type 40) was prepared in the same manner as in Example 12 using each phosphor composition (type 2 to type 10), and then phosphor sheet (type 32 to type 40). An LED package was fabricated using each of these and evaluated. The results are shown in Table 2 below. As shown in Table 2, from the evaluation results of Examples 13 to 21, it was found that the color reproducibility was improved with the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
（実施例２２）
　実施例２２では、表２に示すように無機蛍光体、有機発光材料およびマトリックス樹脂を変更したこと以外は、実施例１２と同様の操作で蛍光体組成物（タイプ１１）を作製した。その後、蛍光体組成物（タイプ１１）を用いて実施例１２と同様の操作で蛍光体シート（タイプ４１）を作製した後、蛍光体シート（タイプ４１）を用いてＬＥＤパッケージを作製し、評価を行った。その結果は、表２に示す。表２に示されるように、実施例２２の評価結果から、本発明の実施の形態に係る蛍光体シートであれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 (Example 22)
In Example 22, a phosphor composition (type 11) was produced in the same manner as in Example 12 except that the inorganic phosphor, the organic light emitting material, and the matrix resin were changed as shown in Table 2. Then, after producing a phosphor sheet (type 41) using the phosphor composition (type 11) in the same manner as in Example 12, an LED package is produced using the phosphor sheet (type 41) and evaluated. Went. The results are shown in Table 2. As shown in Table 2, it was found from the evaluation results of Example 22 that the color reproducibility is improved if the phosphor sheet according to the embodiment of the present invention is used. Moreover, it turned out that durability is also favorable.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
（実施例２３）
　実施例２３では、以下に示すように、蛍光体組成物（タイプ１６）および有機発光材料組成物（タイプ１６）を作製し、これらを用いて、２層蛍光体シートである蛍光体シート（タイプ４２）を作製し、その後、蛍光体シート（タイプ４２）を用いてＬＥＤパッケージを作製し、評価を行った。 (Example 23)
In Example 23, as shown below, a phosphor composition (type 16) and an organic light emitting material composition (type 16) were prepared, and using these, a phosphor sheet (type) that was a two-layer phosphor sheet 42) was manufactured, and then an LED package was manufactured using a phosphor sheet (type 42) and evaluated.
＜蛍光体組成物（タイプ１６）の作製＞
　容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を１５．０ｇ、無機蛍光体としてタイプ３のβ型サイアロン蛍光体（β３）を２０ｇ、ブチルカルビトールを５ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌・脱泡した後、蛍光体組成物（タイプ１６）を作製した。 <Preparation of phosphor composition (type 16)>
Using a polyethylene container with a volume of 100 ml, 15.0 g of type 1 silicone resin (Si1) as a matrix resin, 20 g of type 3 β-sialon phosphor (β3) as an inorganic phosphor, 5 g of butyl carbitol, Added and mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming device, and then a phosphor composition (type 16) was produced.
＜有機発光材料組成物（タイプ１６）の作製＞
　容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を２０．０ｇ、有機発光材料として合成例３の有機発光材料（タイプ２３）を１．２４×１０-3ｇ、トルエンを２ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌・脱泡した後、有機発光材料組成物（タイプ１６）を得た。 <Preparation of Organic Luminescent Material Composition (Type 16)>
Using a polyethylene container with a volume of 100 ml, 20.0 g of type 1 silicone resin (Si1) as the matrix resin and 1.24 × 10 −3 g of the organic light emitting material of synthesis example 3 (type 23) as the organic light emitting material. 2 g of toluene was added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then an organic light emitting material composition (type 16) was obtained.
