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CORRECTED EUROPEAN PATENT SPECIFICATION
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20160113
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Beschreibung
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Description
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Description
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Ansprüche EN
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Claims EN
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Revendications EN
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Ansprüche FR
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Claims FR
fr
Revendications FR
EP
11756217.3
20110314
20120914
ja
en
en
2010063228
20100318
JP
20160113
201602
20130123
201304
20150805
201532
20150420
20160113
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H01L 33/50 20100101AFI20140430BHEP
C09K 11/59 20060101ALI20140430BHEP
C09K 11/64 20060101ALI20140430BHEP
C09K 11/66 20060101ALI20140430BHEP
C09K 11/73 20060101ALI20140430BHEP
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WEISSLICHT-EMITTIERENDE LAMPE UND WEISSLICHT-EMITTIERENDE LED-BELEUCHTUNGSVORRICHTUNG DAMIT
en
WHITE LIGHT EMITTING LAMP, AND WHITE LIGHT LED LIGHTING DEVICE EQUIPPED WITH SAME
fr
LAMPE ÉMETTANT UNE LUMIÈRE BLANCHE, ET DISPOSITIF D'ÉCLAIRAGE À LED À LUMIÈRE BLANCHE ÉQUIPÉ DE CETTE LAMPE
EP-A2- 0 686 997
WO-A1-2010/021346
WO-A2-2005/004202
GB-A- 2 405 409
JP-A- 2007 291 353
JP-A- 2010 004 035
US-A- 6 157 126
US-A1- 2005 093 816
20140509
YAMAKAWA, Masahiko
c/o Intellectual Property Division Toshiba Corporation 1-1, Shibaura 1-Chome
Minato-ku, Tokyo 105-8001
JP
SHIRAKAWA, Yasuhiro
c/o Intellectual Property Division Toshiba Corporation 1-1, Shibaura 1-Chome
Minato-ku, Tokyo 105-8001
JP
USUI, Daichi
c/o Intellectual Property Division Toshiba Corporation 1-1, Shibaura 1-Chome
Minato-ku, Tokyo 105-8001
JP
Kabushiki Kaisha Toshiba
101017825
TOI289-20781WE
1-1 Shibaura 1-chome
Minato-ku Tokyo 105-8001
JP
Toshiba Materials Co., Ltd.
101019571
TOI289-20781WE
8 Shinsugita-Cho
Isogo-Ku Yokohama-Shi Kanagawa 235-0032
JP
Kramer Barske Schmidtchen Patentanwälte PartG mbB
100061463
European Patent Attorneys Landsberger Strasse 300
80687 München
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JP2011055885
20110314
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WO2011115032
20110922
201138
20130123
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Technical Field
The present invention relates to a white light emitting lamp including a semiconductor light emitting element and a white LED lighting apparatus (white LED illumination apparatus) including the white light emitting lamp, and more particularly, to a white light emitting lamp having improved color rendering properties and light emission efficiency and a white LED lighting apparatus including the white light emitting lamp.

Background Art
Light emitting diodes (LEDs) are semiconductor light emitting elements that convert electrical energy into ultraviolet light and visible light thereby to emit the converted light. Such light emitting diodes have a long service life and high reliability, and thus require less frequent replacement when being used as a light source, which is advantageous. LED lamps including an LED chip sealed with a transparent resin or the like are widely applied to: backlights of liquid crystal displays used in, for example, display portions of portable communication equipment, PC peripheral equipment, office automation (OA) equipment, and home electrical equipment; and lighting apparatuses such as signaling equipment, various switches, in-vehicle lamps, and general lighting.
With regard to the color tone of light emitted from the LED lamps, the LED chip is combined with various phosphors having different light emission colors, whereby light ranging from blue color to red color in a visible light region can be achieved in accordance with one's intended use. In particular, LED lamps that emit white light (white LED lamps) are rapidly becoming widespread to be applied to backlights of liquid crystal displays, in-vehicle lamps, and the like, and are expected to significantly expand as an alternative to fluorescent lamps in the future. For example, general fluorescent lamps are made using mercury, and hence the white LED lamps made without using mercury are considered to replace the fluorescent lamps in the future.
