JP2014130998A - Light-emitting device, wavelength conversion member, phosphor composition and mixed phosphor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-emitting device which inhibits a change in hue caused by excitation wavelength deviation and has good binning characteristics.SOLUTION: A light-emitting device comprises a blue semiconductor light-emitting element and a wavelength conversion member. The wavelength conversion member includes: phosphor Y which is represented as the following formula (Y1) and has a peak wavelength of an emission wavelength spectrum when excited at 450 nm is not less than 540 nm and not more than 570 nm: (Y,Ce,Tb,Lu)(Ga,Sc,Al)O(Y1)(x=3, 4.5≤y≤5.5, 10.8≤z≤13.4); and phosphor G which is represented as the following formula (G1) and has a peak wavelength of an emission wavelength spectrum when excited at 450 nm is not less than 520 nm and not more than 540 nm: (Y,Ce,Tb,Lu)(Ga,Sc,Al)O(G1)(x=3, 4.5≤y≤5.5, 10.8≤z≤13.4).

Description

  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.

  Light-emitting devices using semiconductor light-emitting elements are increasing in presence as energy-saving light-emitting devices. On the other hand, various problems have arisen as the development of light-emitting devices using semiconductor light-emitting elements progresses.

  For example, Patent Document 1 has found a problem that color unevenness occurs in the illumination light as the lighting time becomes longer. To cope with this problem, 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).

On the other hand, 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).
Patent Document 3 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).

  In addition, 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, the wavelength of the semiconductor light emitting element is reduced. 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).

JP 2005-228833 A Special table 2009-503831 Special table 2010-500444 gazette JP 2008-135725 A

Although LED binning has been pointed out in several documents, no specific proposal has been made for practical use. When the present inventors examined the combination of the phosphors according to the above documents, 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. Further, in 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. Further, when applied to a light emitting device, 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 The present invention relates to a wavelength conversion member.

  The present inventors have intensively studied 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 or a yellow phosphor is contained. First, it was found that a light-emitting device having sufficient binning characteristics can be provided by using a wavelength conversion member containing a specific green phosphor, and the present invention has been completed.

The present invention includes the following first to fourth inventions.
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 including a blue semiconductor light emitting element and a wavelength conversion member,
The wavelength conversion member 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)
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 _z (G1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

As a second embodiment,
The excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.25 or less.
However, 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.

As a third embodiment,
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.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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.

As a fourth embodiment,
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.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.
8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

In the third and fourth embodiments,
It is preferable that the intensity change rate of the excitation spectrum synthesized by the following calculation formula (Z) 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 excitation spectrum intensity change rate and the weight fraction of the phosphor G are similarly expressed.
Each excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the combined 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.

In the first to fourth embodiments,
In the light emitting device described above, 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, and 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.

In the first to fourth embodiments,
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.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

In the first to fourth embodiments,
In the light emitting device described above, 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

In the light emitting device according to the first to fifth embodiments,
The chromaticity change Δu′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 Δu′v ′ ≦ 0.004. preferable.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ _ave , v) of chromaticity from 445 nm to 455 nm.
' _ave ) represents the distance.

In the first to fifth embodiments,
When the emission wavelength of the blue semiconductor light emitting element is continuously changed from 435 nm to 470 nm, the chromaticity change Δu′v ′ of light emitted from the light emitting device satisfies Δu′v ′ ≦ 0.015. preferable.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ _ave , v) of chromaticity from 435 nm to 470 nm.
' _ave ) represents the distance.

In the first to fifth embodiments,
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 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.
A lighting device including these light emitting devices is also a preferred invention.

2nd invention of this invention is invention which concerns on a wavelength conversion member, The 1st embodiment 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)
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 wavelength conversion member comprising a transparent material.

As a second embodiment,
It is preferable that the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
However, 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.

As a third embodiment,
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.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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.

As a fourth embodiment,
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.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

In the third and fourth embodiments,
It is preferable that the intensity change rate of the excitation spectrum synthesized by the following calculation formula (Z) 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 excitation spectrum intensity change rate and the weight fraction of the phosphor G are similarly expressed.
Each excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the combined 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.

In the first to fourth embodiments,
In the wavelength conversion member described above, 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, 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.

In the first to fourth embodiments,
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.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

In the first to fourth embodiments,
In the wavelength conversion member described above, 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 second 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 wavelength conversion member comprising a transparent material,
The wavelength conversion member whose excitation spectrum intensity change rate in emission wavelength 540nm of this wavelength conversion member is 0.33 or less.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

In the wavelength conversion member according to the first to fifth embodiments,
It is preferable that the chromaticity change Δu′v ′ of light emitted from the wavelength conversion member satisfies Δu′v ′ ≦ 0.004 when the excitation wavelength is continuously changed from 445 nm to 455 nm.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ _ave , v) of chromaticity from 445 nm to 455 nm.
' _ave ) represents the distance.

In the first to fifth embodiments,
It is preferable that the chromaticity change Δu′v ′ of light emitted from the wavelength conversion member satisfies Δu′v ′ ≦ 0.015 when the excitation wavelength is continuously changed from 435 nm to 470 nm.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ _ave , v) of chromaticity from 435 nm to 470 nm.
' _ave ) represents the distance.

A third aspect of the present invention is an invention relating to a phosphor composition, 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)
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,
A phosphor composition comprising a transparent material.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (G1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

As a second embodiment,
When the phosphor 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 preferably 0.25 or less.
However, 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.

As a third embodiment,
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),
When the phosphor composition is formed into a wavelength conversion member, the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is preferably 0.23 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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.

As a fourth embodiment,
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),
When the phosphor composition is molded into a wavelength conversion member, the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member is preferably 0.33 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

In the first to fourth embodiments,
When the phosphor composition described above is formed into a wavelength conversion member by molding the phosphor composition, 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.

In the first to fourth embodiments,
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.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

In the first to fourth embodiments,
In the phosphor composition described above, 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

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)

As a second embodiment,
The rate of change in excitation spectrum intensity at an emission wavelength of 540 nm is preferably 0.40 or less.
However, 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

As a third embodiment,
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),
It is preferable that the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.30 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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

As a fourth embodiment,
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),
It is preferable that the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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

In the first to fourth embodiments,
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 Y has an excitation spectrum intensity at 430 nm in an excitation spectrum at an emission wavelength of 540 nm. Is preferably greater than the excitation spectral intensity at 470 nm.

In the first to fourth embodiments,
Furthermore, it is preferable to include 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.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)

In the first to fourth embodiments,
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 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

According to the first to fourth 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. In particular, by using the phosphor Y and the phosphor G in combination, 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. Compared to the case, 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.
Further, according to the fifth embodiment of the first invention, 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. In particular, in a high color temperature region of a color temperature of 4000 K or higher, 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.
In addition, according to 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.
Further, according to the third and fourth inventions of the present invention, there is provided 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.