＜蛍光体シートの作製＞
　スリットダイコーターを用いて、蛍光体組成物（タイプ１６）を、基材としての“セラピール”ＢＸ９（東レフィルム加工（株）製、平均膜厚５０μｍ）の離型処理面上に塗布し、１２０℃で３０分間加熱、乾燥し、８０μｍ、１００ｍｍ角の蛍光体層を得た。得られた蛍光体層上にスリットダイコーターを用いて、有機発光材料組成物（タイプ１６）を塗布した。その後、１２０℃で３０分間加熱、乾燥し、５０μｍ、１００ｍｍ角の有機発光材料層を形成し、蛍光体シート（タイプ４２）を得た。 <Preparation of phosphor sheet>
Using a slit die coater, the phosphor composition (type 16) was applied onto a release treatment surface of “Therapy” BX9 (produced by Toray Film Processing Co., Ltd., average film thickness 50 μm) as a base material. It was heated and dried at 0 ° C. for 30 minutes to obtain an 80 μm, 100 mm square phosphor layer. An organic light emitting material composition (type 16) was applied on the obtained phosphor layer using a slit die coater. Then, it heated and dried at 120 degreeC for 30 minute (s), the organic light emitting material layer of 50 micrometers and a 100 mm square was formed, and the fluorescent substance sheet (type 42) was obtained.
　実施例２３の評価結果は、表２に示す。表２に示されるように、実施例２３の評価結果から、本発明の実施の形態に係る蛍光体シートであれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 The evaluation results of Example 23 are shown in Table 2. As shown in Table 2, from the evaluation result of Example 23, it was found that the color reproducibility was improved if the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
（実施例２４）
　実施例２４では、以下に示すように、蛍光体組成物（タイプ１７）および有機発光材料組成物（タイプ１７）を作製し、これらを用いて、２層蛍光体シートである蛍光体シート（タイプ４３）を作製し、その後、蛍光体シート（タイプ４３）を用いてＬＥＤパッケージを作製し、評価を行った。 (Example 24)
In Example 24, as shown below, a phosphor composition (type 17) and an organic light-emitting material composition (type 17) were prepared, and using these, a phosphor sheet (type) that is a two-layer phosphor sheet 43), and then an LED package was prepared using a phosphor sheet (type 43) and evaluated.
＜蛍光体組成物（タイプ１７）の作製＞
　容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を１５．０ｇ、無機蛍光体としてタイプ２のＫＳＦ蛍光体（ＫＳＦ２）を２０ｇ、ブチルカルビトールを５ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌・脱泡した後、蛍光体組成物（タイプ１７）を作製した。 <Preparation of phosphor composition (type 17)>
Using a polyethylene container with a volume of 100 ml, add 15.0 g of type 1 silicone resin (Si1) as a matrix resin, 20 g of type 2 KSF phosphor (KSF2) as an inorganic phosphor, and 5 g of butyl carbitol. And mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming device, and then a phosphor composition (type 17) was produced.
＜有機発光材料組成物（タイプ１７）の作製＞
　容積１００ｍｌのポリエチレン製容器を用いて、マトリックス樹脂としてタイプ１のシリコーン樹脂（Ｓｉ１）を２０．０ｇ、有機発光材料として合成例６の有機発光材料（タイプ２６）を１．２４×１０-3ｇ、トルエンを２ｇ、添加して混合した。その後、遊星式撹拌・脱泡装置を用い、１０００ｒｐｍで５分間撹拌・脱泡した後、有機発光材料組成物（タイプ１７）を得た。 <Preparation of organic light emitting material composition (type 17)>
Using a polyethylene container with a capacity of 100 ml, 20.0 g of type 1 silicone resin (Si1) as the matrix resin and 1.24 × 10 −3 g of the organic light emitting material of synthesis example 6 (type 26) as the organic light emitting material. 2 g of toluene was added and mixed. Thereafter, the mixture was stirred and degassed at 1000 rpm for 5 minutes using a planetary stirring and defoaming apparatus, and an organic light emitting material composition (type 17) was obtained.
