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WO2014014079A1 - Dispositif photoémetteur, élément convertisseur de longueur d'onde, composition phosphorescente et mélange phosphorescent - Google Patents

Dispositif photoémetteur, élément convertisseur de longueur d'onde, composition phosphorescente et mélange phosphorescent Download PDF

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Publication number
WO2014014079A1
WO2014014079A1 PCT/JP2013/069607 JP2013069607W WO2014014079A1 WO 2014014079 A1 WO2014014079 A1 WO 2014014079A1 JP 2013069607 W JP2013069607 W JP 2013069607W WO 2014014079 A1 WO2014014079 A1 WO 2014014079A1
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Prior art keywords
phosphor
excitation spectrum
spectrum intensity
wavelength
conversion member
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English (en)
Japanese (ja)
Inventor
覚成 勝本
実 相馬
友幸 来島
吉田　尚史
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority claimed from JP2013043101A external-priority patent/JP2014170895A/ja
Priority claimed from JP2013138464A external-priority patent/JP2014130998A/ja
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to KR1020147036183A priority Critical patent/KR20150035742A/ko
Publication of WO2014014079A1 publication Critical patent/WO2014014079A1/fr
Priority to US14/594,981 priority patent/US20150166888A1/en
Anticipated expiration legal-status Critical
Priority to US15/085,126 priority patent/US20160208164A1/en
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • H10H20/8513—Wavelength conversion materials having two or more wavelength conversion 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8515—Wavelength conversion means not being in contact with the bodies

Definitions

  • the present invention relates to a light emitting device, and particularly to a light emitting device including a blue semiconductor light emitting element. Moreover, it is related with the wavelength conversion member with which a light-emitting device is equipped.
  • Patent Document 1 a problem has been found that color unevenness occurs in the illumination light as the lighting time becomes longer.
  • two types of phosphors that generate visible light of the same color are provided, and the slopes of the excitation spectra of the two types of phosphors are reversed at the emission peak wavelength of the semiconductor light emitting device. It has been proposed (see Patent Document 1).
  • Patent Document 2 discloses "LED binning" as a problem, and discloses a multi-cell LED circuit having a plurality of cells having binning classes depending on emission wavelength characteristics and luminance characteristics, and an impedance element (patent).
  • Reference 2 discloses that the LED is binned from any viewpoint among the light peak wavelength, the light peak intensity, and the forward voltage, and in particular, the chromaticity is self-adjusted according to the fluctuation of the LED excitation wavelength.
  • a “smart” phosphor composition is disclosed (see Patent Document 3).
  • Patent Document 4 proposes a semiconductor light emitting device in which the chromaticity variation is reduced with respect to the fluctuation of the peak wavelength of the semiconductor light emitting element. Specifically, in the vicinity of the peak wavelength of the semiconductor light emitting element, There has been proposed a semiconductor light emitting device having a first phosphor whose excitation intensity increases with an increase, and a second phosphor whose excitation intensity is flattened or decreased as the wavelength increases (see Patent Document 4).
  • Patent Document 3 tried to solve the problem by adding an orange phosphor to the yellow phosphor, but suppressed the change in chromaticity. This is not enough for practical use.
  • Patent Document 4 although an attempt is made to suppress a change in chromaticity by combining a yellow phosphor and an orange phosphor, color rendering properties and light emission efficiency are insufficient.
  • the present invention solves such a problem, and provides a light-emitting device having a binning characteristic that can withstand practical use while maintaining sufficient color rendering properties and luminous efficiency.
  • a phosphor composition capable of forming a wavelength conversion member capable of providing a light emitting device having a binning characteristic that can withstand practical use, and a phosphor composition formed by molding the phosphor composition
  • the present invention relates to a wavelength conversion member.
  • the inventors have conducted intensive research to solve the above problems, and in a light emitting device using a blue semiconductor light emitting element, a wavelength conversion member containing a yellow phosphor and a green phosphor, not containing a yellow phosphor, By using a wavelength conversion member containing a specific green phosphor or a wavelength conversion member containing a specific yellow-green phosphor, it was found that a light-emitting device having sufficient binning characteristics can be provided, and the present invention has been completed. .
  • a first aspect of the present invention is an invention relating to a light emitting device, and a first embodiment thereof is as follows.
  • a light-emitting device that includes phosphor G that is represented by the following general formula (G1) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm. (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the intensity change rate of the following synthetic excitation spectrum is 0.15 or less.
  • the synthetic excitation spectrum is an excitation spectrum in which the excitation spectrum intensity at each wavelength is represented by the following calculation formula (Z).
  • Synthetic excitation spectrum intensity (excitation spectrum intensity of phosphor Y) ⁇ (weight fraction of phosphor Y) + (excitation spectrum intensity of phosphor G) ⁇ (weight fraction of phosphor G) (Z)
  • the weight fraction of phosphor Y is expressed as phosphor Y / (phosphor Y + phosphor G).
  • the weight fraction of the phosphor G is similarly expressed.
  • the synthetic excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the synthetic excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity at 450 nm of the excitation spectrum is 1.0.
  • the phosphor Y has an excitation spectrum intensity at 430 nm smaller than the excitation spectrum intensity at 470 nm in the excitation spectrum at an emission wavelength of 540 nm
  • the phosphor G has an excitation spectrum in an excitation spectrum at an emission wavelength of 540 nm. It is preferable that the excitation spectrum intensity at 430 nm is larger than the excitation spectrum intensity at 470 nm.
  • the light-emitting device described above preferably further includes a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • B1 blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • the composition ratio of the phosphor Y and the phosphor G is preferably 10:90 or more and 90:10 or less.
  • the fifth embodiment in the first invention is as follows.
  • a light emitting device including a blue semiconductor light emitting element and a wavelength conversion member The wavelength conversion member is A phosphor G represented by the following general formula (G4) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm is 520 nm or more and 540 nm or less, The light-emitting device whose excitation spectrum intensity change rate in emission wavelength 540nm of this wavelength conversion member is 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • ⁇ u′v ′ The chromaticity change ⁇ u′v ′ of light emitted from the light emitting device when the emission wavelength of the blue semiconductor light emitting element is continuously changed from 445 nm to 455 nm satisfies ⁇ u′v ′ ⁇ 0.004.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 435 nm to 470 nm. .
  • the red phosphor preferably further contains a red phosphor having an emission peak wavelength of 600 nm or more and less than 640 nm and a half-value width of 2 nm or more and 120 nm or less in a composition weight ratio of 30 to the total amount of the red phosphor. % Or more is preferable.
  • the red phosphor having an emission peak wavelength of 600 nm to less than 640 nm and a half width of 2 nm to 120 nm is (Sr, Ca) AlSiN 3 : Eu or Ca 1-x Al 1-x Si 1 + x N 3-x O x : Eu (where 0 ⁇ x ⁇ 0.5) is preferable.
  • the red phosphor preferably includes a red phosphor having an emission peak wavelength of 640 nm to 670 nm and a half width of 2 nm to 120 nm.
  • the light emitted from the light emitting device preferably has a deviation duv from the light-colored blackbody radiation locus of ⁇ 0.0200 to 0.0200 and a color temperature of 1800 K or more and 7000 K or less. More preferably, the temperature is 2500 or more and 3500 K or less.
  • the average color rendering index Ra is preferably 80 or more.
  • the sixth embodiment in the first invention is as follows.
  • a light emitting device including a blue semiconductor light emitting element and a wavelength conversion member The wavelength conversion member is represented by the following general formula (YG1), and includes a yellow-green phosphor having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 530 nm to 550 nm, In this light-emitting device, the wavelength conversion member has an excitation spectrum intensity change rate at an emission wavelength of 540 nm of 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is preferably 0.13 or less.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the yellow-green phosphor at 450 nm is 1.0. Expressed as a difference.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • the yellow-green phosphor is preferably a yellow-green phosphor represented by the following general formula (YG2).
  • A is one or more elements selected from the group of Y and Lu and containing 90% or more of Y.
  • E is Ga or Ga and Sc.
  • a + b 3, 4.5 ⁇ c + d ⁇ 5.5, 10.8 ⁇ e ⁇ 13.2, 0 ⁇ a ⁇ 0.9, 0.8 ⁇ c ⁇ 1.2)
  • the intensity change of the excitation spectrum of the yellow-green phosphor is 4.0% or less of the excitation light spectrum intensity at 450 nm from 440 nm to 460 nm.
  • the seventh embodiment in the first invention is as follows.
  • a blue semiconductor light emitting device A light-emitting device including a wavelength conversion member containing a yellow-green phosphor,
  • the yellow-green phosphor is represented by the following general formula (YG3), and the difference between the maximum value and the minimum value of the excitation intensity normalized by the excitation intensity of 450 nm when excited at an excitation wavelength of 440 nm to 460 nm is 0.05.
  • the following phosphors (Y, Ce) 3 (Ga, Al) f O g (YG3) (4.5 ⁇ f ⁇ 5.5, 10.8 ⁇ g ⁇ 13.2)
  • the chromaticity change ⁇ u′v ′ from the average chromaticity of the light emitted from the wavelength conversion member when excited at an excitation wavelength of 445 nm to 455 nm is 0.005 or less.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • a red phosphor is further included, and the intensity change of the excitation spectrum of the red phosphor varies from 440 nm to 460 nm, which is 4.0 of the excitation light spectrum intensity at 450 nm. % Or less is preferable.
  • the red phosphor preferably includes a red phosphor having an emission peak wavelength of 620 to 640 nm and a half-value width of 2 nm to 100 nm in a composition weight ratio of 50% or more with respect to the total amount of the red phosphor.
  • the red phosphor is preferably SCASN.
  • the red phosphor further includes a red phosphor having an emission peak wavelength of 640 to 670 nm and a half-value width of 2 nm to 120 nm.
  • the light emitted from the light-emitting device has a deviation duv from the light-colored blackbody radiation locus of ⁇ 0.0200 to 0.0200 and a color temperature of 1800 K or more and 7000 K or less.
  • the blue semiconductor light emitting element and the wavelength conversion member including a yellow-green phosphor may be disposed through a space.
  • a lighting device including these light emitting devices and a backlight including these light emitting devices are also preferable inventions.
  • a wavelength conversion member comprising a transparent material.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the intensity change rate of the following synthetic excitation spectrum is 0.15 or less.
  • the synthetic excitation spectrum is an excitation spectrum in which the excitation spectrum intensity at each wavelength is represented by the following calculation formula (Z).
  • Synthetic excitation spectrum intensity (excitation spectrum intensity of phosphor Y) ⁇ (weight fraction of phosphor Y) + (excitation spectrum intensity of phosphor G) ⁇ (weight fraction of phosphor G) (Z)
  • the weight fraction of phosphor Y is expressed as phosphor Y / (phosphor Y + phosphor G).
  • the weight fraction of the phosphor G is similarly expressed.
  • the synthetic excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the synthetic excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity at 450 nm of the excitation spectrum is 1.0.
  • the phosphor Y has an excitation spectrum intensity at 430 nm lower than the excitation spectrum intensity at 470 nm in the excitation spectrum at an emission wavelength of 540 nm, and the phosphor G has an excitation spectrum at an emission wavelength of 540 nm.
  • the excitation spectrum intensity at 430 nm is preferably larger than the excitation spectrum intensity at 470 nm.
  • the wavelength conversion member described above preferably further includes a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • B1 blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • the composition ratio of the phosphor Y and the phosphor G is preferably 10:90 or more and 90:10 or less.
  • Phosphor G which is represented by the following general formula (G4) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm, A wavelength conversion member comprising a transparent material, A wavelength conversion member having an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member of 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the chromaticity change ⁇ u′v ′ of light emitted from the wavelength conversion member satisfies ⁇ u′v ′ ⁇ 0.004 when the excitation wavelength is continuously changed from 445 nm to 455 nm.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • the chromaticity change ⁇ u′v ′ of light emitted from the wavelength conversion member satisfies ⁇ u′v ′ ⁇ 0.015 when the excitation wavelength is continuously changed from 435 nm to 470 nm.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 435 nm to 470 nm.
  • the sixth embodiment in the second invention is as follows.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is preferably 0.13 or less.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the yellow-green phosphor at 450 nm is 1.0. Expressed as a difference.
  • the chromaticity change ⁇ u′v ′ of light emitted from the light emitting device preferably satisfies ⁇ u′v ′ ⁇ 0.005.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • the yellow-green phosphor is preferably a yellow-green phosphor represented by the following general formula (YG2).
  • A is one or more elements selected from the group of Y and Lu and containing 90% or more of Y.