It is an example in one Embodiment of 1st invention, and is a graph which shows the change of emitted light intensity when changing excitation wavelength from 430 nm to 470 nm about each fluorescent substance of YAG, GYAG, SCASN, and CASN. It is a cross-sectional schematic diagram of the light-emitting device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram of the light-emitting device which concerns on one Embodiment of this invention. It is the figure which plotted the simulation result showing the relationship between the color rendering property by the kind of fluorescent substance, and luminous efficiency. It is the figure which plotted the simulation result showing the relationship between the color rendering property by the kind of fluorescent substance, and luminous efficiency. It is a graph showing the relationship between the composition of the general formula of the phosphor represented by the general formula (m3) and the excitation emission spectrum. It is a graph showing the relationship between the composition of the general formula of the phosphor represented by the general formula (m5) and the excitation emission spectrum. It is a graph which shows the change of emitted light intensity when changing excitation wavelength from 430 nm to 465 nm about each fluorescent substance of YAG, LuAG1, LuAG2, SCASN, and CASN. Moreover, it is a graph which shows together the change of the synthetic | combination excitation spectrum intensity | strength which produced YAG and LuAG1 with the weighted average of 1: 1. It is a graph which shows the change of emitted light intensity when changing excitation wavelength from 430 nm to 470 nm about each fluorescent substance of GYAG1, LuAG1, GLuAG, and YAG. It is the graph showing the excitation spectral intensity change rate in the emission wavelength 540nm of the test piece produced in Experimental Examples 1-3. It is the graph showing the excitation spectrum intensity change rate in the emission wavelength of 540 nm of the test piece produced in Experimental Examples 4-8. It is the graph showing the excitation spectrum intensity change rate in the emission wavelength 540nm of the test piece produced in Experimental Examples 9-12. It is a graph showing the binning characteristic of the light-emitting device produced in Experimental Examples 1-3. It is the graph showing the binning characteristic of the light-emitting device produced in Experimental Examples 4-8. It is the graph showing the binning characteristic of the light-emitting device produced in Experimental Examples 9-12. It is a graph showing the binning characteristic of the light-emitting device produced in Experimental Examples 1-3 and 9-12. It is the graph showing the binning characteristic of the light-emitting device produced in Experimental Examples 4-8. It is the graph showing the excitation spectrum intensity change rate in the emission wavelength 540nm of the fluorescent substance mixture produced in Experimental example 13 and 14. FIG. It is the graph showing the excitation spectrum intensity | strength change rate in the emission wavelength 540nm of the fluorescent substance mixture produced in Experimental Examples 15-20. It is the graph showing the excitation spectrum intensity | strength change rate in luminescence wavelength 540nm of the fluorescent substance mixture produced in Experimental example 21 and 22.

Hereinafter, although this invention is demonstrated using an embodiment, this invention is not limited only to a specific embodiment.
Hereinafter, in the phosphor composition formulas in the present specification, each composition formula is delimited by a punctuation mark (,). In addition, 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 according to the first to fifth embodiments of the first invention 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. And 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. In addition, the wavelength conversion member may have a self-supporting shape due to the contained transparent material or the like. As yet another aspect, the phosphor may be mixed and applied to a resin or the like on a transparent substrate such as glass if necessary.

The wavelength conversion member used in the first embodiment of the first invention 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)
And phosphor G having a peak wavelength of an emission wavelength spectrum of 520 nm to 540 nm when excited at 450 nm, represented by the following general formula (G1).
(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 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.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (m1)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (m2)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)

The light emitting device according to the first embodiment of the first invention is a light emitting device having excellent binning characteristics that can withstand practical use by satisfying the above requirements. In a blue semiconductor light-emitting element serving as a light source of a light-emitting device, 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).
A case where a YAG phosphor that is a typical example of the phosphor Y and a GYAG phosphor that is a typical example of the phosphor G are used in combination will be described with reference to FIG.

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.
As can be understood from FIG. 1, 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.
On the other hand, 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.

In the light emitting device according to the first invention, as a second embodiment, it is preferable that 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 expressed 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. As a result, it was conceived that 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.
When 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. In this embodiment, 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.
Further, the excitation spectrum intensity change rate is preferably 0.03 or more, and more preferably 0.05 or more. When the excitation spectrum intensity change rate is 0.03 or less, the emission spectrum intensity is the same when the excitation wavelength is changed, but the luminance and chromaticity change substantially because the photopic sensitivity is different. There is.

As a third embodiment in the first invention,
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),
It is also preferable that an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.23 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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 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.
Further, when the phosphor is a YAG phosphor, the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties. Moreover, when 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.

As a fourth embodiment in the first invention,
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),
It is also preferable that an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.
Further, when the phosphor is a YAG phosphor, the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties. Moreover, when 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.

In the third and fourth embodiments of the first invention,
It is preferable that the intensity change rate of the excitation spectrum synthesized by the following calculation formula (Z) 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 excitation spectrum intensity change rate and the weight fraction of the phosphor G are similarly expressed.
Each excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the combined 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.

  As described above, 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 excitation spectrum intensity in the vicinity of 450 nm light, which is the wavelength of, was examined in detail. By making 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.

In order to set the excitation spectrum intensity change rate at the emission wavelength of 540 nm of the wavelength conversion member to 0.23 or 0.33 or less in the third and fourth embodiments, respectively, it is represented by the general formula (Z). The synthetic excitation spectrum intensity change rate to be generated may be 0.15 or less in any of the embodiments, 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.

Further, the synthetic excitation spectrum intensity change rate represented by the formula (Z) is more preferably 0.14 or less, and still more preferably 0.12, in any of the embodiments.
The excitation spectrum intensity change rate is preferably 0.02 or more, and more preferably 0.04 or more.

In the first to fourth embodiments of the first invention,
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.
By satisfying this condition, when the excitation wavelength is changed from 430 nm to 470 nm, the emission spectrum other than the excitation wavelength changes from an emission color with a high contribution of phosphor G to an emission color with a high contribution of phosphor Y. Thus, the substantial emission color including the excitation wavelength can always be constant without depending on the excitation wavelength.

Furthermore, in the first to fourth embodiments of the first invention,
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)
As the blue-green phosphor whose peak wavelength of the emission wavelength spectrum when excited at 450 nm is 500 nm or more and 520 nm or less, for example, 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).
_{Lu f Ce g Ga h Al i} O j ··· (B2)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 4.0, 10.8 ≦ j ≦ 13.4)
By including the blue-green phosphor, 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 excitation wavelength change, and better binning characteristics can be achieved.

In the first to fourth embodiments of the first invention,
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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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. By setting it to the above value or less, a good binning effect is exhibited in a range of approximately 430 nm to 465 nm. From a practical point of view, when the emission wavelength of the blue semiconductor light emitting element is continuously changed from 445 nm to 455 nm, the chromaticity change Δu′v ′ of light emitted from the light emitting device is Δu′v ′ ≦ 0. It is preferable to satisfy .004. More preferably, Δu′v ′ ≦ 0.0035 is satisfied.
However, Δu′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. .
Further, the chromaticity change Δu′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 Δu′v ′ ≦ 0.015. Is preferred. Moreover, it is more preferable to satisfy Δu′v ′ ≦ 0.012.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ _ave ) of chromaticity from 435 nm to 470 nm.
, V ′ _ave ).

  In a blue semiconductor light-emitting element serving as a light source of a light-emitting device, 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. In the light emitting device according to the first to fifth embodiments of the first invention, the chromaticity of the emitted light with respect to the variation in the emission peak wavelength of the blue semiconductor light emitting element as the light source by satisfying the above requirements. A light-emitting device having a small change and excellent so-called binning characteristics is preferable.

Chromaticity (u ′ _i , v ′ _i ) of light emitted from the light emitting device at the arbitrary wavelength inm, and an average value (u ′ _ave , v ′ _ave ) of light emitted from the light emitting device at a wavelength in a specific region Is calculated based on the CIE 1976UCS chromaticity diagram. Specifically, 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. Then, the calculated chromaticity (u ′ _i , v ′
_i ) is plotted on the u ′ v ′ chromaticity diagram, and the distance from the average value (u ′ _ave , v ′ _ave ) is obtained by the following mathematical formula, and is defined as the chromaticity change Δu′v ′.