＜蛍光体シートの作製＞
　スリットダイコーターを用いて、蛍光体組成物（タイプ１７）を、基材としての“セラピール”ＢＸ９（東レフィルム加工（株）製、平均膜厚５０μｍ）の離型処理面上に塗布し、１２０℃で３０分間加熱、乾燥し、８０μｍ、１００ｍｍ角の蛍光体層を得た。得られた蛍光体層上にスリットダイコーターを用いて、有機発光材料組成物（タイプ１７）を塗布した。その後、１２０℃で３０分間加熱、乾燥し、５０μｍ、１００ｍｍ角の有機発光材料層を形成し、蛍光体シート（タイプ４３）を得た。 <Preparation of phosphor sheet>
Using a slit die coater, the phosphor composition (type 17) was applied onto a release treatment surface of “THERAPY” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm) as a base material. It was heated and dried at 0 ° C. for 30 minutes to obtain an 80 μm, 100 mm square phosphor layer. An organic light emitting material composition (type 17) was applied onto the obtained phosphor layer using a slit die coater. Then, it heated and dried at 120 degreeC for 30 minute (s), the organic light emitting material layer of 50 micrometers and a 100 mm square was formed, and the fluorescent substance sheet (type 43) was obtained.
　実施例２４の評価結果は、表２に示す。表２に示されるように、実施例２４の評価結果から、本発明の実施の形態に係る蛍光体シートであれば、色再現性が向上することがわかった。また、耐久性も良好なことがわかった。 The evaluation results of Example 24 are shown in Table 2. As shown in Table 2, from the evaluation results of Example 24, it was found that the color reproducibility was improved if the phosphor sheet according to the embodiment of the present invention. Moreover, it turned out that durability is also favorable.
　以上のように、本発明に係る蛍光体組成物、蛍光体シート並びにそれらを用いた形成物、ＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニット、ディスプレイおよびＬＥＤパッケージの製造方法は、高色再現性および高耐久性を双方とも満足する蛍光体組成物、蛍光体シート、蛍光体形成物、ＬＥＤチップ、ＬＥＤパッケージ、発光装置、バックライトユニット、およびディスプレイに適している。 As described above, the phosphor composition according to the present invention, the phosphor sheet, and the formed article using them, the LED chip, the LED package, the light emitting device, the backlight unit, the display, and the manufacturing method of the LED package have high color reproduction. Suitable for a phosphor composition, a phosphor sheet, a phosphor formed product, an LED chip, an LED package, a light emitting device, a backlight unit, and a display that satisfy both the properties and the high durability.
　１　　ＬＥＤチップ
　２　　蛍光体シート
　３　　電極
　４　　蛍光体組成物
　５　　リフレクター
　６　　透明封止材
　７　　実装基板
　８　　金バンプ
　９　　透明接着剤
　１０　基材
　１１　形成物
　１２　パッケージフレーム
　１３　ＬＥＤパッケージ
　１４　基材
　１５　仮固定シート
　１６　加熱圧着ツール
　１７　ＬＥＤウェハ
　１８　蛍光体シート付きＬＥＤチップ
　１９　基材
　２０　蛍光体シート積層体
　２１　パッケージ基板
　２２　パッケージ電極
　２３　両面粘着テープ
　２４　台座
　２５　上部チャンバー
　２６　下部チャンバー
　２７　ダイアフラム
　２８　真空ダイアフラムラミネーター
　２９ａ　吸気口
　２９ｂ　排気口
　３０　切断部分
　３１　蛍光体シート付きＬＥＤチップ
　３２　ＬＥＤパッケージ
　３３　蛍光体シート積層体
　３４　蛍光体層
　３５　有機発光材料層
　３６　無機蛍光体
　３７，３８　積層物 DESCRIPTION OF SYMBOLS 1 LED chip 2 Phosphor sheet 3 Electrode 4 Phosphor composition 5 Reflector 6 Transparent sealing material 7 Mounting board 8 Gold bump 9 Transparent adhesive 10 Base material 11 Formed object 12 Package frame 13 LED package 14 Base material 15 Temporary fixing sheet DESCRIPTION OF SYMBOLS 16 Thermocompression bonding tool 17 LED wafer 18 LED chip with a phosphor sheet 19 Base material 20 Phosphor sheet laminated body 21 Package board 22 Package electrode 23 Double-sided adhesive tape 24 Base 25 Upper chamber 26 Lower chamber 27 Diaphragm 28 Vacuum diaphragm mura terminator 29a Inlet port 29b Exhaust port 30 Cut portion 31 LED chip with phosphor sheet 32 LED package 33 phosphor sheet laminate 34 phosphor layer 35 organic light emitting material layer 36 inorganic phosphor 37, 38 laminate