  • E is Ga or Ga and Sc.
  • a + b 3, 4.5 ⁇ c + d ⁇ 5.5, 10.8 ⁇ e ⁇ 13.2, 0 ⁇ a ⁇ 0.9, 0.8 ⁇ c ⁇ 1.2)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the phosphor Y in the wavelength conversion member has an excitation spectrum intensity at 430 nm in an excitation spectrum at an emission wavelength of 540 nm. It is preferable that the phosphor G in the wavelength conversion member is smaller than the excitation spectrum intensity at 470 nm, and the excitation spectrum intensity at 430 nm is larger than the excitation spectrum intensity at 470 nm in the excitation spectrum at the emission wavelength of 540 nm.
  • the phosphor composition described above preferably further includes a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • B1 blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • the composition ratio of the phosphor Y and the phosphor G is preferably 10:90 or more and 90:10 or less.
  • the fifth embodiment in the third invention is as follows.
  • Phosphor G which is represented by the following general formula (G4) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm, A phosphor composition comprising a transparent material, A phosphor composition, wherein when the home antibody composition is molded into a wavelength conversion member, the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the sixth embodiment in the third invention is as follows.
  • a phosphor composition comprising a transparent material, When the phosphor composition is molded into a wavelength conversion member, the phosphor composition has an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member of 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the yellow-green phosphor is preferably a yellow-green phosphor represented by the following general formula (YG2).
  • A is one or more elements selected from the group of Y and Lu and containing 90% or more of Y.
  • E is Ga or Ga and Sc.
  • a + b 3, 4.5 ⁇ c + d ⁇ 5.5, 10.8 ⁇ e ⁇ 13.2, 0 ⁇ a ⁇ 0.9, 0.8 ⁇ c ⁇ 1.2)
  • a red phosphor is further included.
  • a fourth aspect of the present invention is an invention relating to a phosphor mixture, and a first embodiment thereof is as follows.
  • a phosphor Y represented by the following general formula (Y1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm is 540 nm or more and 570 nm or less;
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (Y1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • a phosphor mixture comprising phosphor G which is represented by the following general formula (G1) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm.
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (G1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • the rate of change in excitation spectrum intensity at an emission wavelength of 540 nm is preferably 0.40 or less.
  • the excitation spectrum intensity change rate of the phosphor mixture is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the phosphor mixture at 450 nm is 1.0. It is represented by
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • the rate of change in excitation spectrum intensity at an emission wavelength of 540 nm is preferably 0.30 or less.
  • the excitation spectrum intensity change rate of the phosphor mixture is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. It is represented by
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
  • the excitation spectrum intensity change rate of the phosphor mixture is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. It is represented by
  • the phosphor Y has an excitation spectrum intensity at 430 nm smaller than that at 470 nm in the excitation spectrum at an emission wavelength of 540 nm, and the phosphor Y has an excitation spectrum intensity at 430 nm in an excitation spectrum at 540 nm. Is preferably greater than the excitation spectral intensity at 470 nm.
  • a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • B1 a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm to 520 nm.
  • composition ratio of the phosphor Y and the phosphor G is preferably 10:90 or more and 90:10 or less.
  • the fifth embodiment in the fourth invention is as follows.
  • a phosphor mixture comprising phosphor G, which is represented by the following general formula (G4) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm,
  • the phosphor mixture wherein an excitation spectrum change rate at an emission wavelength of 540 nm of the phosphor mixture is 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the sixth embodiment in the fourth invention is as follows.
  • a phosphor mixture comprising a yellow-green phosphor represented by the following general formula (YG1) and having an emission wavelength spectrum having a peak wavelength of 530 nm or more and 550 nm or less when excited at 450 nm,
  • the phosphor mixture has an excitation spectrum intensity change rate at an emission wavelength of 575 nm of 0.12 or less.
  • the excitation spectrum intensity change rate of the phosphor mixture is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the phosphor mixture at 450 nm is 1.0. It is represented by
  • a red phosphor is further included.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.00. It is preferable that it is 05 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 440 nm to 460 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the yellow-green phosphor is preferably a yellow-green phosphor represented by the following general formula (YG2).
  • A is selected from the group of Y and Lu, and 1 or 2 or more elements including 90% or more of Y.
  • E is Ga, or Ga and Sc.
  • a + b 3, 4.5 ⁇ c + d ⁇ 5.5, 10.8 ⁇ e ⁇ 13.2, 0 ⁇ a ⁇ 0.9, 0.8 ⁇ c ⁇ 1.2)
  • the first to seventh embodiments of the first invention of the present invention it is possible to provide a light-emitting device that is excellent in binning characteristics and has high luminous efficiency and color rendering.
  • a YAG phosphor that is a typical example of the phosphor Y, or a GYAG phosphor that is a typical example of the phosphor G is used alone.
  • a high total luminous flux can be achieved. For this reason, the amount of electric power input when attempting to achieve the target total luminous flux in the light emitting device is reduced, and more energy saving can be achieved.
  • a LuAG phosphor that is a typical example of the phosphor G is used alone, so that a YAG phosphor that is a typical example of the phosphor Y can be used alone.
  • High total luminous flux can be achieved compared to the case of using.
  • the LuAG phosphor can achieve high color rendering while maintaining a high total luminous flux as compared with the case where the YAG phosphor is used. Therefore, it is possible to refrain from using a phosphor other than the LuAG phosphor.
  • a YAG phosphor that is a representative example of the phosphor Y is used alone.
  • a high total luminous flux can be achieved.
  • a light-emitting device with excellent binning characteristics can be provided. These light-emitting devices not only have excellent binning characteristics, but also have high luminous efficiency and high color rendering, so that they can be put to practical use as lighting devices and backlights equipped with these light-emitting devices. .
  • the luminous efficiency is high and the amount of phosphor used is reduced, there is an economic advantage.
  • the second invention of the present invention it is possible to provide a wavelength conversion member that can provide a light-emitting device that has excellent binning characteristics as described above and has high luminous efficiency and color rendering.
  • a phosphor composition or a phosphor mixture that can provide a light emitting device having excellent binning characteristics as described above and having high luminous efficiency and color rendering. can do.
  • FIG. 10 is a graph showing changes in excitation spectrum intensity at the emission wavelength of 540 nm of the test pieces prepared in Experimental Examples 4 to 8.
  • 10 is a graph showing changes in excitation spectrum intensity at the emission wavelength of 540 nm of the test pieces prepared in Experimental Examples 9-12.
  • 6 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 1 to 3.
  • 9 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 4 to 8.
  • 10 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 9 to 12.
  • 7 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 1 to 3 and 9 to 12.
  • 9 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 4 to 8. It is the graph showing the excitation spectrum intensity change in the luminescence wavelength of 540 nm of the fluorescent substance mixture produced in Experimental example 13 and 14.
  • 6 is a graph showing changes in excitation spectrum intensity at the emission wavelength of 540 nm of the phosphor mixtures prepared in Experimental Examples 15 to 20. It is the graph showing the excitation spectrum intensity
  • 28 is a graph showing binning characteristics of light emitting devices manufactured in Experimental Examples 23 to 27.
  • each composition formula is delimited by a punctuation mark (,).
  • commas when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition.
  • the light emitting device includes a blue semiconductor light emitting element and a wavelength conversion member.
  • the blue semiconductor light emitting device is a semiconductor light emitting device that emits light having an emission peak at 420 nm or more and 475 nm or less.
  • the blue semiconductor light-emitting element preferably emits light having an emission peak at 430 nm to 465 nm, and preferably emits light having an emission peak at 445 nm to 455 nm.
  • the blue semiconductor light emitting element preferably has a half width of 5 nm or more and 30 nm or less from the viewpoint of light emission efficiency.
  • the blue semiconductor light emitting device is preferably a light emitting diode device having a pn junction type light emitting portion formed of a nitrogen gallium based, zinc oxide based or silicon carbide based semiconductor.
  • the wavelength converting member is a wavelength converting member that wavelength-converts at least part of incident light and emits outgoing light having a wavelength different from that of the incident light.
  • the wavelength converting member is at least one of the incident light.
  • a phosphor that emits outgoing light having a wavelength different from that of the incident light.
  • the phosphor is preferably dispersed in a transparent or translucent material that absorbs less visible light such as resin.
  • the wavelength conversion member may have a self-supporting shape due to the contained transparent material or the like.
  • the phosphor may be mixed and applied to a resin or the like on a transparent substrate such as glass if necessary.
  • the phosphor Y is a yellow phosphor having a peak wavelength of an emission wavelength spectrum of 540 nm or more and 570 nm or less when excited at 450 nm, that is, a peak wavelength of the emission wavelength spectrum in a yellow region.
  • a typical example of the phosphor Y is a phosphor represented by the following general formula (1) called a YAG phosphor, but is not limited thereto.
  • Y a (Ce, Tb, Lu) b (Ga, Sc) c Al d O e (1) (A + b 3, 0 ⁇ b ⁇ 0.2, 4.5 ⁇ c + d ⁇ 5.5, 0 ⁇ c ⁇ 0.2, 10.8 ⁇ e ⁇ 13.4)
  • the phosphor G is a green phosphor having a peak wavelength of an emission wavelength spectrum of 520 nm or more and 540 nm or less when excited at 450 nm, that is, a peak wavelength of the emission wavelength spectrum in a green region.
  • Representative examples of the phosphor G include a phosphor represented by the following general formula (m1) called a GYAG phosphor and a fluorescence represented by the following general formula (m2) called a LuAG phosphor.
  • the body is raised, but it is not limited to these.
  • the light-emitting device is a light-emitting device having excellent binning characteristics that can withstand practical use by satisfying the above requirements.
  • variation in emission peak wavelength is usually about 10 nm in many cases.
  • the light-emitting device according to the first embodiment of the first invention has a so-called binning characteristic in which the chromaticity change of the emitted light is small with respect to the variation in the emission peak wavelength of the blue semiconductor light-emitting element as such a light source. It is an excellent light emitting device.
  • Such a light emitting device having excellent binning characteristics can be achieved by using together the phosphor Y represented by the general formula (Y1) and the phosphor G represented by the general formula (G1).
  • Y1 the phosphor Y represented by the general formula (Y1)
  • G1 the phosphor G represented by the general formula (G1).
  • FIG. 1 is a graph showing changes in the excitation emission spectrum when the excitation wavelength is changed from 430 nm to 470 nm for phosphors of YAG, GYAG, SCASN, and CASN.
  • YAG represented by the general formula (Y1) has an increased excitation wavelength and an increased emission intensity at an excitation wavelength from 445 nm to 455 nm.
  • GYAG represented by the general formula (G1) has an increased excitation wavelength and a lower emission intensity at an excitation wavelength from 445 nm to 455 nm. Therefore, by using together the phosphor Y represented by the general formula (Y1) and the phosphor G represented by the general formula (G1), the binning characteristics of the light emitting device according to the first embodiment of the first invention are provided. Can be made excellent.
  • the rate of change in excitation spectrum intensity at the light emission wavelength of 540 nm of the wavelength conversion member is 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is represented by the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. Is done.
  • the excitation spectrum intensity change rate is calculated using the intensity at the emission wavelength of 540 nm.
  • the inventors pay attention to the excitation spectrum intensity of the phosphor, which indicates how much light the phosphor emits at what excitation wavelength, and particularly the wavelength of the light emitted by the blue semiconductor light emitting element.
  • Excitation spectrum intensity in the vicinity of 450 nm light was examined in detail.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member was 0.25 or less, so that high total luminous flux could be achieved in addition to good binning characteristics.
  • the excitation spectrum intensity changes greatly the fluorescence intensity emitted from the phosphor changes greatly when the excitation wavelength changes, and the chromaticity of the light emitted from the light emitting device is shifted.
  • the chromaticity deviation of the light emitted from the wavelength conversion member was suppressed by setting the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member to 0.25 or less.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.24 or less, and more preferably 0.23 or less.
  • the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.23 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.21 or less, and more preferably 0.20 or less. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties.
  • the fluorescent substance G is a GYAG fluorescent substance, it is preferable from a viewpoint of color rendering property that a half value width is 105 to 120 nm.
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.30 or less, and more preferably 0.28 or less. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties.
  • the fluorescent substance G is a LuAG fluorescent substance, it is preferable from a viewpoint of color rendering property that a half value width is 30 nm or more and 120 nm or less.
  • the intensity change rate of the following synthetic excitation spectrum is 0.15 or less.
  • the synthetic excitation spectrum is an excitation spectrum in which the excitation spectrum intensity at each wavelength is represented by the following calculation formula (Z).