In the light emitting device according to the first to fifth embodiments of the first invention, 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 ) is measured, and an 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 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 μm or more, more preferably 1 μm 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. Here, 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%. As a measuring method, for example, 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. After the dispersion, 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 particle size distribution analyzer (Horiba LA-300). The method of measuring in a diameter range 0.1 micrometer-600 micrometers is mentioned. In the above method, when the phosphor particles are aggregated, a dispersing agent may be used. For example, 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.

As an index indicating the degree of particle size distribution, there 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. In the present invention, D _v / D _n is 1.0.
Preferably, it is 1.2 or more, more preferably 1.4 or more. On the other hand, 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.

  Further, as 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. Of these, silane coupling materials (monoalkyltrisilanol, dialkyldisianol, trialkylsilanol, monoalkyltrialkoxysilane, dialkyldialkoxysilane, trialkylalkoxysilane), siloxane having a substituent, silicone, and the like are preferable. By using these third components to surface-treat and coat the phosphor, the affinity to a wavelength conversion member such as a resin, dispersibility, thermal stability, and fluorescence coloring property tend to be improved. The surface treatment and the coating amount are usually 0.01 to 10 parts by weight per 100 parts by weight of the phosphor, and if 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.

  In the first to fifth embodiments of the first invention, the content of the phosphor in the wavelength conversion member depends on the type of the light diffusing material and the resin described later. For example, when 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 with respect to 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.

  For example, when the resin 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.

In the first to fifth embodiments of the first invention, the wavelength conversion member preferably further includes a red phosphor (also referred to as a first red phosphor). By including the first red phosphor, it is possible to improve the color rendering properties of the light emitted from the light emitting device, and it is easy to adjust the light emitting device at a relatively low color temperature.
As the first red phosphor, it is preferable that 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. By using such a red phosphor, it is possible to further improve the color rendering property while making the binning characteristics of the light emitting device sufficient. The lower limit is not particularly limited and is 0% or more.
As red phosphors satisfying such requirements, (Sr, Ca) AlSiN ₃ : Eu, C
a _1-x Al _1-x Si _{1 + x} N _3-x O _x : Eu, 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 ≦ y <0.2) and the like are mentioned, and (Sr, Ca) AlSiN ₃ : Eu or Ca _1-x Al _1-x Si _{1 + x} N _3-x O _x : Eu 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. Examples of red phosphors satisfying such requirements include (Sr, Ca) AlSiN ₃ : Eu, Ca _1−x Al _1−x Si _{1 + x} N _3−x O _x : Eu, 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+, etc. (Sr, Ca
) AlSiN ₃ : Eu or Ca _1−x Al _1−x Si _{1 + x} N _3−x O _x : Eu.
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.

In the first to fifth embodiments of the first invention, 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.
By further including the second red phosphor in addition to the first red phosphor, the phosphor X and the phosphor Y are combined to include at least four types of phosphors. As described above, 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.

As the second red phosphor, it is preferable that 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. Such phosphors include CaAlSiN ₃
: Eu phosphor, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn ⁴⁺ phosphor and the like, and a CaAlSiN ₃ : Eu phosphor is preferable.
When the second red phosphor is contained, 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.
In addition, when the second red phosphor is included, when mixed with the first red phosphor,
When the excitation light wavelength changes from 445 nm to 455 nm, the intensity change of the excitation spectrum of the red phosphor mixture is preferably 5.0% or less, and preferably 3.0% or less of the excitation spectrum by the 455 nm excitation light. It is more preferable that it is 1.0% or less.

  In the first to fifth embodiments of the first invention, other known phosphors can be added to the wavelength conversion member as long as the effects of the present invention are not impaired. Included in the range.

  The wavelength conversion member according to the first to fifth embodiments in 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. In addition, 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 below shows the refractive indexes of resins generally used as transparent materials. In addition, 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.

As the transparent material, various thermoplastic resins, thermosetting resins, photo-curing resins, etc., glass, etc. can be used depending on the application, but polycarbonate resin and silicone resin are transparent, heat-resistant. In view of excellent mechanical properties and flame retardancy, it can be preferably used, polycarbonate resin is more preferable from the viewpoint of versatility, and silicone resin is preferable from the viewpoint of heat resistance.
Hereinafter, the polycarbonate resin will be described in detail.

The polycarbonate resin used in the first to fifth embodiments in the first invention is a polymer having a basic structure having a carbonic acid bond represented by the following general chemical formula (1).

In the 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 carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, 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. Further, 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. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Examples of aromatic dihydroxy compounds among monomers used as raw materials for aromatic polycarbonate resins include dihydroxy compounds such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene, and the like. Benzenes; dihydroxybiphenyls 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'-di Droxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) benzene, 1, Dihydroxydiaryl ethers such as 3-bis (4-hydroxyphenoxy) benzene; 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), 1,1-bis (4-hydroxyphenyl) propane, 2 , 2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4 -Hydroxyphenyl) propane, 1,1-bis (3-tert-butyl) 4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2- (4- Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-hydroxy Phenyl) -2-propyl] benzene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) (4-propenylphenyl) ) Methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4- Loxyphenyl) naphthylmethane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-naphthylethane, 1-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1 -Bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 1-bis (4-hydroxyphenyl) octane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4 -Hydroxyphenyl) hexane, 2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydro) Bis (hydroxyaryl) alkanes such as 1-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) decane; Bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 4-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane 1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy- 3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl)- 3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane, 1,1-bis Bis (hydroxyaryl) cycloalkanes such as (4-hydroxyphenyl) -4-phenylcyclohexane; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) Bisphenols containing cardo structure such as fluorene; 4,4'-dihydroxydiphenylsulfur Dihydroxy diaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Dihydroxydiaryl sulfoxides; dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone;

  Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.

  In addition, 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 the monomer that is a raw material for the aliphatic polycarbonate resin 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-diol; 2,2′-oxy Glycols such as sidiethanol (ie, ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol, spiroglycol; 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1 , 4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxy Ethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4-bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2 -Hydroxyethyl) Aralkyl diols such as ether; 1,2-epoxyethane (ie, ethylene oxide), 1,2-epoxypropane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4 -Cyclic ethers such as epoxycyclohexane, 1-methyl-1,2-epoxycyclohexane, 2,3-epoxynorbornane, 1,3-epoxypropane and the like may be used, and these may be used alone or in combination of two or more May be used in any combination and ratio.

  Among the monomers used as the raw material for the aromatic polycarbonate resin, examples of the carbonate precursor include carbonyl halide and carbonate ester. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of the carbonyl halide include phosgene, haloformates such as a bischloroformate of a dihydroxy compound, and a monochloroformate of a dihydroxy compound.

  Specific examples of the carbonate ester 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. Hereinafter, 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. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. . In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution 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. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in aqueous alkali solution, Usually, in order to control pH in the aqueous alkali solution of reaction to 10-12, it is used at 5 to 10 weight%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and 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. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst 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 of formula; 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.