Known examples of the white LED lamp that has become widespread or is experimentally used at present may include: an LED lamp including a blue LED in combination with a yellow phosphor (such as YAG); and an LED lamp including an ultraviolet LED or violet LED having an emission wavelength of 360 to 440 nm in combination with a mixture of blue (B), green (G), and red (R) phosphors (BGR phosphors). Owing to superior luminance characteristics of the former, the former is currently more widespread than the latter. The light distribution of the former white LED lamp is, however, biased toward blue components and yellow components, and light containing red components is lacking and insufficient. Hence, in the case of even an LED lamp having emission chromaticity sufficient as a light source, the color of reflected light when an object is observed using this light source is significantly different from a natural color observed under sunlight. That is, there is posed a problem such that the color rendering properties of the former are low.
In contrast to the former, the latter white LED lamp including the ultraviolet LED, which unfortunately has luminance inferior to that of the former, has smaller color unevenness in emitted light and projected light, and thus is expected to become a mainstream white lamp in the future. As to the white LED lamp including the ultraviolet LED, lamp characteristics such as luminance (brightness) and color rendering properties are increasingly improved by adjusting characteristics of phosphors and a combination of the phosphors (see Patent Documents 1 and 2). For example, in order to enhance the brightness of the white LED lamp, it is studied to use a yellow phosphor having an emission peak wavelength of 540 to 570 nm in place of a green phosphor having an emission peak wavelength of 500 to 530 nm.
The white LED lamp to which such a mixture phosphor (BYR phosphor) containing the yellow phosphor in place of the green phosphor is applied has higher brightness than that of the white LED lamp containing the BGR phosphor, and thus is expected as a light source for a lighting apparatus. With regard to such a conventional white LED lamp to which the BYR phosphor containing the yellow phosphor is applied, however, a sufficient improvement effect of characteristics thereof cannot necessarily be obtained, and hence further enhancement in luminance and color rendering properties is required for the white LED lamp. Meanwhile, various yellow phosphors that can be used in combination with a blue LED have been proposed.
Known examples of the yellow phosphor that can be used in combination with the blue LED include: a cerium-activated yttrium aluminate phosphor (YAG), a cerium-activated terbium aluminate phosphor (TAG), and a europium-activated alkaline-earth silicate phosphor (BOSS) (see Patent Document 3). With regard to the conventional yellow phosphors, light emission characteristics of the yellow phosphors when being excited by blue light (emission wavelength: 430 to 500 nm) emitted from a blue LED have been studied. On the other hand, light emission characteristics of the yellow phosphors when being excited by light (emission wavelength: of 360 to 440 nm) emitted from an ultraviolet LED or violet LED have not been sufficiently studied, and thus are required to be studied and improved.
In addition, in order to enhance the color rendering properties of white light, a white LED apparatus including a blue LED and an ultraviolet LED in combination with a green phosphor and a red phosphor has also been proposed (see Patent Document 4). The color rendering properties of this white LED apparatus have been improved to some extent. However, because a part of blue light is easily absorbed by the phosphors, there is caused a disadvantage such that the luminance from a light emitting portion easily decreases. US 6157126 discloses a warm white fluorescent lamp comprising blue, green, red and deep red phosphor.

Citation List

Patent Documents
Patent Document 1: Japanese Patent Laid-Open No. 2002-171000 Patent Document 2: Japanese Patent Laid-Open No. 2003-160785 Patent Document 3: Japanese Patent No. 3749243 Patent Document 4: US 2006/0249739 A1

Summary of Invention

Problems to be solved by the Invention
The present invention has an object to provide a white light emitting lamp in which: in the case of combination use of a BGR phosphor containing a blue phosphor, a green phosphor, and a red phosphor with a semiconductor light emitting element such as an LED, a deep red phosphor having a main emission peak in a longer wavelength region than a main emission peak of the red phosphor is further added; and both the red phosphor and the deep red phosphor each having a particular composition are used together, whereby both high luminance and high color rendering properties can be obtained. The present invention has another object to provide a white LED lighting apparatus including such a white light emitting lamp as described above.