  • Synthetic excitation spectrum intensity (excitation spectrum intensity of phosphor Y) ⁇ (weight fraction of phosphor Y) + (excitation spectrum intensity of phosphor G) ⁇ (weight fraction of phosphor G) (Z)
  • the weight fraction of phosphor Y is expressed as phosphor Y / (phosphor Y + phosphor G).
  • the weight fraction of the phosphor G is similarly expressed.
  • the synthetic excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the synthetic excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity at 450 nm of the excitation spectrum is 1.0.
  • the present inventors pay attention to the excitation spectrum intensity of the phosphor, which indicates how much light the phosphor emits at what excitation wavelength, and in particular, the light emitted by the blue semiconductor light emitting element.
  • the synthetic excitation spectrum intensity change rate of the phosphors Y and G 0.15 or less in both the third and fourth embodiments, the fluorescence intensity changes emitted by the phosphors Y and G can be suppressed as a total, Suppressed chromaticity shift.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member may be 0.23 or 0.33 or less in the third and fourth embodiments, respectively. In any of the embodiments, it may be 0.15 or less, and for this, the types and contents of the phosphor Y and the phosphor G may be appropriately adjusted. In any of the above-described embodiments, the phosphor Y and / or the phosphor G to be used are not limited in the rate of change of the individual excitation spectrum intensity as long as the synthetic excitation spectrum intensity is 0.15 or less. The synthetic excitation spectrum intensity of the phosphor G may be 0.15 or less alone.
  • the synthetic excitation spectrum intensity change rate is more preferably 0.14 or less, and still more preferably 0.12, in any of the embodiments.
  • the synthetic excitation spectrum intensity change rate is preferably 0.02 or more, and more preferably 0.04 or more.
  • the phosphor Y has an excitation spectrum intensity at 430 nm lower than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm
  • the phosphor G preferably has an excitation spectrum intensity at 430 nm larger than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm.
  • a blue-green phosphor represented by the following general formula (B1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm is preferably 500 nm or more and 520 nm or less.
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (B1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • a part of Al of the LuAG phosphor as shown by the following general formula (B2) is used.
  • a blue-green phosphor whose emission wavelength is adjusted to 500 nm or more and 520 nm or less by substituting with Ga is mentioned (hereinafter sometimes referred to as GLuAG).
  • the emission intensity in the wavelength region of 500 to 520 nm which cannot be reproduced by the phosphor G and the phosphor Y can be adjusted according to the change of the excitation wavelength, and better binning characteristics can be achieved.
  • the composition ratio of phosphor Y and phosphor G is usually 10:90 or more and 90:10 or less, preferably 12:88 or more and 88:12 or less, more preferably 15:85 or more, 85:15. It is as follows. By satisfying this condition, the shape can be significantly adjusted in the emission spectrum other than the excitation light when the excitation wavelength is changed. If it is outside the above range, the emission spectrum shape that can be adjusted is limited, and binning characteristics may not be improved.
  • the wavelength conversion member used in the fifth embodiment of the first invention is A phosphor G represented by the following general formula (G4) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm is 520 nm or more and 540 nm or less,
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.30 or less, and more preferably 0.28 or less. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the light-emitting devices according to the first to fifth embodiments have a rate of change in excitation spectrum intensity at the emission wavelength of 540 nm of the wavelength conversion member, which is not more than the above value, preferably the rate of change in synthetic excitation spectrum intensity represented by the formula (Z).
  • a good binning effect is exhibited in a range of approximately 430 nm to 465 nm.
  • the chromaticity change ⁇ u′v ′ of light emitted from the light emitting device is ⁇ u′v ′ ⁇ 0. It is preferable to satisfy .004.
  • ⁇ u′v ′ ⁇ 0.0035 is satisfied.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm.
  • the chromaticity change ⁇ u′v ′ of light emitted from the light emitting device when the emission wavelength of the blue semiconductor light emitting element is continuously changed from 435 nm to 470 nm satisfies ⁇ u′v ′ ⁇ 0.015. Is preferred.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 435 nm to 470 nm. .
  • the wavelength conversion member used in the sixth embodiment of the first invention is: A yellowish green phosphor represented by the following general formula (YG1), wherein the peak wavelength of the emission wavelength spectrum when excited at 450 nm is 530 nm or more and 550 nm or less; The excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.25 or less.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is 0.13 or less.
  • the excitation spectrum intensity change rate of the yellow-green phosphor is the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 465 nm when the excitation spectrum intensity of the yellow-green phosphor at 450 nm is 1.0. Expressed as a difference.
  • ⁇ u′v ′ The chromaticity change ⁇ u′v ′ of light emitted from the light emitting device when the emission wavelength of the blue semiconductor light emitting element is continuously changed from 445 nm to 455 nm satisfies ⁇ u′v ′ ⁇ 0.005.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • the said yellow-green fluorescent substance is what is shown by the following general formula (YG2).
  • M a A b E c Al d O e ⁇ (YG2) M is a Ce element.
  • A is one or more elements selected from the group of Y and Lu and containing 90% or more of Y.
  • E is Ga or Ga and Sc.
  • a + b 3, 4.5 ⁇ c + d ⁇ 5.5, 10.8 ⁇ e ⁇ 13.2, 0 ⁇ a ⁇ 0.9, 0.8 ⁇ c ⁇ 1.2)
  • the phosphor represented by the general formula (YG1) has a peak wavelength of an emission wavelength spectrum of 530 nm or more and 550 nm or less when excited at 450 nm, that is, a peak wavelength of an emission wavelength spectrum in a yellow-green region.
  • the phosphors referred to are included.
  • the intensity change of the excitation spectrum of the yellow-green phosphor is preferably 4.0% or less of the intensity of the excitation light spectrum at 450 nm from 440 nm to 460 nm.
  • the intensity change of the excitation spectrum is calculated based on the intensity at 540 nm.
  • the inventors pay attention to the excitation spectrum intensity of the phosphor, which indicates how much light the phosphor emits at what excitation wavelength, and particularly the wavelength of the light emitted by the blue semiconductor light emitting element.
  • Excitation spectrum intensity in the vicinity of 450 nm light was examined in detail. As a result, it has been conceived that a high luminance can be achieved in addition to good binning characteristics when the change rate of the excitation spectrum intensity at the emission wavelength of 540 nm of the wavelength conversion member is 0.25 or less.
  • the excitation spectrum intensity changes greatly the fluorescence intensity emitted from the phosphor changes greatly when the excitation wavelength changes, and the chromaticity of the light emitted from the light emitting device is shifted.
  • the chromaticity deviation of the light emitted from the wavelength conversion member was suppressed by setting the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member to 0.25 or less.
  • the variation in emission peak wavelength is usually about ⁇ 5 nm. Further, even the blue semiconductor light emitting element having the largest variation is about ⁇ 20 nm.
  • the light-emitting device according to this embodiment has excellent binning characteristics in which the chromaticity change of the emitted light is small with respect to the variation in the emission peak wavelength of the blue semiconductor light-emitting element serving as the light source.
  • a light emitting device is preferable.
  • the wavelength conversion member used in the seventh embodiment of the first invention is A phosphor represented by the following general formula (YG3), wherein the difference between the maximum value and the minimum value of the excitation spectrum intensity normalized with the excitation intensity of 450 nm when excited at an excitation wavelength of 440 nm to 460 nm is 0.05 or less Contains yellow-green phosphor.
  • the half width is preferably 105 nm or more and 120 nm or less from the viewpoint of color rendering properties.
  • the difference between the maximum value and the minimum value of the excitation spectrum intensity normalized with the excitation intensity of 450 nm when excited with an excitation wavelength of 440 nm to 460 nm is set to 0.05 or less, thereby reducing the wavelength conversion member.
  • the chromaticity deviation of the emitted light was suppressed. Therefore, by providing the wavelength conversion member, the light emitting device in this embodiment has a chromaticity change ⁇ u′v from the average chromaticity of light emitted from the wavelength conversion member when excited at an excitation wavelength of 445 nm to 455 nm. 'Becomes 0.005 or less.
  • ⁇ u′v ′ is the distance between the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ ave , v ′ ave ) of chromaticity from 445 nm to 455 nm. .
  • the variation in emission peak wavelength is usually about ⁇ 5 nm. Further, even the blue semiconductor light emitting element having the largest variation is about ⁇ 20 nm.
  • the light-emitting device according to the first to seventh embodiments of the first invention satisfies the above requirements, so that the chromaticity of the emitted light with respect to the variation in the emission peak wavelength of the blue semiconductor light-emitting element serving as the light source A light-emitting device having a small change and excellent so-called binning characteristics is preferable.
  • a spectrum of light emitted from the light emitting device is obtained using a 20 inch integrating sphere (LMS-200) manufactured by Labsphere and a spectrometer (Solid Lambda UV-Vis) manufactured by Carl Zeiss, and chromaticity ( u ′ i , v ′ i ) are calculated.
  • the excitation wavelength is changed at least every 5 nm, preferably every 3 nm, more preferably every 2 nm, and even more preferably every 1 nm.
  • the chromaticity (u ′ i , v ′ i ) at an arbitrary wavelength i nm emitted from is measured, and the average value (u ′ ave , v ′ ave ) is calculated. Then, the distance between the chromaticity (u ′ i , v ′ i ) and (u ′ ave , v ′ ave ) at the wavelength inm is obtained. Note that when measuring the average value of the chromaticity of light emitted from the light emitting device, the interval for changing the wavelength may be constant or random.
  • the phosphor represented by the general formula (YG1), the phosphor represented by the general formula (YG2), and the general formula (YG3) The content of the phosphor represented by (2) is not particularly limited, and can be appropriately set according to a request such as a color temperature of light emitted from the light emitting device.
  • the particle size of the phosphor used in the first to fifth embodiments of the first invention is preferably a volume-based median diameter D 50v of 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. . Moreover, the thing of 30 micrometers or less is preferable, and the thing of 20 micrometers or less can be used more preferably.
  • the volume-based median diameter D 50v is a volume-based relative when a sample is measured and a particle size distribution (cumulative distribution) is obtained using a particle size distribution measuring apparatus based on a laser diffraction / scattering method. It is defined as the particle size at which the particle amount is 50%.
  • a phosphor is put in ultrapure water, an ultrasonic disperser (manufactured by Kaijo Co., Ltd.) is used, the frequency is 19 KHz, the ultrasonic intensity is 5 W, and the sample is ultrasonicated for 25 seconds.
  • the transmittance is adjusted to a range of 88% to 92% using a flow cell, and after confirming that the particles are not aggregated, the particle size is measured by a laser diffraction type particle size distribution analyzer (Horiba LA-300). Examples include a method of measuring in a diameter range of 0.1 to 600 ⁇ m.
  • a dispersing agent may be used.
  • the phosphor is put in an aqueous solution containing 0.0003% by weight of Tamol (manufactured by BASF). In the same manner as described above, the measurement may be performed after ultrasonic dispersion.
  • D v / D n is a ratio (D v / D n ) between the volume-based average particle diameter D v and the number-based average particle diameter D n of the phosphor.
  • D v / D n is preferably 1.0 or more, more preferably 1.2 or more, and further preferably 1.4 or more.
  • D v / D n is preferably 25 or less, more preferably 10 or less, and particularly preferably 5 or less. If D v / D n is too large, there will be phosphor particles with significantly different weights, and the phosphor particles will tend to be non-uniformly dispersed in the phosphor layer.
  • the phosphor it is also possible to use a phosphor whose surface is previously coated with a third component.
  • the type of the third component used for coating and the coating method are not particularly limited, and any known third component and method may be used.
  • Examples of the third component include organic acids, inorganic acids, silane treating agents, silicone oil, liquid paraffin, and the like.
  • silane coupling materials dioalkyltrisilanol, dialkyldisianol, trialkylsilanol, monoalkyltrialkoxysilane, dialkyldialkoxysilane, trialkylalkoxysilane
  • siloxane having a substituent, silicone, and the like are preferable.
  • the surface treatment and coating amount are usually 0.01 to 10 parts by weight per 100 parts by weight of the phosphor. If the amount is less than 0.01 parts by weight, the affinity, dispersibility, thermal stability, fluorescence coloring property, etc. The improvement effect is difficult to obtain, and if it exceeds 10 parts by weight, problems such as deterioration of thermal stability, mechanical properties, and fluorescence coloring property are likely to occur.
  • the content of the phosphor in the wavelength conversion member depends on the type of the light diffusing material and the resin described later.