  Examples of the molecular weight modifier 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. Specific examples of such 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, 2-methyl-6-hydroxyphenylacetic acid, and the like. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight modifier is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

  In the reaction, 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. For example, when phosgene is used as the carbonate precursor, 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. In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

(Melted ester exchange method)
In the 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. On the other hand, 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. In addition, 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.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence 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. In the transesterification reaction, 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. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

  When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above. Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, 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.

  In the melt transesterification method, 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. As a specific operation, 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. When performing by a batch type, 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. However, considering the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 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. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to 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 viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated by the following formula (1) by measuring the specific viscosity [η _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 measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  A polycarbonate resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a 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. Further, for example, for the purpose of further improving flame retardancy and impact resistance, 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 A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; Copolymers with oligomers or polymers having an olefin-based structure; for the purpose of improving chemical resistance, they may be configured as copolymers mainly composed of polycarbonate resins, such as copolymers with polyester resin oligomers or polymers. . When used in combination with other thermoplastic resins, 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.

  Further, in order to improve the appearance of the molded product and improve the fluidity, 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. Furthermore, the polycarbonate ligomer contained is preferably 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).

  Further, 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). Examples of the 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. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  However, the regenerated 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 a range not impairing the characteristics of the present invention. For example, 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.

  Here, it illustrates about the preferable additive mix | blended with polycarbonate resin.

  Examples of the heat stabilizer 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.

  Among them, 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.

As antioxidant, a hindered phenolic antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  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. When 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.

  Examples of the release agent 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, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable 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 preferable. Specific examples of such 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.

As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of 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, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic or alicyclic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable.

  Specific examples of such 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.

  Specific examples of 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 tetrastearate and the like.

  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 α-olefin oligomer having 3 to 12 carbon atoms. . Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.

  Among these, 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.

  Examples of the polysiloxane silicone oil 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. When 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.

Examples of the flame retardant 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 fluororesin-based 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.
Examples of 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.

Specific examples of the aromatic phosphate ester flame retardant 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) and bisphenol A bis (diphenyl phosphate). Content of a flame retardant is 0.01-30 weight part normally with respect to 100 weight part of resin.
As the organic acid metal salt flame retardant, 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.
As 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.

  Examples of ultraviolet absorbers 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, and hindered amine compounds. 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.

Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-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 (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl)-
6- (2N-benzotriazol-2-yl) phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.

Specific examples of such 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. "UV5411", "LA-32" manufactured by Adeka Company,
“LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinubin P”, “Tinubin 234”, “Tinubin 326”, “Tinubin 327” manufactured by Ciba Specialty Chemicals , “Tinuvin 328” 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.

Next, the silicone resin will be described in detail.
The silicone resin used in the first to fifth embodiments of the first invention is not particularly limited, but the smaller the absorption in visible light, the smaller the loss of light, which is preferable. In addition, a liquid silicone resin or the like is preferable in terms of mixing with a phosphor and processability to a wavelength conversion member. Especially in 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. Examples thereof include methylhydrosiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, and the like. As 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.

Furthermore, 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,
Examples of commercially available products include Aerosil (registered trademark) of Nippon Aerosil Co., Ltd., WACKER HDK (registered trademark) of Asahi Kasei Wacker Silicone Co., Ltd., and the like. Giving thixotropy is effective in preventing the composition of the raw material composition from becoming non-uniform due to the precipitation of the phosphor.
In particular, when hydrophobic fumed silica whose surface is modified with a trimethylsilyl group, a dimethylsilyl group, a dimethylsilicone chain, or the like is used, thixotropic properties can be imparted to the raw material composition without causing excessive thickening. In other words, a raw material composition having both high fluidity suitable for injection molding and an anti-settling effect of the phosphor can be obtained.
Although there is no restriction | limiting in particular in the addition amount of 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.
In addition, as necessary, 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 fifth embodiments in the first invention may contain a diffusing material. By containing the diffusing material, it is possible to cause the wavelength conversion member to exhibit light diffusibility.
When it contains a diffusing material, it is preferable to contain an inorganic light diffusing material, an organic light diffusing material or bubbles.

Specific examples of 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, Examples of 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.

  Examples of the organic light diffusing material include materials such as a styrene (co) polymer, an acrylic (co) polymer, a siloxane (co) polymer, and a polyamide (co) polymer. Some or all of these molecules of the organic diffusing material may or may not be cross-linked. Here, “(co) polymer” means both “polymer” and “copolymer”.

  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. Further, the average particle diameter is preferably 1 μm or more, and preferably 30 μm or less. The average particle size is a particle size measured with an integrated weight percentage, a particle size distribution meter or the like.

Further, as the diffusing material, the Mohs hardness is preferably less than 8, and more preferably less than 7. By using a diffusion material having such hardness, discoloration of the molded body can be suppressed, and impurities can be prevented from being mixed without damaging the container.
Moreover, as a diffusion material, it is preferable that ratio L / D of the major axis L and the minor axis D is 200 or less. By using a diffusing material in such a range, discoloration of the molded body can be suppressed, and impurities are not mixed without damaging the container. L / D is more preferably 50 or less.
Further, 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 μm or less, preferably 0.1 to 30 μm, more preferably 0.1 to 15 μm, and still more preferably 1 to 5 μm.

  Among the materials described above, in order to increase the light diffusion effect with a small amount, it is preferable to select a material having a large difference between the refractive index of the transparent material and the refractive index of the selected diffusing material. In order not to greatly reduce the luminous efficiency, it is preferable to select a material having high transparency.

  For example, when the transparent material is a polycarbonate resin, 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.

  As the 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. . As the siloxane-based (co) polymer, polyorganosilsesquioxane particles are more preferable, and polymethylsilsesquioxane particles are more preferable.

  In the present invention, 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 μm or less, preferably 30 μm or less, more preferably 10 μm or less, and usually 0.01 μm or more, preferably 0.1 μm 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. May become difficult, and it may be difficult to exhibit sufficient light diffusibility required in the present invention. As a result, it may become difficult to stably control the wavelength conversion efficiency within a preferable range. Here, 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.

In addition, the particle size distribution of the diffusing material may be a monodispersed system or a polydispersed 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).

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. In the present invention, D _v / D _n is preferably 1.0 or more. On the other hand, 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 singly or in combination of two or more kinds having different materials and dimensions. When two or more types are used in combination, 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. For example, 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 diffusion material is determined by the immersion method of YOSHIYAMA et al.
Vol.9, No.1 Spring pp.44-50 (1994)). The measurement temperature is 20 ° C., and the measurement wavelength is 450 nm.

  Table 2 below lists the refractive indices of materials commonly used as diffusing materials. In addition, 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. For example, when 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. On the other hand, 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.

2nd invention of this invention is invention which concerns on a wavelength conversion member, The 1st embodiment is the following,
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)
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 wavelength conversion member including a transparent material.
The wavelength conversion member according to the first to fifth embodiments in the second invention is a member that can absorb part or all of the excitation light and convert it to another wavelength. The description of the first to fifth embodiments in the first invention is applied to the configuration of the wavelength conversion member.

  The manufacturing method of a wavelength conversion member is not specifically limited, What is necessary is just to use a well-known method. For example, a general manufacturing method when the transparent material is a polycarbonate resin is as follows.

  A phosphor and other components such as a diffusing material to be blended as necessary are added to the polycarbonate resin and mixed with various mixers such as a tumbler mixer and a 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 case where the transparent material is a polycarbonate resin and the case where a diffusing material other than air bubbles is contained are illustrated in more detail and preferable conditions.