Means for Solving the Problems
A white light emitting lamp according to one aspect of the present invention comprises:
- a semiconductor light emitting element which is placed on a board and emits ultraviolet light or blue light; and
- a light emitting portion that is formed so as to cover a light emitting surface of the semiconductor light emitting element, the light emitting portion containing a blue phosphor, a green phosphor, a red phosphor and a deep red phosphor that are excited by the light emitted from the semiconductor light emitting element to respectively emit blue light, green light, red light and a deep red light,
- the white light emitting lamp emitting white light by mixing light emission colors from the blue phosphor, the green phosphor, the red phosphor and a deep red phosphor with one another,
- wherein the deep red phosphor has a main emission peak in a longer wavelength region than a main emission peak of the red phosphor,
- said red phosphor comprises at least one component selected from: a europium-activated SiAION phosphor having a composition expressed by a general formula of
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (1)
in which x, α, β, γ, δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3, 5 ≦ β ≦ 9, 1 ≦ γ ≦ 5, 0.5 ≦ δ ≦ 2 and 5 ≦ ω ≦ 15; and a europium-activated CASN phosphor having a composition expressed by a general formula of
(Sr_{1-x-y}, Ca_xEu_y)Al Si N_3 (2)
in which x and y satisfy the following relations 0 < x < 1, 0 < y < 0.2, 0 < x+y < 1; and
- wherein said deep red phosphor comprises a manganese-activated magnesium fluorogermanate phosphor having a composition expressed by a general formula of
α MgO · β MgF_2 · (Ge_{1-x}, Mnx) O_2 (3)
in which α, β and x satisfy the following relations 3.0 ≦ α ≦ 4.0, 0.4 ≦ β ≦ 0.6, 0.001 ≦ x ≦ 0.5.
Specifically, the white light emitting lamp comprises: the semiconductor light emitting element that emits light having a peak wavelength in a range of 370 nm or more and 470 nm or less; and the light emitting portion that is excited by the light emitted from the semiconductor light emitting element to emit the white light. The light emitting portion contains: the blue phosphor that absorbs the light to emit light having a peak wavelength in a range of 440 nm or more and 470 nm or less; the green phosphor that absorbs the light to emit light having a peak wavelength in a range of 530 nm or more and 600 nm or less; the red phosphor that absorbs the light to emit light having a peak wavelength in a range of 610 nm or more and 630 nm or less; and the deep red phosphor that absorbs the light to emit light having a peak wavelength in a range of 640 nm or more and 660 nm or less.
Note that it is important to select such phosphors that enable the main emission peak of the red phosphor and the main emission peak of the deep red phosphor to appear separately from each other in a spectral graph, in order to improve light emission intensity and color rendering properties. An advantage of the present invention is less likely to be obtained using a phosphor having a wide light emission range that overlaps with a light emission range of the red phosphor that emits the light having the peak wavelength in the range of 610 nm or more and 630 nm or less and with a light emission range of the deep red phosphor that emits the light having the peak wavelength in the range of 640 nm or more and 660 nm or less.
Further, in the above-mentioned white light emitting lamp, it is preferable that each of the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor has an average particle diameter in a range of 10 µm or more and 80 µm or less.
Further, in the above-mentioned white light emitting lamp, it is preferable that the light emitting portion includes a transparent resin layer that is formed so as to cover the light emitting surface of the semiconductor light emitting element and the transparent resin layer contains the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor.
Further, in the above-mentioned white light emitting lamp, it is preferable that the light emitting portion includes: a first transparent resin layer that is formed so as to cover the light emitting surface of the semiconductor light emitting element and does not contain the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor; and a second transparent resin layer that is formed so as to cover the first transparent resin layer and contains the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor.
Further, in the above-mentioned white light emitting lamp, it is preferable that the semiconductor light emitting element is a light emitting diode or a laser diode that emits light having a peak wavelength in a range of 370 nm or more and 470 nm or less.
A white LED lighting apparatus according to the present invention is characterized by comprising the above-mentioned white light emitting lamp according to the present invention.

Advantageous Effects of the Invention
In a white light emitting lamp according to the present invention, a deep red phosphor having a main emission peak in a longer wavelength region than a main emission peak of a red phosphor is further added, and both the red phosphor and the deep red phosphor each having a specified composition are used together. Hence, luminance characteristics (light emission efficiency) and color rendering properties can be both enhanced. Such a white light emitting lamp having both the high color rendering properties and the high luminance can be suitably used for lighting (illumination) and other such purposes.