  • the resin is a polycarbonate resin
  • It is usually 0.1 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and usually 50 parts by weight or less, preferably 40 parts by weight or less based on 100 parts by weight of the polycarbonate resin. More preferably, it is 30 parts by weight or less, and still more preferably 20 parts by weight or less. If the content of the phosphor is too small, the wavelength conversion effect of the phosphor tends to be difficult to obtain, and if it is too large, the mechanical properties may deteriorate, which is not preferable.
  • the resin when it is a silicone resin, it is usually 0.1 parts by weight or more, preferably 1 part by weight or more, more preferably 3 parts by weight or more, and usually 80 parts by weight with respect to 100 parts by weight of the silicone resin. Part or less, preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less. If the content of the phosphor is too small, the wavelength conversion effect of the phosphor tends to be difficult to obtain, and if it is too large, the mechanical properties may deteriorate, which is not preferable.
  • the wavelength conversion member preferably further includes a red phosphor (also referred to as a first red phosphor).
  • a red phosphor also referred to as a first red phosphor.
  • the intensity change of the excitation spectrum when the excitation light wavelength is changed from 445 nm to 455 nm is 5.0% or less of the excitation spectrum by the excitation light of 455 nm. It is more preferably 0% or less, and further preferably 1.0% or less.
  • red phosphors satisfying such requirements (Sr, Ca) AlSiN 3 : Eu, Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (where 0 ⁇ x ⁇ 0 .5), K 2 SiF: Mn 4+ , Eu y (Sr, Ca, Ba) 1-y : Al 1 + x Si 4 ⁇ x O x N 7 ⁇ x (where 0 ⁇ x ⁇ 4, 0 ⁇ (Sr, Ca) AlSiN 3 : Eu or Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (where 0 ⁇ x ⁇ 0. 5) is preferable.
  • the first red phosphor is preferably a red phosphor having an emission peak wavelength of 600 nm to less than 640 nm and a half-value width of 2 nm to 120 nm.
  • red phosphors satisfying such requirements, (Sr, Ca) AlSiN 3 : Eu, Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (where 0 ⁇ x ⁇ 0 .5), Eu y (Sr, Ca, Ba) 1-y : Al 1 + x Si 4-x O x N 7-x (where 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 0.2), K 2 SiF: Mn 4+ , (Sr, Ca) AlSiN 3 : Eu or Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (provided that 0 ⁇ x ⁇ 0.
  • the first red phosphor having an emission peak wavelength of 600 nm or more and less than 640 nm and a half width of 2 nm or more and 120 nm or less preferably includes 30% or more, preferably 40% or more in terms of the composition weight ratio with respect to the total amount of the red phosphor. Is more preferable, and it is particularly preferable to include 50% or more. Further, it is preferably 95% or less, more preferably 90% or less, and particularly preferably 85% or less.
  • a red phosphor in addition to the first red phosphor described above or in place of the first red phosphor, a red phosphor (hereinafter also referred to as a second red phosphor). Preferably). More preferably, two kinds of red phosphors are included.
  • the phosphor X and the phosphor Y are combined to include at least four types of phosphors.
  • the light emitting device including the four types of phosphors can be selected to be a light emitting device that can achieve high conversion efficiency in addition to the good color rendering by adding the red phosphor. The degree of freedom increases. This is explained by the result of simulation described later.
  • the intensity change of the excitation spectrum when the excitation light wavelength is changed from 445 nm to 455 nm is 5.0% or less of the excitation spectrum by the excitation light of 455 nm. It is more preferably 0% or less, and further preferably 1.0% or less.
  • a red phosphor having an emission peak wavelength of 640 nm to 670 nm and a half width of 2 nm to 120 nm is preferable.
  • Examples of such a phosphor include CaAlSiN 3 : Eu phosphor, 3.5MgO ⁇ 0.5MgF 2 ⁇ GeO 2 : Mn 4+ phosphor, and the like is preferably a CaAlSiN 3 : Eu phosphor.
  • the content is not particularly limited as long as the effects of the present invention are not impaired, but the composition weight ratio with respect to the total amount of the red phosphor is 0.0% or more, 50. It is preferably 0% or less.
  • the intensity of the excitation spectrum of the red phosphor mixture when the excitation light wavelength is changed from 445 nm to 455 nm when mixed with the first red phosphor.
  • the change is preferably 5.0% or less of the excitation spectrum by 455 nm excitation light, more preferably 3.0% or less, and further preferably 1.0% or less.
  • a red phosphor also referred to as a first red phosphor
  • strength change of the excitation spectrum when the excitation light wavelength changes from 440 nm to 460 nm is 4.0% or less of the excitation spectrum by 450 nm excitation light. It is more preferably 0% or less, and further preferably 1.0% or less.
  • the lower limit is not particularly limited and is 0% or more.
  • the first red phosphor is preferably a red phosphor having an emission peak wavelength of 620 nm or more and less than 640 nm and a half width of 2 nm or more and 100 nm or less.
  • red phosphors satisfying such requirements (Sr, Ca) AlSiN 3 : Eu, Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (where 0 ⁇ x ⁇ 0.5 ), Eu y (Sr, Ca, Ba) 1-y : Al 1 + x Si 4 ⁇ x O x N 7 ⁇ x (where 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 0.2), K 2 SiF: Mn 4+ and the like, and (Sr, Ca) AlSiN 3 : Eu or Ca 1 ⁇ x Al 1 ⁇ x Si 1 + x N 3 ⁇ x O x : Eu (where 0 ⁇ x ⁇ 0.5) is preferable.
  • the (Sr, Ca) AlSiN 3: Eu is, M a A b D c E d X e (wherein, M is Eu, 1 A is selected from Mg, Ca, Sr, the group consisting of Ba 1 or 2 or more elements, D is Si, E is an essential element of Al, and is selected from the group consisting of B, Al, Ga, In, Sc, Y, La, Gd, and Lu.
  • X is an essential element, and X is one or more elements selected from the group consisting of O, N, and F.
  • the first red phosphor having an emission peak wavelength of 620 nm or more and less than 640 nm and a half width of 2 nm or more and 100 nm or less preferably includes 30% or more, preferably 40% or more in a composition weight ratio with respect to the total amount of the red phosphor Is more preferable, and it is particularly preferable to include 50% or more.
  • red phosphor hereinafter also referred to as a second red phosphor
  • a red phosphor hereinafter also referred to as a second red phosphor
  • two kinds of red phosphors are included.
  • the second red phosphor in addition to the good color rendering due to the addition of the red phosphor, the degree of freedom regarding the type and amount of the phosphor that can be selected in order to achieve a light emitting device that can achieve high conversion efficiency Will increase.
  • the intensity change of the excitation spectrum when the excitation light wavelength is changed from 440 nm to 460 nm is 5.0% or less of the excitation spectrum by 450 nm excitation light. It is more preferably 0% or less, and further preferably 1.0% or less.
  • a red phosphor having an emission peak wavelength of 640 nm to 670 nm and a half width of 2 nm to 120 nm is preferable.
  • Examples of such a phosphor include CaAlSiN 3 : Eu phosphor, 3.5MgO ⁇ 0.5MgF 2 .GeO 2 : Mn 4+ phosphor, and the like is preferably a CaAlSiN 3 : Eu phosphor.
  • the content is not particularly limited as long as the effects of the present invention are not impaired, but the composition weight ratio with respect to the total amount of the red phosphor is 0.0% or more and 50.0%. The following is preferable.
  • the intensity of the excitation spectrum of the red phosphor mixture when the excitation light wavelength is changed from 440 nm to 460 nm when mixed with the first red phosphor.
  • the change is preferably 5.0% or less of the excitation spectrum by 450 nm excitation light, more preferably 3.0% or less, and further preferably 1.0% or less.
  • the wavelength conversion member according to the first to seventh embodiments of the first invention includes a transparent material.
  • the transparent material is not particularly limited as long as it can transmit light without substantially absorbing light, and can be used for dispersing the phosphor, but has a refractive index of 1.3 to 1.7. It is preferable.
  • the measuring method of the refractive index of a transparent material is as follows. The measurement temperature is 20 ° C., measured by the prism coupler method. The measurement wavelength is 450 nm.
  • Table 1 shows the refractive index of a resin generally used as a transparent material.
  • the refractive index of each resin in Table 1 is a general reference value, and the refractive index of each resin is not necessarily limited to the value in Table 1.
  • These resins used as the transparent material described above may be used alone or in combination of two or more. Moreover, the copolymer of these resin may be sufficient.
  • thermoplastic resins thermosetting resins, photocurable resins, etc., glass, etc.
  • polycarbonate resin and silicone resin are transparent and heat resistant.
  • polycarbonate resin is more preferable from the viewpoint of versatility
  • silicone resin is preferable from the viewpoint of heat resistance.
  • the polycarbonate resin will be described in detail.
  • the polycarbonate resin used in the first to seventh embodiments of the first invention is a polymer having a basic structure having a carbonic acid bond represented by the following general chemical formula (1).
  • X 1 is generally a hydrocarbon, but X 1 into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.
  • the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, either of which can be used.
  • aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.
  • the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned.
  • a polyhydroxy compound or the like may be reacted.
  • a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
  • the polycarbonate polymer may be linear or branched.
  • the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units.
  • the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer.
  • such a polycarbonate polymer is a thermoplastic resin.
  • aromatic dihydroxy compounds include dihydroxy compounds such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene, and the like.
  • Benzenes such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl; 2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxy Dihydroxynaphthalenes such as naphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; 2 , 2'- Hydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) benzene, 1,3 Dihydroxydiary
  • Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone;
  • bis (hydroxyaryl) alkanes are preferred, and bis (4-hydroxyphenyl) alkanes are preferred, and 2,2-bis (4-hydroxyphenyl) propane (ie, in terms of impact resistance and heat resistance) Bisphenol A) is preferred.
  • 1 type may be used for an aromatic dihydroxy compound, and it may use 2 or more types together by arbitrary combinations and a ratio.
  • Examples of monomers used as raw materials for aliphatic polycarbonate resins include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, Cycloalkanediols such as 2,2,4,4-tetramethyl-cyclobutane-1,3-di
  • examples of the carbonate precursor include carbonyl halide and carbonate ester.
  • 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.
  • carbonyl halide examples include phosgene, haloformates such as bischloroformate of dihydroxy compounds, and monochloroformate of dihydroxy compounds.
  • carbonate ester examples include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as
  • the method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
  • an interfacial polymerization method a melt transesterification method
  • a pyridine method a ring-opening polymerization method of a cyclic carbonate compound
  • a solid phase transesterification method of a prepolymer a prepolymer.
  • the interfacial polymerization method and the melt transesterification method which are particularly suitable among these methods, will be specifically described.
  • Interfacial polymerization method In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence.
  • a molecular weight adjusting agent terminal terminator
  • an antioxidant may be present to prevent the oxidation of the dihydroxy compound.
  • the dihydroxy compound and the carbonate precursor are as described above.
  • phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.
  • organic solvent inert to the reaction examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. .
  • 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.
  • alkali compound contained in the alkaline aqueous solution examples include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred.
  • 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the concentration of the alkali compound in the alkaline aqueous solution is not limited, but is usually used at 5 to 10% by weight in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12.
  • the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11.
  • the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.
  • polymerization catalyst examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride; Examples include pyridine, guanine, guanidine salts, and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the molecular weight modifier examples include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol, mercaptans, and phthalimides, among which aromatic phenols are preferred.
  • aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol.
  • Substituted phenols vinyl group-containing phenols such as isopropanyl phenol, epoxy group-containing phenols, carboxyl group-containing phenols such as o-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid.
  • a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound.
  • the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set.
  • the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
  • the reaction temperature is usually 0 to 40 ° C.
  • the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).
  • melt transesterification method for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.
  • the dihydroxy compound is as described above.
  • examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.
  • carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. Is more preferable.
  • the upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.
  • the amount of terminal hydroxyl groups tends to have a large effect on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method.
  • a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like.
  • the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.
  • the mixing ratio is as described above.
  • a more aggressive adjustment method there may be mentioned a method in which a terminal terminator is mixed separately during the reaction.
  • the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like.
  • 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.
  • a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the reaction temperature is usually 100 to 320 ° C.
  • the pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less.
  • a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
  • the melt polycondensation reaction can be performed by either a batch method or a continuous method.
  • the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily.
  • the melt polycondensation reaction is preferably carried out continuously.
  • a catalyst deactivator may be used as necessary.
  • a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof.
  • 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.
  • the molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined.
  • the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16,000 or more, more preferably 18, 000 or more, and usually 40,000 or less, preferably 30,000 or less.
  • the viscosity average molecular weight can be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed.
  • Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.
  • the intrinsic viscosity [ ⁇ ] is a value calculated by the following formula (1) by measuring the specific viscosity [ ⁇ sp ] at each solution concentration [C] (g / dl).
  • the terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. Moreover, it is 10 ppm or more normally, Preferably it is 30 ppm or more, More preferably, it is 40 ppm or more. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more.
  • the unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin.
  • the measuring method is a colorimetric determination by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)).
  • the polycarbonate resin may be used alone or in combination of two or more in any combination and ratio.
  • the polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination.
  • a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy
  • the proportion of the polycarbonate resin in the resin component is preferably 50% by weight or more, more preferably 60% by weight or more, and 70% by weight or more. Further preferred.
  • the polycarbonate resin may contain a polycarbonate oligomer.
  • the viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less.
  • the polycarbonate ligomer contained is preferably 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).
  • the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin).
  • used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets.
  • non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
  • the recycled polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention.
  • Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.
  • the above-mentioned transparent material can contain various known additives as necessary within the range not impairing the characteristics of the present invention.
  • heat stabilizer, antioxidant, mold release agent, flame retardant, flame retardant aid, UV absorber, lubricant, light stabilizer, plasticizer, antistatic agent, thermal conductivity improver, conductivity improver, Coloring agents, impact resistance improving agents, antibacterial agents, chemical resistance improving agents, reinforcing agents, laser marking improving agents, refractive index adjusting agents and the like can be mentioned.
  • the specific kind and amount of these additives can be selected from known suitable materials for transparent materials.
  • the heat stabilizer examples include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.
  • triphenyl phosphite tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.
  • the content of the heat stabilizer is usually 0.0001 parts by weight or more, preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. It is not more than parts by weight, preferably not more than 0.5 parts by weight, more preferably not more than 0.3 parts by weight, still more preferably not more than 0.1 parts by weight. If the amount of the heat stabilizer is too small, it is difficult to obtain the effect of improving the heat stability. If the amount is too large, the heat stability may be lowered.
  • antioxidants examples include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl).
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • the content of the antioxidant is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 1 part by weight or less, preferably 0.5 part by weight with respect to 100 parts by weight of the polycarbonate resin. Part or less, more preferably 0.3 part by weight or less.
  • the content of the antioxidant is less than the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.
  • release agent examples include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.
  • the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids.
  • the aliphatic carboxylic acid includes alicyclic carboxylic acid.
  • preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
  • aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.
  • the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol for example, the same one as the aliphatic carboxylic acid can be used.
  • the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.
  • alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastea
  • Examples of the aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
  • the aliphatic hydrocarbon includes alicyclic hydrocarbons.
  • paraffin wax polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
  • the number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
  • polysiloxane silicone oil examples include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.
  • the content of the release agent is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 5 parts by weight or less, preferably 3 parts by weight or less, relative to 100 parts by weight of the polycarbonate resin. More preferably, it is 1 part by weight or less, and still more preferably 0.5 part by weight or less.
  • the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.
  • the flame retardant examples include organic flame retardants such as halogen-based, phosphorus-based, organic acid metal salt-based, silicone-based, organic halogen compounds, antimony compounds, phosphorus compounds, nitrogen compounds, inorganic flame retardants, and flame retardant aids. And fluorine resin flame retardant aids.
  • a flame retardant and a flame retardant aid can be used in combination, or a plurality of flame retardants can be used in combination. Among these, phosphorus flame retardants, organic acid metal salt flame retardants, and fluororesin flame retardant aids are preferred.
  • phosphorus flame retardants include aromatic phosphate esters, and phosphazene compounds such as phenoxyphosphazene and aminophosphazene having a bond between a phosphorus atom and a nitrogen atom in the main chain.
  • aromatic phosphate ester flame retardant examples include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4 ′ -Biphenol bis (dixylenyl phosphate), bisphenol A bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4 ' -Biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.
  • the content of the flame retardant is usually 0.01 to 30 parts by weight with respect to 100 parts by weight of the resin.
  • an organic sulfonic acid metal salt is preferable, and a fluorine-containing organic sulfonic acid metal salt is particularly preferable.
  • Specific examples thereof include potassium perfluorobutane sulfonate.
  • Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate, and the like.
  • Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like.
  • Examples of the nitrogen-based compound include melamine, cyanuric acid, melamine cyanurate, and the like.
  • Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, silicon compound, boron compound and the like.
  • the fluorine-based flame retardant aid a fluoroolefin resin is preferable, and a tetrafluoroethylene resin having a fibril structure can be exemplified.
  • the fluorine-based flame retardant aid may be in a powder form, a dispersion form, a powder form in which a fluororesin is coated with another resin, or any form.
  • the ultraviolet absorber examples include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, etc. Examples include ultraviolet absorbers. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting an organic ultraviolet absorber, the polycarbonate resin composition of the present invention tends to have good transparency and mechanical properties.
  • benzotriazole compound examples include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2,2′-methylenebis [4- (1,
  • benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd.
  • UV5411 Adeka's “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, Ciba Specialty Chemicals' “Chinubin P”, “Chinubin” 234 ",” Tinubin 326 “,” Tinubin 327 “,” Tinubin 28 ", and the like.
  • the preferable content of the ultraviolet absorber is 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and 5 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. More preferably, it is 1 part by weight or less, and still more preferably 0.5 part by weight or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the silicone resin used in the first to seventh embodiments of the first invention is not particularly limited. However, the smaller the absorption in visible light, the smaller the loss of light, which is preferable.
  • a liquid silicone resin or the like is preferable in terms of mixing with a phosphor and processability to a wavelength conversion member.
  • the liquid silicone resin using an addition curing type that cures by hydrosilylation reaction, no by-product is generated at the time of curing, and there is no problem that the pressure in the mold does not become abnormally high, This is particularly preferable because sink marks and bubbles are hardly generated in the molded product, and further, since the curing speed is high, the molding cycle can be shortened.
  • the addition curing type liquid silicone resin contains an organopolysiloxane having a hydrosilyl group (first component), an organopolysiloxane having an alkenyl group (second component), and a curing catalyst.
  • a typical example of the first component is a polydiorganosiloxane having two or more hydrosilyl groups in the molecule, specifically, a polydiorganosiloxane having hydrosilyl groups at both ends, and a polypolyorganosiloxane having both ends blocked with trimethylsilyl groups.
  • the second component those having at least two vinyl groups bonded to silicon atoms in one molecule are preferably used.
  • An organopolysiloxane that serves both as the first component and the second component that is, an organopolysiloxane having both a hydrosilyl group and an alkenyl group in one molecule may be used. Further, the first component and the second component may be used alone, or two or more kinds of the first component and / or the second component may be used in combination.
  • the curing catalyst is a catalyst for promoting the addition reaction between the hydrosilyl group in the first component and the alkenyl group in the second component.
  • examples thereof include platinum black, second platinum chloride, chloroplatinic acid, chloride.
  • Platinum group metal catalysts such as a reaction product of platinum acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, a platinum-based catalyst such as platinum bisacetoacetate, a palladium-based catalyst, and a rhodium-based catalyst.
  • a curing catalyst may be used independently and may use 2 or more types together.
  • fumed silica can be added to the silicone resin for the purpose of imparting thixotropic properties to the raw material composition.
  • Fumed silica is an ultrafine particle having a large specific surface area of 50 m 2 / g or more, and commercially available products include Aerosil (registered trademark) of Nippon Aerosil Co., Ltd. and WACKER HDK (Asahi Kasei Silicone Co., Ltd.). Registered trademark). Giving thixotropy is effective in preventing the composition of the raw material composition from becoming non-uniform due to the precipitation of the phosphor.
  • thixotropic properties can be imparted to the raw material composition without causing excessive thickening.
  • a raw material composition having both high fluidity suitable for injection molding and an anti-settling effect of the phosphor can be obtained.
  • a fumed silica Usually 0.1 weight part or more with respect to 100 weight part of silicone resins, Preferably it is 0.5 weight part or more, Especially preferably, it is 1 weight part or more, Usually 20 It is not more than parts by weight, preferably not more than 18 parts by weight, particularly preferably not more than 15 parts by weight. If the amount is less than 0.1 parts by weight, high fluidity suitable for injection molding and the effect of preventing the settling of the phosphor cannot be sufficiently obtained. It is not preferable because the properties cannot be obtained.
  • the raw material composition is a curing rate control agent, anti-aging agent, radical inhibitor, ultraviolet absorber, adhesion improver, flame retardant, surfactant, storage stability improver, ozone deterioration prevention.
  • Additives such as an agent, a light stabilizer, a plasticizer, a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, and a release agent can be added.
  • the wavelength conversion member of the first to seventh embodiments in the first invention may contain a diffusing material.
  • a diffusing material By containing the diffusing material, it is possible to cause the wavelength conversion member to exhibit light diffusibility.
  • it contains a diffusing material it is preferable to contain an inorganic light diffusing material, an organic light diffusing material or bubbles.
  • inorganic light diffusing materials include silicon dioxide (silica), white carbon, fused silica, talc, magnesium oxide, zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, boron oxide, boron nitride, aluminum nitride, and nitride.
  • Silicon calcium carbonate, barium carbonate, magnesium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium sulfate, calcium silicate, magnesium silicate, aluminum silicate, sodium silicate aluminide, zinc silicate, zinc sulfide,
  • the material include glass particles, glass fibers, glass flakes, mica, wollastonite, zeolite, sepiolite, bentonite, montmorillonite, hydrotalcite, kaolin, and potassium titanate.
  • These inorganic light diffusing materials may be treated with various surface treatment agents such as a silane coupling agent, a titanate coupling agent, methyl hydrogen polysiloxane, and a fatty acid-containing hydrocarbon compound. It may be coated with an active inorganic compound.
  • organic light diffusing material examples include materials such as styrene (co) polymers, acrylic (co) polymers, siloxane (co) polymers, and polyamide (co) polymers. Some or all of these molecules of the organic diffusing material may or may not be cross-linked.
  • (co) polymer means both “polymer” and “copolymer”.
  • the diffusion material preferably contains at least one selected from the group consisting of silica, glass, calcium carbonate, mica, crosslinked acrylic (co) polymer particles, and siloxane (co) polymer particles. Further, the average particle diameter is preferably 1 ⁇ m or more, and preferably 30 ⁇ m or less. The average particle size is a particle size measured with an integrated weight percentage, a particle size distribution meter or the like.
  • the Mohs hardness is preferably less than 8, and more preferably less than 7.
  • a diffusion material having such hardness it is preferable that ratio L / D of the major axis L and the minor axis D is 200 or less.
  • L / D is more preferably 50 or less.
  • the diffusing material when adjusting the transmittance of the wavelength conversion member by the diffusing material, for example, a diffusing material having a small average particle diameter is added, a diffusing material having a large refractive index difference from the transparent material is added, or Adjustment by lowering the transmittance of the wavelength conversion member can be performed by increasing the amount of addition.
  • the average particle size of the diffusing material is usually 100 ⁇ m or less, preferably 0.1 to 30 ⁇ m, more preferably 0.1 to 15 ⁇ m, still more preferably 1 to 5 ⁇ m.
  • the diffusing agent may be a crosslinked acrylic (co) polymer particle, a crosslinked particle of a copolymer of an acrylic compound and a styrene compound, a siloxane (co) polymer particle, an acrylic It is preferable to use hybrid crosslinked particles of a compound and a compound containing a silicon atom, and it is more preferable to use crosslinked acrylic (co) polymer particles and siloxane (co) polymer particles.
  • crosslinked acrylic (co) polymer particles polymer particles composed of a non-crosslinkable acrylic monomer and a crosslinkable monomer are more preferable, and polymer particles obtained by crosslinking methyl methacrylate and trimethylolpropane tri (meth) acrylate are more preferable.
  • siloxane-based (co) polymer polyorganosilsesquioxane particles are more preferable, and polymethylsilsesquioxane particles are more preferable.
  • polymethylsilsesquioxane particles are particularly preferable in terms of excellent thermal stability.
  • the dispersion shape of the diffusing material in the wavelength conversion member may be substantially spherical, plate-like, needle-like, or indefinite, but is preferably substantially spherical in that there is no anisotropy in the light scattering effect.
  • the average dimension of the diffusing material is usually 100 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and usually 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more. If the average size of the diffusing material is out of the above range, the light diffusivity is likely to fluctuate greatly due to subtle differences in the content of the diffusing material and the difference in particle size, and the light diffusing property should be controlled stably.