  A polycarbonate resin, a phosphor, a diffusing material, and other additives are mixed with a tumbler mixer, and then melt-kneaded using a single screw or twin screw extruder. As a melt-kneading condition, 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. In addition, when the phosphor is hard, it is preferable to use 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.

  What is necessary is just to select a screw rotation speed and discharge amount suitably in view of the production speed, the load to an extruder, and the state of a resin pellet. 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. When 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. .

  In addition, the said polycarbonate resin composition pellet is an example of the fluorescent substance composition which is 3rd invention of this invention.

The third invention of the present invention is an invention relating to a phosphor composition, and the first embodiment in the third invention 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)
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)
And a transparent material.

  The phosphor composition is not limited to a pellet, but a pellet is preferable from the viewpoint of flowability and ease of handling. In the method for molding the phosphor composition according to the first to fifth embodiments in the third invention into a wavelength conversion member, the explanations of the first to fifth embodiments in the second invention are applied, respectively. Moreover, the description of the 1st thru | or 5th embodiment in 1st invention is applied about the structure of a fluorescent substance composition, respectively.

The fourth invention of the present invention is an invention related to a phosphor mixture, and 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 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)

As a second embodiment,
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 rate of change in excitation spectrum intensity 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 the 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. .

As a third embodiment,
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),
It is also preferable that the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.30 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
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 435 nm to 470 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 excitation spectrum intensity change rate can be measured in the same manner as described above. More specifically, an emission peak at 540 nm is monitored to obtain an excitation spectrum in the wavelength range of 435 nm to 470 nm, and 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.

  Further, when the phosphor is a YAG phosphor, the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties. Moreover, when 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.

As a fourth embodiment,
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),
It is also preferable that the excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
The excitation spectrum intensity change rate of the phosphor mixture is from 435 nm when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0 when the excitation spectrum intensity of the wavelength conversion member at 450 nm is 1.0. It is represented by the difference between the maximum value and the minimum value of the excitation spectrum intensity in the range of 465 nm. 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 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.

  Further, when the phosphor is a YAG phosphor, the half width is preferably 100 nm or more and 130 nm or less from the viewpoint of color rendering properties. Moreover, when 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 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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 rate of change in excitation spectrum intensity 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 fifth embodiments in the first invention is applied to other configurations of the phosphor mixture according to the first to fifth embodiments in the fourth invention. The description of the first to fifth embodiments of the second invention is applied to the method of kneading and molding the phosphor mixture with a silicone resin or polycarbonate resin to obtain a wavelength conversion member. Specifically, the method described in Examples can be used.

  Hereinafter, the structure of the light emitting device according to the first to fifth embodiments of the first invention will be described with reference to the drawings.

FIG. 2 is a schematic diagram illustrating an example of a light emitting device including a wavelength conversion member according to the first to fifth 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.
Instead of the blue semiconductor light emitting element 1, a purple semiconductor light emitting element can also be used. 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. In FIG. 2, 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.
For example, in FIG. 3, 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. As such a wiring board, alumina ceramic, resin, glass epoxy, composite resin containing filler in resin, or the like can be used. Further, as the reflection plate placed on the chip mounting surface 2a of the wiring board 2, a resin containing a white pigment such as alumina powder, silica powder, magnesium oxide, titanium oxide, zirconium oxide, zinc oxide, 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 a part of 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. Examples of 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 preferably contains a small amount of a diffusing material together with the phosphor. Examples of 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 μm or more, more preferably 100 μm or more, and particularly preferably 1.0 mm or more. On the other hand, between the wavelength conversion member 3 and the blue semiconductor light emitting element 1 If the distance is too large, the light emitting area of the wavelength conversion member is enlarged and the amount of phosphor used is increased. Therefore, 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 device 10 is preferably provided in a general lighting device and used as a general lighting device that emits white light. When applied to such a use, the light emitting device 10 is configured such that the light emitted from the light emitting device has a deviation duv from the light-color black body radiation locus of −0.0200 to 0.0200, and the color temperature. Is preferably 1800K or more and 7000K or less, and more preferably 5000K or less.
In particular, it exhibits excellent binning characteristics in a light emitting device that emits a warm white color having a color temperature of 2500 K or more and 3500 K or less.
The light emitting devices according to the first to fifth embodiments of the first invention emit light having high color rendering properties. In the light emitting devices according to the first to fifth embodiments of the first invention, 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. When applied to such a use, the light emitting device 10 is configured such that the light emitted from the light emitting device has a deviation duv from the light-color black body radiation locus of −0.0200 to 0.0200, and the color temperature. Is preferably 5000K or more and 20000K or less, and more preferably 15000K or less.

  Hereinafter, although the present invention will be described in more detail with reference to examples and simulations, it is needless to say that the present invention is not limited to the following embodiments.

<1. First Embodiment>
<1-1-1. Simulation of color rendering and luminous efficiency 1>
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.
In the simulation, 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.

In FIG. 4, a straight line located on the left side shows a case where simulation is performed using three types of phosphors, YAG, GYAG, and CASN. This indicates that this relationship is a trade-off relationship. 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.

On the other hand, 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.
Thus, it can be understood that the light emitting device according to this embodiment 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.
In addition, in the case of 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.

<1-1-2. Simulation of color rendering and luminous efficiency 2>
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.
In the simulation, 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.

  In FIG. 5, 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). This indicates that this relationship is a trade-off relationship. 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.

On the other hand, 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 the embodiment of the present invention including YAG and LuAG, but compared with the upper straight line and the lower straight line. Thus, 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.
Thus, it can be understood that the light-emitting device according to the embodiment of the present invention 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.
In addition, in the case of a light-emitting device using four types of phosphors, which is a light-emitting device according to a preferred embodiment of the present invention, 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.

<1-2. Synthesis of phosphor>
<1-2-1. Synthesis of phosphors GYAG1-4>
Next, among the phosphors represented by the general formula (m1), Y _a Ce _b Ga _c Al _d O _e (m3
In order to measure how the excitation spectrum is changed by changing the value of c, the five types of phosphors (YAG, GYAG1, GYAG2 shown in Table 6-1 described later) are measured. , GYAG3, GYAG4). Note that a = 2.94, b = 0.06, c + d = 5, and e = 12. The synthesis method followed the method of Huh et al. (Bull. Korean Chem. Soc. 2002, Vol. 23, No. 1, p.1435-1438).

<1-2-2. Synthesis of phosphor LuAG1>
In order that the charged composition of each raw material of the phosphor is Lu _2.91 Ce _0.09 Al _5.0 O ₁₂ , 409.57 g of Lu ₂ O ₃ , 180.33 g of Al ₂ O ₃ , 10.96 g of CeO ₂ and flux Each 27.6 g of BaF ₂ was weighed and sufficiently stirred and mixed, and then closely packed in an alumina crucible. This was placed in a resistance heating type electric furnace equipped with a temperature controller, heated to 1500 ° C. in a hydrogen-containing nitrogen atmosphere, allowed to cool to room temperature, and subjected to sieving treatment and hydrochloric acid washing treatment to obtain the phosphor LuAG1 (average particle size of 12 μm). )

<1-2-3. Synthesis of phosphor LuAG2>
In order that the charging composition of each raw material of the phosphor is Lu _2.85 Ce _0.15 Al _5.0 O ₁₂ , 401.12 g of Lu ₂ O ₃ , 180.33 g of Al ₂ O ₃ , 18.27 g of CeO ₂ and flux Each 27.6 g of BaF ₂ was weighed and sufficiently stirred and mixed, and then closely packed in an alumina crucible. This was placed in a resistance heating type electric furnace equipped with a temperature controller, heated to 1500 ° C. in a hydrogen-containing nitrogen atmosphere, allowed to cool to room temperature, and subjected to sieving and hydrochloric acid washing treatment to obtain the phosphor LuAG2 (average particle size 9 μm). )

<1-2-4. Synthesis of YAG phosphor, GLuAG phosphor, SCASN phosphor, CASN phosphor>
In the manufacturing method described in JP-A-2006-265542, the YAG phosphor and the GLuAG phosphor are converted into the manufacturing method described in JP-A-2008-7751, and the SCASN phosphor is converted into JP-A-2006-008721. CASN phosphors were obtained by the described process.