Brief Description of the Drawings
- [Fig. 1] Fig. 1 is a cross-sectional view illustrating a configuration of a white light emitting lamp according to an embodiment of the present invention.
- [Fig. 2] Fig. 2 is a cross-sectional view illustrating a modified example of the white light emitting lamp illustrated in Fig. 1.
- [Fig. 3] Fig. 3 is a graph showing example emission spectra of four types of B, G, R, and DR phosphors applied to the present invention.
- [Fig. 4] Fig. 4 is a graph showing an example emission spectrum of a white LED lamp according to the embodiment of the present invention.
- [Fig. 5] Fig. 5 is a graph showing an example emission spectrum of a white LED lamp including a light emitting portion that is formed using only a conventional B, G, R phosphors without using a DR phosphor.

Mode for Carrying Out the Invention
Hereinafter, a mode for carrying out the present invention will be explained with reference to the accompanying drawings. Fig. 1 is a cross-sectional view illustrating a configuration of an embodiment in which a white light emitting lamp of the present invention is applied to a white LED lamp. The white LED lamp 1 illustrated in Fig. 1 includes an LED chip 2 as an excitation source (light source). The excitation source is not limited to the LED chip 2. A semiconductor light emitting element such as a light emitting diode and a laser diode having an emission peak wavelength in a range of 370 nm or more and 470 nm or less is used as the excitation source of the white light emitting lamp.
Various light emitting diodes such as InGaN-based, GaN-based, and AlGaN-based diodes are used as the LED chip 2 as the excitation source. It is preferable that an emission peak wavelength of the LED chip 2 fall within a range of 370 nm or more and 430 nm or less. The LED chip 2 as described above is used together with a BGR-DR phosphor which is obtained by combining a BGR phosphor with a deep red (DR) phosphor, whereby the white LED lamp 1 having high luminance and excellent color reproducibility can be achieved. Herein, the light emitting diode as the excitation source is expressed as the LED chip 2, and the light emitting lamp for finally obtaining white light emission is expressed as the white LED lamp 1.
The LED chip 2 is mounted on a wiring board 3. A cylindrical frame body 4 is provided on the wiring board 3, and an inner wall surface of the frame body 4 is formed as a reflective layer. At least a surface of the frame body 4 is made of an electrically conductive material such as metal, and constitutes part of electrical wiring for the LED chip 2. An upper electrode 2a of the LED chip 2 is electrically connected to the frame body 4 by a bonding wire 5. A lower electrode 2b of the LED chip 2 is electrically and mechanically connected to a metal wiring layer 6 of the wiring board 3. A transparent resin 7 fills a space defined by the frame body 4, and the LED chip 2 is embedded in the transparent resin layer 7.
The transparent resin layer 7 in which the LED chip 2 is embedded contains phosphors 8 for obtaining white light. The phosphors 8 dispersed in the transparent resin layer 7 are excited by light emitted from the LED chip 2, to thereby emit the white light. That is, the transparent resin layer 7 in which the phosphor 8 is dispersed functions as a light emitting portion 9 that emits the white light. The light emitting portion 9 is placed so as to cover a light emitting surface of the LED chip 2. The transparent resin layer 7 is made of, for example, a silicone resin or an epoxy resin. Note that configurations of the wiring board 3, the frame body 4, and the like are designed appropriately.
As illustrated in Fig. 2, the light emitting portion 9 may include a first transparent resin layer 7A not containing the phosphor 8 and a second transparent resin layer 7B containing the phosphor 8. The first transparent resin layer 7A is placed so as to cover the light emitting surface of the LED chip 2, and the second transparent resin layer 7B is placed so as to cover the first transparent resin layer 7A. The light emitting portion 9 having the configuration as described above contributes to enhancement in the light emission efficiency of the white LED lamp 1. The first transparent resin layer 7A is placed in a range of, for example, 500 to 2,000 µm from the light emitting surface of the LED chip 2.