Claims (50)

  1. 　発光体からの発光光を該発光光よりも長波長の光へ変換する、一般式（１）で表される有機化合物および無機蛍光体と、
    　前記有機化合物および前記無機蛍光体と混合して連続相を形成するマトリックス樹脂と、
    　を含有することを特徴とする蛍光体組成物。
    Figure JPOXMLDOC01-appb-C000001
     （Ｒ1、Ｒ2、Ａｒ1～Ａｒ5およびＬは同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、複素環基、ハロゲン、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ｍはｍ価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金から選ばれる少なくとも一種である。）     An organic compound and an inorganic phosphor represented by the general formula (1), which convert light emitted from the light emitter into light having a longer wavelength than the light emitted;
    A matrix resin mixed with the organic compound and the inorganic phosphor to form a continuous phase;
    A phosphor composition comprising:
    Figure JPOXMLDOC01-appb-C000001
     (R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from beryllium, magnesium, chromium, iron, nickel, copper, zinc, platinum It is also a kind.)
  2. 　前記有機化合物を表す一般式（１）において、Ｍがホウ素であり、Ｌがフッ素または含フッ素アリール基であり、ｍ－１が２であることを特徴とする請求項１に記載の蛍光体組成物。 The phosphor composition according to claim 1, wherein, in the general formula (1) representing the organic compound, M is boron, L is fluorine or a fluorine-containing aryl group, and m-1 is 2. object.
  3. 　前記有機化合物を表す一般式（１）において、Ａｒ5が一般式（２）で表される基であることを特徴とする請求項１または２に記載の蛍光体組成物。
    Figure JPOXMLDOC01-appb-C000002
     （ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基からなる群より選ばれる。ｋは１～３の整数である。ｋが２以上である場合、ｒはそれぞれ同じでも異なってもよい。）     The phosphor composition according to claim 1 or 2, wherein in the general formula (1) representing the organic compound, Ar 5 is a group represented by the general formula (2).
    Figure JPOXMLDOC01-appb-C000002
     (R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
  4. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のフェニル基であることを特徴とする請求項１～３のいずれか一つに記載の蛍光体組成物。 4. The general formula (1) representing the organic compound, wherein Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted phenyl group. The phosphor composition according to one.
  5. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4のうち少なくとも一つが、一般式（３）で表される基であることを特徴とする請求項１～４のいずれか一つに記載の蛍光体組成物。
    Figure JPOXMLDOC01-appb-C000003
     （Ｒ3はアルキル基、シクロアルキル基、アルコキシ基およびアルキルチオ基からなる群より選ばれる。ｎは１～３の整数である。ｎが２以上の場合、各Ｒ3は同じでも異なってもよい。）     5. The general formula (1) representing the organic compound, wherein at least one of Ar 1 to Ar 4 is a group represented by the general formula (3). The phosphor composition described in 1.
    Figure JPOXMLDOC01-appb-C000003
     (R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .)
  6. 　前記有機化合物を表す一般式（１）において、Ａｒ1とＡｒ2とが異なる構造の基である、または、Ａｒ3とＡｒ4とが異なる構造の基であることを特徴とする請求項１～５のいずれか一つに記載の蛍光体組成物。 In the general formula (1) representing the organic compound, Ar 1 and Ar 2 are groups having different structures, or Ar 3 and Ar 4 are groups having different structures. 6. The phosphor composition according to any one of 5 above.