<1-2-5. Phosphor particle size and emission peak wavelength>
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.

<1-3-1. Measurement of excitation spectrum intensity 1>
The peak wavelength and chromaticity coordinates of the emission spectrum were measured for five types of phosphors, YAG phosphors and GYAG1-4 phosphors synthesized as described above. The results are shown in Table 6-1.

  Next, with respect to the phosphor YAG and the phosphors GYAG1 to GYAG4, excitation spectra were measured at room temperature (25 ° C.) using a fluorescence spectrophotometer F-4500 manufactured by Hitachi. 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. An excitation intensity change curve in each phosphor is shown in FIG.

As shown in FIG. 6A, for the GYAG phosphor represented by the general formula (m3), when the value of c is small as in the case of c = 1.0, the excitation wavelength is increased. There is almost no decrease in the normalized excitation spectrum that accompanies it, and it cannot cope with the increase in the normalized excitation spectrum of the YAG phosphor represented by the general formula (l). On the other hand, in the case of c = 1.6, the case of 2, the case of 2.5 corresponds to an increase in the normalized excitation spectrum of the YAG phosphor represented by the general formula (l).
Therefore, 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.

Next, of the phosphor represented by the general formula _{(m1), Y f (Ce} , Tb, Lu) g Ga h Sc i Al j O k ··· value of i for the phosphor represented by (m5) In order to measure how the excitation spectrum changes, the five types of phosphors shown in Table 6-2 below (SC-1, SC-2, SC-3, SC-4, SC-5) was synthesized. It is assumed that f = 2.88, g = 0.12, h = 0, k = 12, and the composition formula Y _2.88 Ce _0.09 Tb _0.03 Sc
A phosphor represented by _i Al _j O ₁₂ was synthesized according to the method of Huh et al. using Sc ₂ O ₃ as a raw material.
With respect to the five types of phosphors synthesized as described above, the peak wavelength and chromaticity coordinates of the emission spectrum were measured (Table 6-2). In addition, the normalized excitation spectrum of the phosphor when the excitation light was changed from 440 nm to 460 nm was measured and calculated. The relative intensity was determined with the intensity of the normalized excitation spectrum when excited by 450 nm excitation light of each phosphor being 1. The results are shown in FIG.

<1-3-2. Measurement of excitation spectrum intensity 2>
Next, with respect to the phosphors YAG and LuAG1-2, the excitation spectrum intensity change was calculated in the same manner as described above except that the wavelength range was changed from 430 nm to 465 nm. An excitation intensity change curve in each phosphor is shown in FIG. Furthermore, 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.
Here, the spectral intensity change rate in the range of 430 nm to 465 nm of each phosphor was obtained and summarized in Table 7-1. The rate of change in spectral intensity was calculated as the maximum value-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.

As can be understood from FIG. 7 and Table 7-1, YAG represented by the general formula (1) increases at the excitation wavelength from 430 nm to 465 nm and the emission intensity increases. The spectral intensity change rate is 15.4%.
On the other hand, 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%.
Furthermore, 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%.
Thus, by containing the green phosphor represented by the general formula (X), or by using the yellow phosphor and the green phosphor represented by the general formula (X) together in a desired ratio, The rate of change of the synthetic excitation spectrum intensity can be adjusted to 12% or less.

In order to adjust the synthetic excitation spectrum intensity change rate to 12% or less, for example, a phosphor G having an excitation spectrum intensity change rate of 12% or less may be used.
Further, when 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 12% or less. Or a phosphor Y having a maximum excitation spectrum intensity in the range of 430 nm to 465 nm and 450 nm or more, and a phosphor G having a minimum excitation spectrum intensity in the range of 430 nm to 465 nm of 450 nm or more. preferable.

<1-3-3. Measurement of excitation spectrum intensity 3>
Next, with respect to the phosphors YAG, GYAG1 and LuAG1, the intensity change of the excitation spectrum was calculated in the same manner as described above except that the wavelength range was changed from 430 nm to 470 nm. The excitation intensity change curve in each phosphor is shown in FIG.
Here, the spectrum intensity change rate in the range of 430 nm to 470 nm of each phosphor was determined and summarized in Table 7-2. 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, assuming that the excitation spectrum intensity at an excitation wavelength of 450 nm was 1.0.

Further, 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.
Here, the spectral intensity change rate was calculated as the maximum value-minimum value of the spectral intensity in the range of 430 nm to 470 nm, with the excitation spectral intensity at the excitation wavelength of 450 nm being 1.0.

Thus, by containing the GYAG phosphor represented by the general formula (m1), or by combining the phosphor Y represented by the general formula (l) and the phosphor GYAG at a desired ratio. The synthetic excitation spectrum intensity change rate can be adjusted to 15% or less.
In order to adjust the synthetic excitation spectrum intensity change rate to 15% or less, for example, a phosphor G having an excitation spectrum intensity change rate of 15% or less may be used.
Furthermore, when 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. Or, 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.

<1-4. Production of wavelength conversion member and light emitting device>
The phosphors were weighed and mixed so as to have a total amount of 10 g at the weight ratios described in the phosphor mixture examples 1 to 11 shown in Table 9.

For Experimental Examples 1 to 3 and 9 to 12 using Resin A, each material was weighed so as to have a total weight of 10 g at a weight ratio shown in Table 10, 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.
For Experimental Examples 4 to 8 using Resin B, each material was weighed so as to have a total weight of 50 g at a weight ratio shown in Table 10, 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 analysis of the phosphor GYAG1 was 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.

Next, 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 then molded by heating and curing at 150 ° C. for 5 minutes and then at 200 ° C. for 20 minutes. Then, after obtaining a test piece for optical properties, vacuum-drying the phosphor-containing polycarbonate resin compositions according to Experimental Examples 4 to 8 at 120 ° C. for 2 hours, using a hot press molding machine (for example, manufactured by Imoto Seisakusho Co., Ltd.), It is melt-pressed at 4 MPa for 2 minutes, and then cooled at 20 ° C. and 1 MPa for 5 minutes using a water-cooled press (for example, manufactured by Imoto Seisakusho) to produce a sheet having a thickness of 1.2 mm. A test piece was punched out from the obtained sheet in a disk shape of 15 mmφ.

  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 for the obtained thickness disk specimen. The obtained excitation spectrum intensities are shown in FIGS. Tables 14 to 16 show the excitation spectrum intensity change rate 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.

<1-5. Luminescent characteristics>
Furthermore, 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.