The phosphor 8 for obtaining the white light contains a blue (B) phosphor, a green (G) phosphor, a red (R) phosphor, and a deep red (DR) phosphor that each absorbs the light emitted from the LED chip 2 (for example, ultraviolet light or violet light). The blue (B) phosphor emits light having a peak wavelength in a range of 440 nm or more and 470 nm or less, the green (G) phosphor emits light having a peak wavelength in a range of 535 nm or more and 570 nm or less, the red (R) phosphor emits light having a peak wavelength in a range of 590 nm or more and 630 nm or less, and the deep red (DR) phosphor emits light having a peak wavelength in a range of 640 nm or more and 660 nm or less. The phosphor 8 is a mixture phosphor (BGR-DR phosphor) of the BGR phosphor and the deep red (DR) phosphor. Note that, the BGR-DR phosphor 8 may contain two or more types of phosphors of the same color, and may supplementarily contain a yellow phosphor or the like having a light emission color other than blue (B), green (G), red (R), and deep red (DR). It is preferable to bind in advance the B, G, R, and DR phosphors of the BGR-DR phosphor 8 together using a binder and disperse the BGR-DR phosphor 8 in the binding state into the transparent resin layer 7.
Electrical energy applied to the white LED lamp 1 is converted by the LED chip 2 into the ultraviolet light or the violet light. The light emitted from the LED chip 2 is then further converted by the BGR-DR phosphor 8 dispersed in the transparent resin layer 7 into light having a longer wavelength. Light emission colors from the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor contained in the BGR-DR phosphor 8 are mixed with one another, and the resultant light is emitted as the white light as a whole from the white LED lamp 1. In the case where the peak wavelengths of the phosphors constituting the BGR-DR phosphor 8 respectively fall within the above-mentioned ranges, the white light having excellent luminance and color rendering properties can be obtained.
The blue (B) phosphor of the phosphors constituting the BGR-DR phosphor 8 is made of a europium-activated alkaline-earth chlorophosphate phosphor having a composition expressed by a general formula of
(Sr_{1-x-y-z}, Ba_x, Ca_y, Eu_z)_5 (PO_4)_3Cl (4)
(where x, y, and z are numbers that respectively satisfy 0 ≤ x < 0.5, 0 ≤ y ≤ 0.1, and 0.005 ≤ z < 0.1).
The europium-activated alkaline-earth chlorophosphate phosphor having the composition expressed by Formula (4) is excellent in, particularly, the absorption efficiency of ultraviolet light or violet light having a peak wavelength in a range of 370 to 430 nm.
The green (G) phosphor of the phosphors constituting the BGR-DR phosphor 8 is made of at least one of:
- a europium and manganese-activated aluminate phosphor having a composition expressed by a general formula of
(Ba_{1-x-y-z}, Sr_x, Ca_y, Eu_z)(Mg_{1-u}Mn_u)Al_{10}O_{17} (5)
(where x, y, z, and u are numbers that respectively satisfy 0 ≤ x < 0.2, 0 ≤ y < 0.1, 0.005 < z < 0.5, and 0.1 < u < 0.5);
- a europium and manganese-activated silicate phosphor having a composition expressed by a general formula of
(Sr_{1-x-y-z-u}, Ba_x, Mg_y, Eu_z, Mn_u)_2SiO_4 (6)
(where x, y, z, and u are numbers that respectively satisfy 0.1 ≤ x ≤ 0.35, 0.025 ≤ y ≤ 0.105, 0.025 ≤ z ≤ 0.25, and 0.0005 ≤ u ≤ 0.02), and
- a europium-activated SiAlON phosphor having a composition expressed by a general formula of
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (7)
in which x, α ,β, γ ,δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3,12 ≦ β ≦ 14, 2 ≦ γ ≦ 3.5, 1 ≦ δ ≦ 3 and 20 ≦ ω ≦ 22.