  • the average dimension of the diffusing material is a 50% average dimension based on volume, and is the value of the median diameter (D50) of the volume standard particle size distribution measured by laser or diffraction scattering method.
  • the particle size distribution of the diffusing material may be a monodisperse system or a polydisperse system having several peak tops. However, it is preferable that the particle size distribution is narrow and the particle size is almost a single particle size (monodispersion or particle size distribution close to monodispersion).
  • D v / D n As an index indicating the degree of distribution of the particle size of the diffusing material, there is a ratio (D v / D n ) between the volume-based average particle size D v and the number-based average particle size D n of the diffusing material.
  • D v / D n is preferably 1.0 or more.
  • D v / D n is preferably 5 or less. If D v / D n is too large, there will be diffusing materials with significantly different weights, and the dispersion of the diffusing material tends to be non-uniform in the wavelength conversion member.
  • the inorganic light diffusing material, the organic light diffusing material, and the bubbles used as the diffusing material described above may be used alone or in combination of two or more different materials and dimensions.
  • the refractive index of the diffusing material is calculated by the volume average of a plurality of diffusing materials.
  • the refractive index of the diffusing material is preferably 1.0 or more and 1.9 or less.
  • the diffusing material is preferably highly transparent and excellent in light transmittance.
  • the extinction coefficient may be 10 ⁇ 2 or less, preferably 10 ⁇ 3 or less, and more preferably 10 ⁇ . 4 or less, particularly preferably 10 ⁇ 6 or less.
  • the refractive index of the diffusing material can be measured by the immersion method (Aerosol Research Vol. 9, No. 1 Spring pp. 44-50 (1994)) of YOSHIYAMA et al. The measurement temperature is 20 ° C., and the measurement wavelength is 450 nm.
  • Table 2 below lists the refractive indices of materials generally used as diffusion materials.
  • the refractive index of each material in Table 2 is a general reference value, and the refractive index of each material is not necessarily limited to the value in Table 2.
  • the content of the diffusing material in the wavelength conversion member depends on the type of transparent material.
  • the transparent material is a polycarbonate resin and the diffusing material is polymethylsilsesquioxane particles
  • the content is 100 parts by weight of the polycarbonate resin.
  • it is usually 0.1 parts by weight or more, preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, and usually 10.0 parts by weight or less, preferably 7.0 parts by weight or less. More preferably, it is 3.0 parts by weight or less. If the content of the diffusing material is too small, the diffusing effect is insufficient, and if it is too large, the mechanical identification may decrease, which is not preferable.
  • a wavelength conversion member including a transparent material The wavelength conversion member according to the first to sixth
  • the manufacturing method of the wavelength conversion member is not particularly limited, and a known method may be used.
  • a general manufacturing method when the transparent material is a polycarbonate resin is as follows.
  • phosphor and diffusing material blended into polycarbonate resin if necessary, and mix with various mixers such as tumbler mixer and Henschel mixer. Mixing may be performed by mixing all raw materials at once, or by dividing several raw materials and mixing them. Thereafter, it is melt-kneaded with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like to obtain resin composition pellets.
  • various mixers such as tumbler mixer and Henschel mixer.
  • Mixing may be performed by mixing all raw materials at once, or by dividing several raw materials and mixing them. Thereafter, it is melt-kneaded with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like to obtain resin composition pellets.
  • the transparent material is polycarbonate resin and the case where a diffusing material other than air bubbles is contained is illustrated in more detail and preferable conditions.
  • Polycarbonate resin, phosphor, diffusing material, and other additives are mixed with a tumbler mixer and then melt kneaded using a single screw or twin screw extruder.
  • a screw composed mainly of a forward-flight flight screw element is used as a screw so as not to apply excessive pruning force.
  • the frequent use of a screw element that strongly applies a cutting force, such as a reverse feed flight screw or a kneading screw element, is undesirable because it causes discoloration of the resin.
  • a screw and cylinder made of a material that has been subjected to an abrasion-resistant treatment that is difficult to cut.
  • the kneading temperature is preferably in the range of 230 to 340 ° C. If the measured resin temperature exceeds 340 ° C., discoloration tends to occur, which is not preferable. If the resin temperature is less than 230 ° C., the melt viscosity of the polycarbonate resin is too high, and the mechanical load on the extruder increases.
  • a particularly preferable kneading temperature is in the range of 240 to 300 ° C.
  • the screw rotation speed and discharge amount may be appropriately selected in view of the production speed, the load on the extruder, and the state of the resin pellets. Moreover, it is preferable to install one or more vent structures in the extruder for releasing air entrained with the raw material and gas generated by heating out of the extruder system.
  • a wavelength conversion member is formed using the polycarbonate resin composition pellets obtained as described above.
  • the method for forming the wavelength deformable member is not particularly limited, and may be formed by a known method according to the required specifications. Examples thereof include sheet / film extrusion molding, profile extrusion molding, vacuum molding, injection molding, blow molding, injection blow molding, rotational molding, foam molding, and the like. Among these, it is preferable to adopt an injection molding method. Furthermore, if necessary, the molded body can be further processed by welding, bonding, cutting, and the like.
  • the diffusing material is a bubble
  • the bubble may be formed in the member by a method such as blending of a blowing agent, nitrogen gas injection, supercritical gas injection, or the like.
  • the wavelength conversion member may be an embodiment of a wavelength conversion member formed only from the phosphor composition, or may be formed by applying the phosphor composition on a transparent substrate such as glass or an acrylic plate, and may be used as the wavelength conversion member. .
  • the polycarbonate resin composition pellet is an example of the phosphor composition according to the third invention of the present invention.
  • the third invention of the present invention is an invention relating to a phosphor composition
  • the first embodiment of the third invention is:
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (Y1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • Phosphor G which is represented by the following general formula (G1) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm,
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (G1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • a transparent material
  • the phosphor composition is not limited to a pellet, but is preferably a pellet from the viewpoint of flowability and ease of handling.
  • the explanation of the first to sixth embodiments in the second invention is applied, respectively.
  • the description of the first to seventh embodiments in the first invention is applied to the configuration of the phosphor composition.
  • the fourth invention of the present invention is an invention related to a phosphor mixture
  • the first embodiment is A phosphor Y represented by the following general formula (Y1) and having a peak wavelength of an emission wavelength spectrum when excited at 450 nm is 540 nm or more and 570 nm or less;
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (Y1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • It is a phosphor mixture containing phosphor G which is represented by the following general formula (G1) and has a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 520 nm or more and 540 nm or less.
  • (Y, Ce, Tb, Lu) x (Ga, Sc, Al) y O z (G1) (X 3, 4.5 ⁇ y ⁇ 5.5, 10.8 ⁇ z ⁇ 13.4)
  • the excitation spectrum intensity change rate at a fluorescence wavelength of 540 nm is preferably 0.40 or less.
  • the excitation spectrum intensity change rate of the phosphor mixture is expressed by the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm when the excitation spectrum intensity of the phosphor mixture at 450 nm is 1.0. Is done.
  • the excitation spectrum intensity change rate is calculated using the intensity at the emission wavelength of 540 nm.
  • the excitation spectrum intensity change rate can be determined by measuring the excitation spectrum of the phosphor mixture at room temperature (25 ° C.) using a fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. More specifically, the emission peak at 540 nm is monitored to obtain an excitation spectrum in the wavelength range of 430 nm to 470 nm, the excitation spectrum intensity at an excitation wavelength of 450 nm is 1.0, and the excitation wavelength is from 430 nm to 470 nm. It is obtained by calculating the intensity change of the excitation spectrum when changed to.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.36 or less, and more preferably 0.33 or less. By setting it within this range, an abrupt change in the emission spectrum according to the excitation wavelength change can be suppressed, and good binning characteristics can be obtained. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more. When the excitation spectrum is 0.03 or less, the emission spectrum intensity when the excitation wavelength is changed is the same, but since the photopic sensitivity is different, the luminance and chromaticity may change substantially, which is not preferable. .
  • the phosphor Y is a phosphor represented by the following general formula (Y2)
  • the phosphor G is a phosphor represented by the following general formula (G2)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.30 or less.
  • the excitation spectrum intensity change rate can be measured in the same manner as described above. More specifically, the emission peak at 540 nm is monitored to obtain an excitation spectrum in the wavelength range of 435 nm to 470 nm, the excitation spectrum intensity at an excitation wavelength of 450 nm is 1.0, and the excitation wavelength is from 435 nm to 470 nm. It is obtained by calculating the intensity change of the excitation spectrum when changed to.
  • the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.28 or less, and more preferably 0.25 or less. By setting it within this range, an abrupt change in the emission spectrum according to the excitation wavelength change can be suppressed, and good binning characteristics can be obtained.
  • the excitation spectrum intensity is desirably 0.03 or more, and more preferably 0.05 or more.
  • the phosphor is a YAG phosphor
  • the half width is 100 nm or more and 130 nm or less.
  • the fluorescent substance G is a GYAG fluorescent substance
  • a half value width is 105 to 120 nm.
  • the phosphor Y is a phosphor represented by the following general formula (Y3)
  • the phosphor G is a phosphor represented by the following general formula (G3)
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
  • the excitation spectrum intensity change rate can be measured in the same manner as described above. More specifically, the emission peak at 540 nm is monitored to obtain an excitation spectrum in the wavelength range of 435 nm to 465 nm, the excitation spectrum intensity at an excitation wavelength of 450 nm is 1.0, and the excitation wavelength is from 435 nm to 465 nm. It is obtained by calculating the intensity change of the excitation spectrum when changed to.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less, and more preferably 0.20 or less. By setting it within this range, an abrupt change in the emission spectrum according to the excitation wavelength change can be suppressed, and good binning characteristics can be obtained. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the phosphor is a YAG phosphor
  • the half width is 100 nm or more and 130 nm or less.
  • the fluorescent substance G is a LuAG fluorescent substance
  • a half value width is 30 nm or more and 120 nm or less.
  • the fifth embodiment is as follows.
  • a phosphor mixture comprising phosphor G, which is represented by the following general formula (G4) and has an emission wavelength spectrum having a peak wavelength of 520 nm or more and 540 nm or less when excited at 450 nm,
  • the phosphor mixture has an excitation spectrum change rate of 0.25 nm or less at an emission wavelength of 540 nm.
  • the excitation spectrum intensity change rate of the wavelength conversion member is the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 435 nm to 465 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. expressed.
  • the excitation spectrum intensity change rate can be determined by measuring the excitation spectrum of the phosphor mixture at room temperature (25 ° C.) using a fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. More specifically, the emission peak at 540 nm is monitored to obtain an excitation spectrum in the wavelength range of 435 nm to 465 nm, the excitation spectrum intensity at an excitation wavelength of 450 nm is 1.0, and the excitation wavelength is from 435 nm to 465 nm. It is obtained by calculating the intensity change of the excitation spectrum when changed to.
  • the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less, and more preferably 0.20 or less. By setting it within this range, an abrupt change in the emission spectrum according to the excitation wavelength change can be suppressed, and good binning characteristics can be obtained. Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more.
  • the description of the first to seventh embodiments in the first invention is applied to the other configurations of the phosphor mixture according to the first to sixth embodiments in the fourth invention.
  • the description of the first to sixth embodiments in the second invention is applied to the method of kneading and molding the phosphor mixture with silicone resin or polycarbonate resin to obtain the wavelength conversion member. Specifically, the method described in Examples can be used.
  • FIG. 2 is a schematic diagram illustrating an example of a light emitting device including a wavelength conversion member according to the first to seventh embodiments of the first invention.
  • the semiconductor light emitting device 10 includes at least a blue semiconductor light emitting element 1 and a wavelength conversion member 3 as its constituent members.
  • the blue semiconductor light emitting element 1 emits excitation light for exciting the phosphor contained in the wavelength conversion member 3.
  • the blue semiconductor light emitting element 1 usually emits excitation light having a peak wavelength of 425 nm to 475 nm, and preferably emits excitation light having a peak wavelength of 430 nm to 465 nm.
  • the number of blue semiconductor light emitting elements 1 can be appropriately set depending on the intensity of excitation light required by the apparatus.
  • the violet semiconductor light emitting device usually emits excitation light having a peak wavelength of 390 nm to 425 nm, and preferably emits excitation light having a peak wavelength of 395 to 415 nm.
  • the blue semiconductor light emitting element 1 is mounted on the chip mounting surface 2 a of the wiring board 2.
  • a wiring pattern (not shown) for supplying electrodes to these blue semiconductor light emitting elements 1 is formed on the wiring substrate 2 to constitute an electric circuit.
  • the wavelength conversion member 3 is displayed on the wiring board 2, but the present invention is not limited to this, and the wiring board 2 and the wavelength conversion member 3 may be arranged via other members.