<1-6. Measurement of Δu'v '>
Next, regarding the light emitting devices manufactured in Experimental Examples 1 to 12, the change in chromaticity Δu′v ′ when the excitation light source is changed to a xenon spectral light source and the excitation wavelength is changed from 445 nm to 455 nm.
Was measured. Spectral light source manufactured by Spectra Corp., Labsphere 20 inch integrating sphere (LMS-200) and Carl Zeiss spectroscope (Solid Lambda)
The change in chromaticity was observed by UV-Vis). Excitation wavelength is 445 nm, 448 nm,
The chromaticities at 450 nm, 452 nm, 454 nm, and 455 nm were measured, the average values (u ′ _ave , v ′ _ave ) were calculated, and the distance from the average value was measured.
The results are shown in Table 18 and FIGS.

For the semiconductor light emitting devices fabricated in Experimental Examples 1 to 12, the change in chromaticity Δu′v ′ was measured 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. Spectral light source made by Spectra Corp., 20 inches made by Labsphere
The change in chromaticity was observed using a ch integrating sphere (LMS-200) and a spectroscope manufactured by Carl Zeiss (Solid Lambda UV-Vis). Excitation wavelength is 430 nm, 440
In the case of nm, 450 nm, 460 nm, 470 nm, or 425 nm, 435 nm, 445 nm, 455 nm, 465 nm, and 475 nm, the average values (u ′ _ave , v ′ _ave ) are calculated and averaged The distance from the value was measured.
The results are shown in Tables 19 and 20 and FIGS.

  From the above, it is understood that the light emitting devices according to the first to fifth embodiments of the first invention can achieve high total luminous flux (light emission efficiency) while maintaining high color rendering. Moreover, it is understood from FIGS. 10-1 to 10-3 and FIGS. 11-1 to 11-2 that the light-emitting device of the present invention exhibits good binning characteristics.

<1-7. Excitation spectrum intensity change rate of phosphor mixture>
As Experimental Examples 13 to 22, the phosphors were weighed and mixed so as to have a total amount of 1 g at the weight ratios described in the phosphor mixing examples 1 to 7 and 9 to 11. The obtained mixed powder (mixture consisting only of phosphors and not including a transparent material) was subjected to excitation spectrum intensity measurement at 540 nm to 470 nm using a Hitachi spectrofluorometer F-4500. The excitation spectrum intensity change rate was calculated. The obtained excitation spectrum intensities are shown in FIGS. 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.

<2. Second embodiment>
The description of the example in the first embodiment described above is applied to the example in this embodiment.

<3. Third Embodiment>
<3-1. Simulation of color rendering and luminous efficiency>
In the present embodiment, <1-1-1. The description of the color rendering property and luminous efficiency simulation 1> is applied.

<3-2. Synthesis of phosphor>
About the synthesis | combination of the fluorescent substance in this embodiment, it is <1-2-1. In 1st embodiment mentioned above. Synthesis of phosphor GYAG1-4>, <1-2-4. The description of synthesis of YAG phosphor, GLuAG phosphor, SCASN phosphor, CASN phosphor> is applied.
The phosphor particle size and emission peak wavelength 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>
In the present embodiment, <1-3-1. Measurement of excitation spectrum intensity 1> and <1-3-3. The description of GYAG1 and YAG described in Measurement of excitation spectral intensity 3> applies.

<3-4. Production of wavelength conversion member and light emitting device>
In this embodiment, <1-4. In the first embodiment described above. The explanation of phosphor mixing examples 3 to 11 and experimental examples 4 to 9 described in “Manufacturing wavelength conversion member and light-emitting device” is applied.

<3-5. Luminescent characteristics>
In this embodiment, <1-5. In the first embodiment described above. The description of Experimental Examples 4 to 8 described in “Luminescent characteristics” is applied.

<3-6. Measurement of Δu'v '>
In this embodiment, <1-6. In the first embodiment described above. The description of Experimental Examples 4 to 8 described in “Measurement of Δu′v ′>” is applied.

<3-7. Excitation spectrum intensity change rate of phosphor mixture>
In this embodiment, <1-7. In the first embodiment described above. The explanation of Experimental Examples 15 to 20 described in “Excitation spectrum intensity change rate of phosphor mixture> is applied.

<4. Fourth Embodiment>
<4-1. Simulation of color rendering and luminous efficiency>
In this embodiment, <1-1-2. In the first embodiment described above. The description of color rendering and luminous efficiency simulation 2> is applied.

<4-2. Synthesis of phosphor>
About the synthesis | combination of the fluorescent substance in this embodiment, it is <1-2-2 in 1st embodiment mentioned 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 phosphor particle size and emission peak wavelength 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.

<4-3. Measurement of excitation spectrum intensity>
In this embodiment, <1-3-2 in the first embodiment described above. Measurement of excitation spectrum intensity 2> and <1-3-3. The description of LuAG1 and YAG described in Measurement of excitation spectral intensity 3> applies.

<4-4. Production of wavelength conversion member and light emitting device>
In this embodiment, <1-4. In the first embodiment described above. The explanation 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.

<4-5. Luminescent characteristics>
In this embodiment, <1-5. In the first embodiment described above. The description of Experimental Examples 1 to 3 described in “Luminescent Characteristics> is applied.

<4-6. Measurement of Δu'v '>
In this embodiment, <1-6. In the first embodiment described above. The description of Experimental Examples 1 to 3 described in Measurement of Δu′v ′> is applied.

<4-7. Excitation spectrum intensity change rate of phosphor mixture>
In this embodiment, <1-7. In the first embodiment described above. The explanation of Experimental Examples 13, 14, and 20 described in “Excitation spectrum intensity change rate of phosphor mixture> is applied.

<5. Fifth embodiment>
<5-1. Simulation of color rendering and luminous efficiency>
In this embodiment, <1-1-2. In the first embodiment described above. The description of color rendering and luminous efficiency simulation 2> is applied.

<5-2. Synthesis of phosphor>
About the synthesis | combination of the fluorescent substance in this embodiment, it is <1-2-2 in 1st embodiment mentioned 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 phosphor particle size and emission peak wavelength are described in <1-2-5. The description of LuAG1, YAG, SCASN, CASN described in “Particle size and emission peak wavelength of phosphor” is applied.

<5-3. Measurement of excitation spectrum intensity>
In this embodiment, <1-3-2 in the first embodiment described above. Measurement of excitation spectrum intensity 2> and <1-3-3. The description of LuAG1 and YAG described in Measurement of excitation spectral intensity 3> applies.

<5-4. Production of 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 “Manufacturing wavelength conversion member and light-emitting device” is applied.

<5-5. Luminescent characteristics>
In this embodiment, <1-5. In the first embodiment described above. The description of Experimental Examples 1 to 3 described in “Luminescent Characteristics> is applied.

<5-6. Measurement of Δu'v '>
In this embodiment, <1-6. In the first embodiment described above. The description of Experimental Examples 1 to 3 described in Measurement of Δu′v ′> is applied.

<5-7. Excitation spectrum intensity change rate of phosphor mixture>
In this embodiment, <1-7. In the first embodiment described above. The explanation of Experimental Examples 13, 14, and 20 described in “Excitation spectrum intensity change rate of phosphor mixture> is applied.