The red phosphor of the phosphors constituting the BGR-DR phosphor 8 comprises at least one component selected from:
- a europium-activated SiAlON phosphor having a composition expressed by a general formula of
(Sr_{1-x}, Eu_x)_α Sip Al_γ O_δ N_ω (1)
in which x, α ,β , γ ,δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3, 5 ≦ β ≦ 9, 1 ≦ γ ≦ 5, 0.1 ≦ δ ≦ 2 and 5 ≦ ω ≦ 15; and
- a europium-activated CASN phosphor having a composition expressed by a general formula of
(Sr_{1-x-y}, Ca_x Eu_y) Al Si N_3 (2)
in which x and y satisfy the following relations 0 < x < 1 , 0 < y < 0.2, 0 < x+y < 1 .
The deep red (DR) phosphor of the phosphors constituting the BGR-DR phosphor 8 is made of a manganese-activated magnesium fluorogermanate phosphor having a composition expressed by a general formula of
αMgO · βMgF_2 · (Ge_{1-x}Mn_x)O_2 (3)
(where α, β and x are numbers that respectively satisfy 3.0 ≤ α ≤ 4.0, 0.4 ≤ β ≤ 0.6, and 0.001 ≤ x ≤ 0.5).
In the case where the coefficients α and β in the manganese-activated magnesium fluorogermanate phosphor having the composition of formula (3) respectively fall within the above-mentioned ranges, improvement effects of the emission luminance and the color rendering properties can be obtained. A content of Mn is set to a range of 0.001 to 0.5 in terms of a value of x in formula (3). If the value of x is less than 0.001, an intensification effect of the red light emitting components cannot be sufficiently obtained. If the value of x exceeds 0.5, a decrease in the green light emitting components of 535 to 570 nm becomes problematic, even allowing for an increase effect of the red light emitting components of 600 to 700 nm, and the light emission efficiency decreases as a whole. Accordingly, it is more preferable to set the value of x to a range of 0.002 to 0.2.
Fig. 3 is a graph showing: an emission spectrum (B) of the Eu-activated alkaline-earth chlorophosphate phosphor ((Sr_{0.95}, Ba_{0.043}, EU_{0.007})_5(PO_4)_3Cl); an emission spectrum (G) of the europium and manganese-activated silicate phosphor (Sr_{1.48}, Ba_{0.32}, Mg_{0.095}, Eu_{0.1}, Mn_{0.005})_2SiO_4); an emission spectrum (R) of the europium-activated SiAlON phosphor ((Si_{1.6}Eu_{0.4})Si_7Al_3ON_{13}; and an emission spectrum (DR) of the manganese-activated magnesium fluorogermanate phosphor (3.5MgO · 0.5MgF_2 · (Ge_{0.99}Mn_{0.01})O_2, in comparison with one another.
As is apparent from Fig. 3, the manganese- activated magnesium fluorogermanate phosphor (DR) has a main emission peak in a longer wavelength region than a main emission peak of the conventional red phosphor (R), and the light emission intensity between 630 nm and 670 nm is increased, leading to enhancement in red tinge. As a result, the red light emitting components can be intensified and enforced.
The red phosphor is known to be inferior to the blue phosphor and the green phosphor in the light emission efficiency for ultraviolet light or violet light having a wavelength in a range of 370 to 430 nm. To address such a problem, the deep red light emitting components are intensified by the manganese-activated magnesium fluorogermanate phosphor (DR), and this enables enhancement in the luminance and color rendering properties of the white light obtained by mixing the colors from the blue, green, and red light emitting components with one another.
That is, insufficient light emission of the red phosphor is intensified with the combination use of the conventional red light emitting phosphor and the manganese- activated magnesium fluorogermanate phosphor (DR), and the luminance balance is thus enhanced, leading to enhancement in the luminance of the white light. Further, such enhancement in the luminance balance leads to enhancement in the color rendering properties of the white light.
In the green phosphor having the composition expressed by formula (6), the light emission of Mn is added to the emission spectrum of the Eu-activated alkaline-earth silicate phosphor, whereby the red light emitting components are considered to be intensified. In order to obtain such an effect, a content of Mn is set to a range of 0.0005 to 0.02 in terms of a value of u in formula (6). If the value of u is less than 0.0005, an intensification effect of the red light emitting components cannot be sufficiently obtained.
On the other hand, if the value of u exceeds 0.02, a decrease in the green light emitting components of 535 to 570 nm becomes problematic, even allowing for an increase effect of the red light emitting components of 600 to 700 nm. It is more preferable to set the value of u to a range of 0.005 to 0.02.