  7. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする請求項１または２に記載の蛍光体組成物。 3. The general formula (1) representing the organic compound, wherein Ar 1 to Ar 4 may be the same or different and each represents a substituted or unsubstituted alkyl group. Phosphor composition.
  8. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする請求項７に記載の蛍光体組成物。 The phosphor composition according to claim 7, wherein in general formula (1) representing the organic compound, at least one of R 1 and R 2 is hydrogen.
  9. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ２のうち少なくとも一つが電子吸引基であることを特徴とする請求項７に記載の蛍光体組成物。 8. The phosphor composition according to claim 7, wherein in the general formula (1) representing the organic compound, at least one of R 1 and R 2 is an electron withdrawing group.
  10. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする請求項３に記載の蛍光体組成物。 4. The phosphor according to claim 3, wherein in the general formula (1) representing the organic compound, Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted alkyl group. Composition.
  11. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする請求項１０に記載の蛍光体組成物。 11. The phosphor composition according to claim 10, wherein in the general formula (1) representing the organic compound, at least one of R 1 and R 2 is hydrogen.
  12. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ２のうち少なくとも一つが電子吸引基であることを特徴とする請求項１０に記載の蛍光体組成物。 The phosphor composition according to claim 10, wherein in the general formula (1) representing the organic compound, at least one of R 1 and R 2 is an electron withdrawing group.
  13. 　前記有機化合物のＡｒ5を表す一般式（２）において、ｒが電子吸引基であることを特徴とする請求項１０～１２のいずれか一つに記載の蛍光体組成物。 The phosphor composition according to any one of claims 10 to 12, wherein in the general formula (2) representing Ar 5 of the organic compound, r is an electron withdrawing group.
  14. 　前記無機蛍光体の発光スペクトルが５００～７００ｎｍの領域にピークを有することを特徴とする請求項１～６のいずれか一つに記載の蛍光体組成物。 The phosphor composition according to any one of claims 1 to 6, wherein the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
  15. 　前記無機蛍光体がβ型サイアロン蛍光体であることを特徴とする請求項１～６のいずれか一つに記載の蛍光体組成物。 The phosphor composition according to any one of claims 1 to 6, wherein the inorganic phosphor is a β-type sialon phosphor.
  16. 　前記β型サイアロン蛍光体の発光スペクトルが５３５～５５０ｎｍの領域にピークを有することを特徴とする請求項１５に記載の蛍光体組成物。 The phosphor composition according to claim 15, wherein the emission spectrum of the β-type sialon phosphor has a peak in a region of 535 to 550 nm.
  17. 　前記β型サイアロン蛍光体の平均粒径が１６μｍ以上、１９μｍ以下であることを特徴とする請求項１６に記載の蛍光体組成物。 The phosphor composition according to claim 16, wherein the β-sialon phosphor has an average particle size of 16 μm or more and 19 μm or less.
  18. 　前記無機蛍光体がＫＳＦ蛍光体であることを特徴とする請求項７～１３のいずれか一つに記載の蛍光体組成物。 The phosphor composition according to any one of claims 7 to 13, wherein the inorganic phosphor is a KSF phosphor.
  19. 　前記ＫＳＦ蛍光体の平均粒径が１０μｍ以上、４０μｍ以下であることを特徴とする請求項１８に記載の蛍光体組成物。 The phosphor composition according to claim 18, wherein the KSF phosphor has an average particle size of 10 µm or more and 40 µm or less.
  20. 　前記マトリックス樹脂がシリコーン樹脂であることを特徴とする請求項１～１９のいずれか一つに記載の蛍光体組成物。 The phosphor composition according to any one of claims 1 to 19, wherein the matrix resin is a silicone resin.