DESCRIPTION OF SYMBOLS 10 Light-emitting device 1 Blue semiconductor light-emitting element 2 Wiring board 2a Chip mounting surface 3 Wavelength conversion member 4 Frame

Claims (46)

A light emitting device including a blue semiconductor light emitting element and a wavelength conversion member,
The wavelength conversion member 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)
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 _z (G1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4) The light emitting device according to claim 1, wherein the wavelength conversion member has an excitation spectrum intensity change rate of 0.25 or less at an emission wavelength of 540 nm.
However, 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 light-emitting device according to claim 1, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.23 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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 light emitting device according to claim 1, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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 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 has an excitation spectrum intensity at 430 nm higher than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm.
The light-emitting device according to claim 1. Furthermore, it contains the blue-green fluorescent substance which is shown by the following general formula (B1) and has a peak wavelength of an emission wavelength spectrum when excited at 450 nm of 500 nm or more and 520 nm or less. The light emitting device according to claim 1.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)   The light emitting device according to any one of claims 1 to 5, wherein a composition ratio of the phosphor Y and the phosphor G is 10:90 or more and 90:10 or less. The light-emitting device according to claim 3 or 4, wherein an intensity change rate of an excitation spectrum synthesized by the following calculation formula (Z) 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 excitation spectrum intensity change rate and the weight fraction of the phosphor G are similarly expressed.
Each excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the combined 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. 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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 Δu′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 Δu′v ′ ≦ 0.004. Item 10. The light emitting device according to any one of Items 1 to 9.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ _ave , v) of chromaticity from 445 nm to 455 nm.
' _ave ) represents the distance. The chromaticity change Δu′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 Δu′v ′ ≦ 0.015. Item 11. The light emitting device according to any one of Items 1 to 10.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ _ave , v) of chromaticity from 435 nm to 470 nm.
' _ave ) represents the distance.   The light-emitting device according to claim 1, further comprising a red phosphor.   The red phosphor includes a 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 in a composition weight ratio of 30% or more with respect to the total amount of the red phosphor. 12. The light emitting device according to 12. The 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 is (Sr, Ca) AlSiN ₃ : Eu or Ca _1-x Al _1-x S
The light emitting device according to claim 13, wherein i _{1 + x} N _3−x O _x : Eu.   The light emitting device according to any one of claims 12 to 14, wherein the red phosphor 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 has a deviation duv from a 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 light emitting device according to claim 1.   The light emitted from the light emitting device has a deviation duv from a light-colored black body radiation locus of -0.0200 to 0.0200, and a color temperature of 2500 to 3500K. The light emitting device according to claim 1.   The light emitting device according to claim 1, wherein the average color rendering index Ra is 80 or more.   The illuminating device provided with the light-emitting device of any one of Claim 1 to 18. 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)
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 wavelength conversion member comprising a transparent material. The wavelength conversion member according to claim 20, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
However, 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 wavelength conversion member according to claim 20, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.23 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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 wavelength conversion member according to claim 20, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.33 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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 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 has an excitation spectrum intensity at 430 nm higher than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm.
The wavelength conversion member according to any one of claims 20 to 23. The 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 500 nm to 520 nm: 25. The wavelength conversion member of Claim 1.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)   The wavelength conversion member according to any one of claims 20 to 24, wherein a composition ratio of the phosphor Y and the phosphor G is 10:90 or more and 90:10 or less. The wavelength conversion member according to claim 22 or 23, wherein the intensity change rate of the excitation spectrum synthesized by the following calculation formula (Z) 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 excitation spectrum intensity change rate and the weight fraction of the phosphor G are similarly expressed.
Each excitation spectrum intensity change rate is represented by the difference between the maximum value and the minimum value of the combined 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. 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,
The wavelength conversion member whose excitation spectrum intensity change rate in emission wavelength 540nm of this wavelength conversion member is 0.33 or less.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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. 29. The chromaticity change Δu′v ′ of light emitted from the wavelength conversion member when the excitation wavelength is continuously changed from 445 nm to 455 nm satisfies Δu′v ′ ≦ 0.004. The wavelength conversion member of any one of Claims 1.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 445 nm to 455 nm and the average value (u ′ _ave , v) of chromaticity from 445 nm to 455 nm.
' _ave ) represents the distance. 30. The chromaticity change Δu′v ′ of light emitted from the wavelength conversion member when the excitation wavelength is continuously changed from 435 nm to 470 nm satisfies Δu′v ′ ≦ 0.015. The wavelength conversion member of any one of Claims 1.
However, Δu′v ′ is the chromaticity (u ′ _i , v ′ _i ) at an arbitrary wavelength inm from 435 nm to 470 nm and the average value (u ′ _ave , v) of chromaticity from 435 nm to 470 nm.
' _ave ) represents the distance. 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)
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,
A phosphor composition comprising a transparent material.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (G1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4) 32. The phosphor composition according to claim 31, wherein when the phosphor composition is molded into a wavelength conversion member, an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.25 or less.
However, 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),
32. The phosphor composition according to claim 31, wherein when the phosphor composition is molded into a wavelength conversion member, an excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength conversion member is 0.23 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.
8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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),
32. The phosphor composition according to claim 31, wherein when the phosphor composition is molded into a wavelength converting member, the excitation spectrum intensity change rate at an emission wavelength of 540 nm of the wavelength converting member is 0.33 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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. When the phosphor composition is molded into a wavelength conversion member,
The phosphor Y in the wavelength conversion member has an excitation spectrum intensity at 430 nm smaller than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm.
The phosphor G in the wavelength conversion member 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.
The phosphor composition according to any one of claims 31 to 34. The 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 500 nm or more and 520 nm or less: 36. 2. The phosphor composition according to item 1.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)   36. The phosphor composition according to any one of claims 31 to 35, wherein a composition ratio of the phosphor Y and the phosphor G is 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 phosphor composition comprising a transparent material,
A phosphor composition, wherein when the phosphor 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.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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. 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) 40. The phosphor mixture according to claim 39, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.40 or less.
However, 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),
40. The phosphor mixture according to claim 39, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.30 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (G2)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 1.2 ≦ c ≦ 2.6, 10.8 ≦ e ≦ 13.4)
However, 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),
40. The phosphor mixture according to claim 39, wherein an excitation spectrum intensity change rate at an emission wavelength of 540 nm is 0.25 or less.
Y _a (Ce, Tb, Lu) _b (Ga, Sc) _c Al _d O _e (Y3)
(A + b = 3, 0 ≦ b ≦ 0.2, 4.5 ≦ c + d ≦ 5.5, 0 ≦ c ≦ 0.2, 10.8 ≦ e ≦ 13.4)
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G3)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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 lower than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm,
The phosphor Y has an excitation spectrum intensity at 430 nm higher than an excitation spectrum intensity at 470 nm in an excitation spectrum at an emission wavelength of 540 nm.
43. The phosphor mixture according to any one of claims 39 to 42. The 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 500 nm or more and 520 nm or less. 2. The phosphor mixture according to item 1.
(Y, Ce, Tb, Lu) _x (Ga, Sc, Al) _y O _z (B1)
(X = 3, 4.5 ≦ y ≦ 5.5, 10.8 ≦ z ≦ 13.4)   44. The phosphor mixture according to any one of claims 39 to 43, wherein a composition ratio of the phosphor Y and the phosphor G is 10:90 or more and 90:10 or less. 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 the excitation spectrum change rate at an emission wavelength of 540 nm of the phosphor mixture is 0.25 or less.
Lu _f (Ce, Tb, Y) _g (Ga, Sc) _h Al _i O _j (G4)
(F + g = 3, 0 ≦ g ≦ 0.2, 4.5 ≦ h + i ≦ 5.5, 0 ≦ i ≦ 0.2, 10.8 ≦ j ≦ 13.4)
However, 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.

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