Eu is an activator for obtaining mainly green light emission. In order to obtain the green light emission, a content of Eu is set to a range of 0.025 to 0.25 in terms of a value of z in the formula (6). If the content of Eu falls out of the above-mentioned range, the intensity and the like of the green light emitting components is decreased. It is more preferable to set the content of Eu to a range of 0.05 to 0.2 in terms of the value of z.
The intensification effect of the red light emitting components produced by the Eu and Mn-activated alkaline-earth silicate phosphor is remarkable particularly in the case where the phosphor is excited by ultraviolet light or violet light having a peak wavelength in a range of 370 to 430 nm.
Note that the red components of the emission spectrum are slightly enhanced even in the case where the Eu and Mn-activated alkaline-earth silicate phosphor is excited by blue light (light emitted from a blue LED) having a peak wavelength of 440 to 470 nm.
The Eu and Mn-activated alkaline-earth silicate phosphor having the composition expressed by the formula (6) is suitable particularly for the green phosphor of the white LED lamp 1 including, as the excitation source, the LED chip 2 having a peak wavelength in a range of 370 to 430 nm.
Meanwhile, simple addition of Mn to a conventional Eu-activated alkaline-earth silicate phosphor ((Sr, Ba, Eu)_2SiO_4 phosphor) does not suffice to obtain excellent light emission characteristics, because the phosphor is colored during preparation thereof. In order to prevent such coloring, in the green phosphor of the present embodiment, Mg is further added to the Eu and Mn-activated alkaline-earth silicate phosphor ((Sr, Ba, Eu, Mn)_2SiO_4 phosphor).
The addition of Mg to the (Sr, Ba, Eu, Mn)_2SiO_4 phosphor enables maintaining light emission characteristics as the green phosphor. In order to obtain the above-mentioned coloring prevention effect, a content of Mg is set to a range of 0.025 to 0.105 in terms of a value of y in the formula (6).
If the value of y is less than 0.025, the coloring prevention effect for the green phosphor cannot be sufficiently obtained. On the other hand, if the value of y exceeds 0.105, the green light emitting components having a wavelength of 535 to 570 nm decrease. It is more preferable to set the value of y to a range of 0.075 to 0.105.
In the case of using the Eu and Mn-activated alkaline-earth silicate phosphor as the green phosphor, a content of Ba is set to a range of 0.1 to 0.35 in terms of a value of x in the formula (4). If the content of Ba falls out of the above-mentioned range, a crystal structure and the like of the alkaline-earth silicate would change, so that the alkaline-earth silicate becomes a phosphor tinged with green. It is more preferable to set the value of x to a range of 0.1 to 0.3.
The blue phosphor and the red phosphor of the phosphors constituting the BGR-DR phosphor 8 may be various phosphors as long as the used phosphors efficiently absorb the light emitted from the LED chip 2 (particularly, the ultraviolet light or the violet light). In particular, in consideration of the combination with the green phosphor made of the Eu and Mn-activated alkaline-earth silicate phosphor, it is preferable that the blue phosphor be made of at least one selected from a Eu-activated alkaline-earth chlorophosphate phosphor and a Eu-activated aluminate phosphor, and it is preferable that the red phosphor be made of a Eu-activated lanthanum oxysulfide phosphor.
It is preferable that the Eu-activated alkaline-earth chlorophosphate phosphor as the blue phosphor have a composition expressed by a general formula:
(Sr_{1-x-y-z}, Ba_x, Ca_y, Eu_z)_5(PO_4)_3Cl (4)
(where x, y, and z are numbers that respectively satisfy 0 ≤ x < 0.5, 0 ≤ y < 0.1, and 0.005 ≤ z < 0.1).
The Eu-activated alkaline-earth chlorophosphate phosphor that satisfies the composition of the formula (4) has high absorption efficiency of the light emitted from the LED chip 2, and can be excellently combined with the green phosphor expressed by each of the formulae (5), (6) and (7).