  21. 　発光体からの発光光を該発光光よりも長波長の光へ変換する、一般式（１）で表される有機化合物および無機蛍光体と、
    　少なくとも前記無機蛍光体と混合して連続相を形成するマトリックス樹脂と、
    　を含有することを特徴とする蛍光体シート。
    Figure JPOXMLDOC01-appb-C000004
     （Ｒ1、Ｒ2、Ａｒ1～Ａｒ５およびＬは同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、複素環基、ハロゲン、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ｍはｍ価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金から選ばれる少なくとも一種である。）     An organic compound and an inorganic phosphor represented by the general formula (1), which convert light emitted from the light emitter into light having a longer wavelength than the light emitted;
    A matrix resin that is mixed with at least the inorganic phosphor to form a continuous phase;
    A phosphor sheet comprising:
    Figure JPOXMLDOC01-appb-C000004
     (R 1 , R 2 , Ar 1 to Ar 5 and L may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, An ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, or a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron Less selected from beryllium, magnesium, chromium, iron, nickel, copper, zinc, platinum Both are also a kind.)
  22. 　前記無機蛍光体と前記マトリックス樹脂とを含有する蛍光体層と、一般式（１）で表される前記有機化合物を含有する有機発光材料層との積層構造を含むことを特徴とする請求項２１に記載の蛍光体シート。 23. A laminated structure of a phosphor layer containing the inorganic phosphor and the matrix resin and an organic light emitting material layer containing the organic compound represented by the general formula (1) is included. The phosphor sheet according to 1.
  23. 　前記有機化合物を表す一般式（１）において、Ｍがホウ素であり、Ｌがフッ素または含フッ素アリール基であり、ｍ－１が２であることを特徴とする請求項２１または２２に記載の蛍光体シート。 23. The fluorescence according to claim 21 or 22, wherein in the general formula (1) representing the organic compound, M is boron, L is fluorine or a fluorine-containing aryl group, and m-1 is 2. Body sheet.
  24. 　前記有機化合物を表す一般式（１）において、Ａｒ5が一般式（２）で表される基であることを特徴とする請求項２１～２３のいずれか一つに記載の蛍光体シート。
    Figure JPOXMLDOC01-appb-C000005
     （ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、ホスフィンオキシド基からなる群より選ばれる。ｋは１～３の整数である。ｋが２以上である場合、ｒはそれぞれ同じでも異なってもよい。）     The phosphor sheet according to any one of claims 21 to 23, wherein in the general formula (1) representing the organic compound, Ar 5 is a group represented by the general formula (2).
    Figure JPOXMLDOC01-appb-C000005
     (R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
  25. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のフェニル基であることを特徴とする請求項２１～２４のいずれか一つに記載の蛍光体シート。 25. In the general formula (1) representing the organic compound, Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted phenyl group. The phosphor sheet according to one.
  26. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4のうち少なくとも一つが、一般式（３）で表される基であることを特徴とする請求項２１～２５のいずれか一つに記載の蛍光体シート。
    Figure JPOXMLDOC01-appb-C000006
     （Ｒ3はアルキル基、シクロアルキル基、アルコキシ基およびアルキルチオ基からなる群より選ばれる。ｎは１～３の整数である。ｎが２以上の場合、各Ｒ3は同じでも異なってもよい。）     The general formula (1) representing the organic compound, wherein at least one of Ar 1 to Ar 4 is a group represented by the general formula (3). The phosphor sheet according to 1.
    Figure JPOXMLDOC01-appb-C000006
     (R 3 is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. N is an integer of 1 to 3. When n is 2 or more, each R 3 may be the same or different. .)
  27. 　前記有機化合物を表す一般式（１）において、Ａｒ1とＡｒ2とが異なる構造の基である、または、Ａｒ3とＡｒ4とが異なる構造の基であることを特徴とする請求項２１～２６のいずれか一つに記載の蛍光体シート。 22. In the general formula (1) representing the organic compound, Ar 1 and Ar 2 are groups having different structures, or Ar 3 and Ar 4 are groups having different structures. 26. The phosphor sheet according to any one of 26.