  • the wiring substrate 2 and the wavelength conversion member 3 are arranged via the frame body 4.
  • the frame body 4 may have a tapered shape in order to give light directivity.
  • the frame 4 may be a reflective material.
  • the wiring board 2 is excellent in electrical insulation, has good heat dissipation, and preferably has a high reflectance, but on the surface where the blue semiconductor light emitting element 1 is not present on the chip mounting surface of the wiring board 2, Alternatively, a reflective plate having a high reflectance can be provided on at least a part of the inner surface of another member that connects the wiring substrate 2 and the wavelength conversion member 3.
  • the reflectance of such a wiring board or reflector is preferably 80% or more.
  • alumina ceramic, resin, glass epoxy, composite resin containing filler in resin, or the like can be used.
  • a resin containing a white pigment such as alumina powder, silica powder, magnesium oxide, titanium oxide, zirconium oxide, zinc oxide, or zinc sulfide is used. It can.
  • Preferred resins include silicone resin, polycarbonate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, fluorine-based resin and the like.
  • the wavelength conversion member 3 converts the wavelength of part of the incident light emitted from the blue semiconductor light emitting element 1 and emits outgoing light having a wavelength different from that of the incident light.
  • the wavelength conversion member 3 contains a transparent material and a phosphor G, and preferably further contains a phosphor Y.
  • the resin in which the phosphor is dispersed include polycarbonate resin, polyester resin, acrylic resin, epoxy resin, and silicone resin.
  • the wavelength conversion member 3 contains a small amount of a diffusing material together with the phosphor.
  • the diffusing material include inorganic light diffusing materials, organic light diffusing materials, and bubbles.
  • the diffusing material preferably contains at least one selected from the group consisting of silica, glass, calcium carbonate, mica, crosslinked acrylic (co) polymer particles, and siloxane (co) polymer particles.
  • the wavelength conversion member 3 has a distance from the blue semiconductor light emitting element 1. That is, the wavelength conversion member 3 and the blue semiconductor light emitting element 1 are separated from each other. There may be a gap between the wavelength conversion member 3 and the blue semiconductor light emitting element 1 or may be filled with a filler. Thus, by the aspect which has distance between the wavelength conversion member 3 and the blue semiconductor light-emitting device 1, deterioration of the phosphor contained in the wavelength conversion member 3 and the wavelength conversion member by the heat which the blue semiconductor light-emitting device 1 emits is suppressed. can do.
  • the distance between the blue semiconductor light emitting element 1 and the wavelength conversion member 3 is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and particularly preferably 1.0 mm or more.
  • the distance between the wavelength conversion member 3 and the blue semiconductor light emitting element 1 is preferably 1.0 m or less, 500 mm or less is further preferable, and 100 mm or less is particularly preferable.
  • the light emitting device 10 can be suitably applied as a light emitting device used for general illumination.
  • the light emitting devices according to the first to fifth embodiments of the first invention are preferably provided in a general lighting device and used as a general lighting device that emits white light.
  • the light emitting device 10 has a light output emitted from the light emitting device having a deviation duv from the light-colored blackbody radiation locus of ⁇ 0.0200 to 0.0200 and a color temperature. Is preferably 1800K or more and 7000K or less, and more preferably 5000K or less.
  • the light emitting devices according to the first to fifth embodiments of the first invention emit light having high color rendering properties.
  • the average color rendering index Ra is preferably 80 or more, more preferably 82 or more, and further preferably 85 or more.
  • the light emitting device 10 is provided in an image display device and can be used as an image display device that emits white light.
  • the light emitting device 10 When applied to such a use, the light emitting device 10 has a light output emitted from the light emitting device having a deviation duv from the light-colored blackbody radiation locus of ⁇ 0.0200 to 0.0200 and a color temperature. Is preferably 5000K or more and 20000K or less, and more preferably 15000K or less.
  • the light emitting device according to the sixth to seventh embodiments of the first invention can be suitably applied as a light emitting device used for general illumination or a light emitting device used for a backlight.
  • the general lighting device including the light emitting device according to the sixth to seventh embodiments of the first invention is preferably a general lighting device that emits white light.
  • the light emitted from the light emitting device has a deviation duv from the black body radiation locus of the light color of ⁇ 0.0200 to 0.0200, and the color The temperature is preferably 1800K or more and 7000K or less.
  • the light emitting device according to the sixth to seventh embodiments of the first invention when applied to a backlight, the light emitting device according to the sixth to seventh embodiments of the first invention emits light from the light emitting device.
  • the light to be emitted preferably has a color temperature higher than 7000K and lower than 20000K.
  • FIG. 4 and Table 3 show simulation results when the phosphors represented by the general formula (m1) performed by the present inventors are used, and the color rendering properties of light emitted from the light emitting device depending on the type of the phosphors. It shows how the luminous efficiency changes.
  • a chip having a peak wavelength of 453 nm was used as an excitation source, and four types of fluorescence of YAG, GYAG, SCASN, and CASN (each measured data such as an emission spectrum of a phosphor used in an experimental example described later) was used.
  • the wavelength conversion member was comprised using 3 types of fluorescent substance among the bodies. Then, by adjusting the content ratio of each phosphor so that the emission color from the wavelength conversion member becomes 2700K, it was simulated how the relationship between the color rendering properties and the emission efficiency changes.
  • the straight line located on the left side shows a case where simulation is performed using three types of phosphors, YAG, GYAG, and CASN, and the color rendering property (CRI) of light emitted from the light emitting device and the light flux (Lumen).
  • CRI color rendering property
  • the straight line located on the right side is located on the lower side when three types of phosphors are used: YAG, GYAG, and SCASN.
  • the straight line located on the upper side is located on the lower side when three types of phosphors are used, GYAG, SCASN, and CASN.
  • the straight lines indicate the simulation results for the case where three types of phosphors, YAG, SCASN, and CASN, are used, both of which show the color rendering properties (CRI) of light emitted from the light emitting device and the light flux (Lumen). ) Is a trade-off relationship.
  • the left straight line and the right straight line represent the color rendering properties and light flux of the light emitted from the light emitting device according to this embodiment including YAG and GYAG, but compared with the upper straight line and the lower straight line, It can be understood that the slope of the straight line is large. That is, although the relationship between the color rendering property (CRI) of the light emitted from the light emitting device and the light beam (Lumen) is a trade-off relationship, the light emitting device can suppress the reduction of the light beam accompanying the improvement in the color rendering property. I understand.
  • the light emitting device including YAG and GYAG is a light emitting device capable of achieving both high color rendering properties and conversion efficiency in addition to good binning characteristics.
  • a light-emitting device using four types of phosphors which is a light-emitting device according to a preferred embodiment of this embodiment, light emitted by the light-emitting device within the range surrounded by these four straight lines It is possible to arbitrarily set the relationship between the color rendering property (CRI) and the luminous flux (Lumen) of light. Therefore, in a preferred embodiment of this embodiment, the degree of freedom in selecting a phosphor for producing a light emitting device having binning characteristics and having both color rendering properties and conversion efficiency is improved.
  • CRI color rendering property
  • Luen luminous flux
  • FIG. 5 and Table 4 show simulation results when the phosphors represented by the general formula (m2) performed by the present inventors are used, and the color rendering properties of the light emitted from the light emitting device depending on the types of the phosphors. It shows how the luminous efficiency changes.
  • a chip with a peak wavelength of 453 nm was used as an excitation source, and four types of fluorescence of YAG, LuAG, SCASN, and CASN (each measured data such as an emission spectrum of a phosphor used in an experimental example described later) were used.
  • the wavelength conversion member was comprised using the body. Then, by adjusting the content ratio of each phosphor so that the emission color from the wavelength conversion member becomes 2700K, it was simulated how the relationship between the color rendering properties and the emission efficiency changes.
  • the straight line located on the left side shows a case where three types of phosphors YAG, LuAG, and CASN are used for simulation, and the color rendering properties (CRI) of light emitted from the light emitting device and the light flux (Lumen).
  • CRI color rendering properties
  • the straight line located on the right side is located on the lower side when three types of phosphors, YAG, LuAG, and SCASN are used.
  • the straight line located on the upper side is located on the lower side when three types of phosphors, LuAG, SCASN, and CASN, are used.
  • the straight lines indicate the simulation results for the case where three types of phosphors, YAG, SCASN and CASN, are used, both of which show the color rendering properties (CRI) of the light emitted from the light emitting device and the light flux (Lumen). ) Is a trade-off relationship.
  • the straight line on the left side and the straight line on the right side represent the color rendering properties and the luminous flux of the light emitted from the light emitting device according to the embodiment of the present invention including YAG and LuAG, but compared with the upper straight line and the lower straight line.
  • the slope of the straight line is large. That is, although the relationship between the color rendering property (CRI) of the light emitted from the light emitting device and the light beam (Lumen) is a trade-off relationship, the light emitting device can suppress the reduction of the light beam accompanying the improvement in the color rendering property. I understand.
  • the light-emitting device including YAG and LuAG is a light-emitting device capable of achieving both high color rendering properties and conversion efficiency in addition to good binning characteristics.
  • the light emitted from the light-emitting device is within the range surrounded by these four straight lines. It is possible to arbitrarily set the relationship between the color rendering properties (CRI) and the luminous flux (Lumen) of light. Therefore, in a preferred embodiment of the present invention, the degree of freedom in phosphor selection for producing a light emitting device having binning characteristics and having both color rendering properties and conversion efficiency is improved.
  • Table 5 shows the particle diameter and emission peak wavelength of the phosphor synthesized by the above method. Note that only GYAG1 is shown for the GYAG phosphor, and only LuAG1 is shown for the LuAG phosphor.
  • excitation spectra of the phosphor YAG and the phosphors GYAG1 to GYAG4 were measured at room temperature (25 ° C.) using a fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. More specifically, the emission peak at 540 nm was monitored to obtain an excitation spectrum in the wavelength range of 430 nm to 470 nm. Furthermore, the intensity change of the excitation spectrum was calculated when the excitation spectrum intensity at an excitation wavelength of 450 nm was 1.0 and the excitation wavelength was changed from 430 nm to 470 nm. The excitation intensity change curve for each phosphor is shown in FIG.
  • GYAG represented by the general formula (m3) of the present invention can provide a light-emitting device having excellent binning characteristics when the value of c is 1.2 or more and 2.6 or less. Further, the value of c is preferably 2.4 or less, more preferably 1.8 or less.
  • FIG. 7 shows a synthetic excitation spectrum intensity change obtained by calculating the excitation spectrum intensity at each wavelength of YAG and LuAG1 by a 50:50 weighted average.
  • the spectral intensity change rate in the range of 430 nm to 465 nm of each phosphor was determined and summarized in Table 7-1.
  • the rate of change in spectral intensity was calculated as the maximum-minimum value of the spectral intensity in the range of 430 nm to 465 nm, with the excitation spectral intensity at an excitation wavelength of 450 nm being 1.0.
  • YAG represented by the general formula (1) has an increased excitation wavelength and an increased emission intensity at the excitation wavelength from 430 nm to 465 nm.
  • the spectral intensity change rate is 15.4%.
  • LuAG1 and LuAG2 represented by the general formula (m2) have a peak in the vicinity of 450 nm and show a peak-shaped excitation spectrum intensity. Moreover, the rate of change in the intensity of each excitation spectrum is 10.2% and 8.6%.
  • the spectral intensity change rate of the synthetic excitation spectrum calculated by the 50:50 weighted average of YAG represented by the general formula (l) and LuAG1 represented by the general formula (m2) is 11.1%.
  • the rate of change of the synthetic excitation spectrum intensity can be adjusted to 12% or less.
  • a phosphor G having an excitation spectrum intensity change rate of 12% or less may be used.
  • the phosphor Y it is preferable to use the phosphor Y and the phosphor G whose excitation spectrum intensity change rates are both 12% or less.
  • Table 8 shows the spectrum of the synthetic excitation spectrum at each weight fraction of YAG represented by the general formula (l), GYAG1 represented by the general formula (m1), and LuAG1 represented by the general formula (m2).
  • the intensity change rate was shown.
  • the spectral intensity change rate was calculated as the maximum value-minimum value of the spectrum intensity in the range of 430 nm to 470 nm, with the excitation spectrum intensity at the excitation wavelength of 450 nm being 1.0.
  • the synthetic excitation spectrum intensity change rate can be adjusted to 15% or less.
  • a phosphor G having an excitation spectrum intensity change rate of 15% or less may be used.