  28. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする請求項２１～２３のいずれか一つに記載の蛍光体シート。 24. In the general formula (1) representing the organic compound, Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted alkyl group. The phosphor sheet according to one.
  29. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする請求項２８に記載の蛍光体シート。 In the general formula (1) representing the organic compound, the phosphor sheet according to claim 28, wherein at least one of R 1 and R 2 are hydrogen.
  30. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが電子吸引基であることを特徴とする請求項２８に記載の蛍光体シート。 29. The phosphor sheet according to claim 28, wherein in the general formula (1) representing the organic compound, at least one of R 1 and R 2 is an electron withdrawing group.
  31. 　前記有機化合物を表す一般式（１）において、Ａｒ1～Ａｒ4は、それぞれ同じでも異なっていてもよく、置換もしくは無置換のアルキル基であることを特徴とする請求項２４に記載の蛍光体シート。 25. The phosphor according to claim 24, wherein in the general formula (1) representing the organic compound, Ar 1 to Ar 4 may be the same or different and each is a substituted or unsubstituted alkyl group. Sheet.
  32. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが水素であることを特徴とする請求項３１に記載の蛍光体シート。 In the general formula (1) representing the organic compound, the phosphor sheet according to claim 31, wherein at least one of R 1 and R 2 are hydrogen.
  33. 　前記有機化合物を表す一般式（１）において、Ｒ1およびＲ2のうち少なくとも一つが電子吸引基であることを特徴とする請求項３１に記載の蛍光体シート。 32. The phosphor sheet according to claim 31, wherein in the general formula (1) representing the organic compound, at least one of R 1 and R 2 is an electron withdrawing group.
  34. 　前記有機化合物のＡｒ5を表す一般式（２）において、ｒが電子吸引基であることを特徴とする請求項３１～３３のいずれか一つに記載の蛍光体シート。 The phosphor sheet according to any one of claims 31 to 33, wherein in the general formula (2) representing Ar 5 of the organic compound, r is an electron withdrawing group.
  35. 　前記無機蛍光体の発光スペクトルが５００～７００ｎｍの領域にピークを有することを特徴とする請求項２１～２７のいずれか一つに記載の蛍光体シート。 The phosphor sheet according to any one of claims 21 to 27, wherein the emission spectrum of the inorganic phosphor has a peak in a region of 500 to 700 nm.
  36. 　前記無機蛍光体がβ型サイアロン蛍光体であることを特徴とする請求項２１～２７のいずれか一つに記載の蛍光体シート。 The phosphor sheet according to any one of claims 21 to 27, wherein the inorganic phosphor is a β-type sialon phosphor.
  37. 　前記β型サイアロン蛍光体の発光スペクトルが５３５～５５０ｎｍの領域にピークを有することを特徴とする請求項３６に記載の蛍光体シート。 The phosphor sheet according to claim 36, wherein the emission spectrum of the β-type sialon phosphor has a peak in the region of 535 to 550 nm.
  38. 　前記β型サイアロン蛍光体の平均粒径が１６μｍ以上、１９μｍ以下であることを特徴とする請求項３７に記載の蛍光体シート。 The phosphor sheet according to claim 37, wherein the β-sialon phosphor has an average particle diameter of 16 µm or more and 19 µm or less.
  39. 　前記無機蛍光体がＫＳＦ蛍光体であることを特徴とする請求項２８～３４のいずれか一つに記載の蛍光体シート。 The phosphor sheet according to any one of claims 28 to 34, wherein the inorganic phosphor is a KSF phosphor.
  40. 　前記ＫＳＦ蛍光体の平均粒径が１０μｍ以上、４０μｍ以下であることを特徴とする請求項３９に記載の蛍光体シート。 The phosphor sheet according to claim 39, wherein the KSF phosphor has an average particle diameter of 10 µm or more and 40 µm or less.
  41. 　前記マトリックス樹脂がシリコーン樹脂であることを特徴とする請求項２１～４０のいずれか一つに記載の蛍光体シート。 The phosphor sheet according to any one of claims 21 to 40, wherein the matrix resin is a silicone resin.
  42. 　請求項１～２０のいずれか一つに記載の蛍光体組成物またはその硬化物を含有することを特徴とする形成物。 A formed product comprising the phosphor composition according to any one of claims 1 to 20 or a cured product thereof.
  43. 　請求項２１～４１のいずれか一つに記載の蛍光体シートまたはその硬化物を発光面に備えることを特徴とするＬＥＤチップ。 An LED chip comprising the phosphor sheet according to any one of claims 21 to 41 or a cured product thereof on a light emitting surface.
  44. 　請求項１～２０のいずれか一つに記載の蛍光体組成物の硬化物を備えることを特徴とするＬＥＤパッケージ。 An LED package comprising a cured product of the phosphor composition according to any one of claims 1 to 20.
  45. 　請求項２１～４１のいずれか一つに記載の蛍光体シートまたはその硬化物を備えることを特徴とするＬＥＤパッケージ。 An LED package comprising the phosphor sheet according to any one of claims 21 to 41 or a cured product thereof.
  46. 　請求項１～２０のいずれか一つに記載の蛍光体組成物を用いたＬＥＤパッケージの製造方法であって、
    　ＬＥＤチップが設置されているパッケージフレームに前記蛍光体組成物を注入する注入工程と、
    　前記注入工程の後、封止材で前記ＬＥＤチップを封止する封止工程と、
    　を少なくとも含むことを特徴とするＬＥＤパッケージの製造方法。     A method for producing an LED package using the phosphor composition according to any one of claims 1 to 20,
    An injection step of injecting the phosphor composition into a package frame in which an LED chip is installed;
    After the injection step, a sealing step of sealing the LED chip with a sealing material;
    A method for manufacturing an LED package, comprising:
  47. 　請求項２１～４１のいずれか一つに記載の蛍光体シートを用いたＬＥＤパッケージの製造方法であって、
    　複数の区画に分割された状態にある前記蛍光体シートの一の区画を、一のＬＥＤチップの発光面に対向させる位置合わせ工程と、
    　対向させた前記蛍光体シートの前記一の区画と前記一のＬＥＤチップの発光面とを、加熱圧着ツールにより加熱しながら加圧して接着する接着工程と、
    　を少なくとも含むことを特徴とするＬＥＤパッケージの製造方法。     A method of manufacturing an LED package using the phosphor sheet according to any one of claims 21 to 41,
    An alignment step in which one section of the phosphor sheet in a state divided into a plurality of sections is opposed to the light emitting surface of one LED chip;
    An adhesion step in which the one section of the phosphor sheet opposed to the light emitting surface of the one LED chip is pressed and bonded while being heated by a thermocompression bonding tool;
    A method for manufacturing an LED package, comprising:
  48. 　請求項４２に記載の形成物と、
    　前記形成物に含まれる蛍光体組成物によって発光光が色変換される発光体であるＬＥＤチップを有するＬＥＤパッケージと、
    　を備えることを特徴とする発光装置。     A formation according to claim 42;
    An LED package having an LED chip that is a light-emitting body in which emitted light is color-converted by the phosphor composition contained in the formation;
    A light emitting device comprising:
  49. 　請求項４４または４５に記載のＬＥＤパッケージを含むことを特徴とするバックライトユニット。 A backlight unit comprising the LED package according to claim 44 or 45.
  50. 　請求項４４または４５に記載のＬＥＤパッケージを含むことを特徴とするディスプレイ。 A display comprising the LED package according to claim 44 or 45.
PCT/JP2016/077529 2015-09-29 2016-09-16 Phosphor composition, phosphor sheet, and molded article using same, led chip, led package, light-emitting device, backlight unit, display, and method for manufacturing led package WO2017057074A1 (en)

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