  • the phosphor Y is contained, it is preferable to use the phosphor Y and the phosphor G whose excitation spectrum intensity change rates are both 15% or less.
  • the phosphor Y having the maximum value of the excitation spectrum intensity in the range of 430 nm to 470 nm is 450 nm or more and the phosphor G having the minimum value of the excitation spectrum intensity in the range of 430 nm to 470 nm is 450 nm or more. preferable.
  • each material was weighed at a weight ratio shown in Table 10 so that the total weight was 10 g, and a vacuum defoaming kneader V-mini300 manufactured by EME was used. Was used for defoaming and kneading at 1200 rpm for 3 minutes at room temperature to obtain a phosphor-containing silicone resin composition.
  • Resin B each material was weighed at a weight ratio shown in Table 10 so that the total weight was 50 g, and a lab plast mill 10C100 manufactured by Toyo Seiki Co., Ltd. and a mixer type (R60) were used. It was melt kneaded at 260 ° C. and 100 rpm for 5 minutes to obtain phosphor-containing polycarbonate resin compositions, respectively.
  • the composition of the phosphor GYAG1 was analyzed and as shown in Table 11.
  • the molar ratio was calculated from the analysis results obtained in Table 11.
  • a result is shown in Table 12 with the molar ratio at the time of preparation.
  • the phosphor-containing silicone resin compositions according to Experimental Examples 1 to 3 and 9 to 12 are cast so as to have a thickness of 62 mm and a thickness of 1 mm, and are molded by heating and curing at 150 ° C. for 5 minutes and subsequently at 200 ° C. for 20 minutes.
  • a test piece for optical properties was obtained, and the phosphor-containing polycarbonate resin compositions according to Experimental Examples 4 to 8 were vacuum-dried at 120 ° C. for 2 hours, and then heated at 260 ° C. using a hot press molding machine (for example, manufactured by Imoto Seisakusho). It is melt-pressed at 4 MPa for 2 minutes, and then cooled at 20 ° C.
  • the excitation spectrum intensity measurement at an emission wavelength of 540 nm was performed in the range of 430 nm to 470 nm using the Hitachi spectrofluorometer F-4500, and the excitation spectrum intensity change rate was calculated.
  • the obtained excitation spectrum intensities are shown in FIGS. 9-1 to 9-3 and Table 13.
  • Tables 14 to 16 show the excitation spectrum intensity change rates in the range of 435 nm to 465 nm, the range of 435 nm to 470 nm, and the range of 430 nm to 465 nm calculated from the spectrum in each experimental example.
  • the light-emitting device which can obtain white light was produced by irradiating the obtained disc test piece with the blue light light-emitted from LED chip (peak wavelength 450nm).
  • the emission spectrum was observed from the apparatus using a 20 inch integrating sphere manufactured by Sphere Optics and a spectroscope USB2000 manufactured by Ocean Optics, and chromaticity, luminous flux, and Ra were measured. Table 17 shows the measurement results.
  • the change in chromaticity ⁇ u′v ′ when the excitation light source was changed to a xenon spectral light source and the excitation wavelength was changed from 425 nm to 475 nm was measured.
  • the spectral light source used was Spectracorp, and the change in chromaticity was observed with a 20 inch integrating sphere (LMS-200) manufactured by Labsphere and a spectroscope manufactured by Carl Zeiss (Solid Lambda UV-Vis).
  • the light emitting devices according to the first to fifth embodiments of the first invention can achieve a high total luminous flux (light emission efficiency) while maintaining high color rendering properties. Further, from FIGS. 10-1 to 10-3 and FIGS. 11-1 to 11-2, it is understood that the light-emitting device of the present invention exhibits good binning characteristics.
  • Excitation spectrum intensity change rate of phosphor mixture As Experimental Examples 13 to 22, each phosphor was weighed and mixed so as to have a total amount of 1 g at the weight ratio described in the phosphor mixing examples 1 to 7 and 9 to 11. The obtained mixed powder (mixture consisting only of phosphor and not including transparent material) was measured for excitation spectrum intensity at 430 nm to 470 nm at emission wavelength 540 nm using Hitachi spectrofluorometer F-4500. The excitation spectrum intensity change rate was calculated. The obtained excitation spectrum intensities are shown in FIGS. 12-1 to 12-3 and Table 21.
  • Table 22 shows excitation spectrum intensity change rates in the range of 430 nm to 470 nm, the range of 435 nm to 470 nm, and the range of 435 nm to 465 nm calculated from the spectrum in each experimental example.
  • Second embodiment> The description of the example in the first embodiment described above is applied to the example in this embodiment.
  • phosphor> Regarding the synthesis of the phosphor in the present embodiment, ⁇ 1-2-1 in the first embodiment described above.
  • the description of synthesis of YAG phosphor, GLuAG phosphor, SCASN phosphor, CASN phosphor> is applied.
  • the particle diameter and emission peak wavelength of the phosphor are described in ⁇ 1-2-5.
  • the description of GYAG1, GLuAG, YAG, SCASN, CASN described in “Particle size and emission peak wavelength of phosphor” is applied.
  • ⁇ 3-3 Measurement of excitation spectrum intensity>
  • ⁇ 1-3-1 Measurement of excitation spectrum intensity 1>
  • ⁇ 1-3-3 The description of GYAG1 and YAG described in Measurement of excitation spectral intensity 3> applies.
  • wavelength conversion member and light emitting device> In this embodiment, ⁇ 1-4. In the first embodiment described above. The descriptions of phosphor mixing examples 3 to 11 and experimental examples 4 to 9 described in “Manufacturing of wavelength conversion member and light emitting device> are applied.
  • Luminescent characteristics In the present embodiment, ⁇ 1-5. The description of Experimental Examples 4 to 8 described in “Luminescent characteristics” is applied.
  • ⁇ 4-2 Synthesis of phosphor> Regarding the synthesis of the phosphor in the present embodiment, ⁇ 1-2-2 in the first embodiment described above. Synthesis of phosphor LuAG1>, ⁇ 1-2-3. Synthesis of phosphor LuAG2>, ⁇ 1-2-4. The description of synthesis of YAG phosphor, GLuAG phosphor, SCASN phosphor, CASN phosphor> is applied. The particle diameter and emission peak wavelength of the phosphor are described in ⁇ 1-2-5. The descriptions of LuAG1, GLuAG, YAG, SCASN, CASN described in “Particle size and emission peak wavelength of phosphor” are applied.
  • wavelength conversion member and light emitting device> In this embodiment, ⁇ 1-4. In the first embodiment described above. The description of phosphor mixing examples 1, 2, 8 to 10 and experimental examples 1 to 3 described in “Manufacturing of wavelength conversion member and light emitting device> is applied.
  • phosphor> Regarding the synthesis of the phosphor in the present embodiment, ⁇ 1-2-2 in the first embodiment described above.
  • the description of synthesis of YAG phosphor, GLuAG phosphor, SCASN phosphor, CASN phosphor> is applied.
  • the particle diameter and emission peak wavelength of the phosphor are described in ⁇ 1-2-5.
  • LuAG1, YAG, SCASN, CASN described in “Particle size and emission peak wavelength of phosphor” is applied.
  • wavelength conversion member and light emitting device> In this embodiment, ⁇ 1-4. In the first embodiment described above. The description of phosphor mixing examples 1, 2, 8, and 9 and experimental examples 1 to 3 described in “Production of wavelength conversion member and light-emitting device> is applied.
  • Synthesis of phosphor GYAG6 (hereinafter also referred to as “synthesis example 2”)> 23.71 g of Y 2 O 3 and 155.56 g of Al 2 O 3 so that the charged composition of each raw material of the phosphor becomes Y 2.91 Ce 0.09 Al 4.2 Ga 0.8 O 12.
  • a phosphor GYAG6 (average particle size 15 ⁇ m) was prepared in the same manner as in Synthesis Example 1 except that 54.47 g of Ga 2 O 3 , 11.25 g of CeO 2 and 27.6 g of BaF 2 as a flux were respectively weighed. Obtained.
  • Synthesis of phosphor GYAG7 (hereinafter also referred to as “Synthesis Example 3”)> 245.01 g of Y 2 O 3 and 156.43 g of Al 2 O 3 so that the charged composition of each raw material of the phosphor is Y 2.97 Ce 0.03 Al 4.2 Ga 0.8 O 12
  • a phosphor GYAG7 (average particle size 12 ⁇ m) was prepared in the same manner as in Synthesis Example 1 except that 54.78 g of Ga 2 O 3 , 3.77 g of CeO 2 and 27.6 g of BaF 2 as a flux were respectively weighed. Obtained.
  • Synthesis of phosphor GYAG8 (hereinafter also referred to as “synthesis example 4”)> 23.62 g of Y 2 O 3 , 146.58 g of Al 2 O 3 , and Ga 2 O so that the charged composition of each raw material of the phosphor is Y 2.94 Ce 0.06 Al 4 Ga 1 O 12.
  • Phosphor GYAG8 (average particle size 11 ⁇ m) was obtained in the same manner as in Synthesis Example 1, except that 67.37 g of Ce 3 , 7.42 g of CeO 2 and 27.6 g of BaF 2 as a flux were respectively weighed.
  • Synthesis of YAG phosphor, SCASN phosphor and CASN phosphor (among these, synthesis of YAG phosphor is also referred to as “synthesis example 5” below)>
  • the YAG phosphor is described in JP-A-2008-7751
  • the SCASN phosphor is described in JP-A-2006-008721.
  • the CASN phosphor was obtained by the manufacturing method.
  • the particle size and the weight median diameter d50 were measured by a laser diffraction particle size distribution analyzer LA-300 manufactured by Horiba. Specifically, it is a value obtained from a frequency-based particle size distribution curve measured by a laser diffraction / scattering method in which a phosphor is dispersed in an aqueous solution.
  • the phosphors shown in Synthesis Examples 1 to 4 have an excitation spectrum intensity change of 4.0% or less of the excitation light spectrum intensity at 450 nm in the wavelength range of 440 to 460 nm, and 440 to 460 nm. A stable emission spectrum is obtained upon excitation.
  • each material phosphor, additive, silicone resin
  • a vacuum defoaming kneader V-mini300 manufactured by EME Defoaming and kneading for 3 minutes at 1200 rpm gave a phosphor-containing silicone resin composition.
  • the obtained silicone resin composition was cast into a 20 mm ⁇ glass vial so as to have a thickness of 1 mm, and cured by heating at 150 ° C. for 5 minutes and then at 200 ° C. for 20 minutes.
  • a characteristic test piece (wavelength conversion member) was obtained.
  • a light-emitting device capable of obtaining white light was produced by irradiating the obtained test piece having a thickness of 1 mm and 20 mm ⁇ with blue light emitted from an LED chip (peak wavelength: 450 nm).
  • the emission spectrum was observed from the apparatus using a 20 inch integrating sphere manufactured by Sphere Optics and a spectroscope USB2000 manufactured by Ocean Optics, and chromaticity, luminous flux (lumen), and Ra were measured. The measurement results are shown in Table 25.
  • the excitation spectrum at 540 nm emission was measured using a spectrofluorometer F-4500 manufactured by Hitachi, and the excitation intensity at 450 nm was 1.0.
  • the relative excitation intensity at 430 nm to 470 nm was calculated.
  • the difference between the maximum value and the minimum value of the relative excitation spectrum intensity in the wavelength range of 430 to 470 nm is 0.25 or less
  • the difference between the maximum value and the minimum value of the relative excitation spectrum intensity in the wavelength range of 440 to 460 nm is 0.13 or less
  • a stable emission spectrum is obtained at 430 to 470 nm excitation, and particularly stable at 440 to 460 nm. Is obtained.
  • Chromaticity and lumen values are measured for excitation wavelengths of 445 nm, 448 nm, 450 nm, 452 nm, 454 nm, and 455 nm, respectively.
  • the average value (u ′ ave , v ′ ave ) is calculated and then averaged The distance from the value was calculated, and in the lumen value, the relative luminance was calculated when the lumen having an excitation wavelength of 455 nm was set to 1. These are shown in FIG. 13 and Table 27, respectively.
  • the light emitting device using the phosphor in the present invention has high luminance and good binning characteristics.
  • the difference between the maximum value and the minimum value of the relative excitation spectrum intensity in the wavelength range of 430 to 465 nm is 0.12 or less
  • the difference between the maximum value and the minimum value of the relative excitation spectrum intensity in the wavelength range of 440 to 460 nm is 0.05 or less
  • a stable emission spectrum is obtained at 430 to 465 nm excitation, and particularly stable emission spectrum at 440 to 460 nm. Is obtained.

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