It is preferable that the Eu-activated aluminate phosphor have a composition expressed by a general formula:
(Ba_{1-x-y-z}, Sr_x, Ca_y, Eu_z)(Mg_{1-u}Mn)Al_{10}O_{17} (5)
(where x, y, z, and u are numbers that respectively satisfy 0 ≤ x < 0.2, 0 ≤ y < 0.1, 0.005 < z < 0.5, and 0.1 < u < 0.5).
The Eu-activated aluminate phosphor that satisfies the composition of the formula (5) has high absorption efficiency of the light emitted from the LED chip 2 and is excellent.
In addition, another used green phosphor is a europium and manganese-activated silicate phosphor having a composition expressed by a general formula:
(Sr_{1-x-y-z-u}, Ba_x, Mg_y, Eu_z, Mn_u)_2SiO_4 (6)
(where x, y, z, and u are numbers that respectively satisfy 0.1 ≤ x ≤ 0.35, 0.025 ≤ y ≤ 0.105, 0.025 ≤ z ≤ 0.25, and 0.0005 ≤ u ≤ 0.02).
Further, still another green phosphor is a europium- activated SiAlON phosphor having a composition expressed by a general formula of:
(Sr_{1-x}, EU_x)_α Si_β Al_γ O_δ N_ω (7)
(where x, α ,β , γ ,δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3,12 ≦ β ≦ 14, 2 ≦ γ ≦ 3.5, 1 ≦ δ ≦ 3 and 20 ≦ ω ≦ 22).
It is preferable that a europium- activated SiAlON phosphor as a red phosphor has a composition expressed by a general formula of:
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (1)
in which x, α, β, γ, δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3, 5 ≦ β ≦ 9, 1 ≦ γ ≦ 5, 0.1 ≦ δ ≦ 2 and 5 ≦ ω ≦ 15.
The europium- activated SiAlON phosphor as the red phosphor satisfying the composition of the general formula (1) has high absorption efficiency of the light emitted from the LED chip 2, and can be excellently combined with the green phosphor expressed by each of Formulae (5), (6) and (7).
In addition, another used red phosphor is a europium-activated CASN phosphor having a composition expressed by a general formula of:
(Sr_{1-x-y}, Ca_x Eu_y) Al Si N_3 (2)
in which x and y satisfy the following relations 0 < x < 1 , 0 < y < 0.2, 0 < x+y < 1.
The europium- activated CASN phosphor satisfying the composition of the general formula (2) also has high absorption efficiency of the light emitted from the LED chip 2, and can be excellently combined with the green phosphor expressed by each of the formulae (5), (6) and (7).
It is preferable that the manganese-activated magnesium fluorogermanate phosphor as the deep red phosphor has a composition expressed by a general formula of:
αMgO · βMgF2 · (Ge_{1-x}Mn_x)O_2 (3)
(where α, β, and x are numbers that respectively satisfy 3.0 ≤ α ≤ 4.0, 0.4 ≤ β ≤ 0.6, and 0.001 ≤ x ≤ 0.5).
The manganese-activated magnesium fluorogermanate phosphor that satisfies the composition of the formula (3) has the main emission peak in a longer wavelength region than the main emission peak of the red phosphor (R), and the light emission intensity between 630 nm to 670 nm is increased, leading to enhancement in red tinge. As a result, the red light emitting components can be intensified, and the color rendering properties can be effectively improved.
Fig. 4 shows an example emission spectrum of the white LED lamp 1 containing the BGR-DR phosphor 8 containing the blue (B), green (G), red (R), and deep red (DR) phosphors described above. Fig. 4 shows the emission spectrum obtained when the ultraviolet light from the LED chip having a current value of 20 mA and a peak value of 400 nm is converted by the BGR-DR phosphor into white light having an (x, y) chromaticity value (x = 0.300 to 0.350, y = 0.300 to 0.350).
The following characteristic values can be obtained by the combination of the phosphors described above. A peak value of the blue light emitting components is 450 nm, a peak value of the green light emitting components is 570 nm, a peak value of the red light emitting components is 630 nm, and a peak value of the deep red light emitting components is 660 nm. The luminance (brightness) is equal to or more than 370 mcd, and the average color rendering index (Ra) is equal to or more than 98.
In contrast, Fig. 5 shows an example emission spectrum of the white LED lamp 1 containing only the blue (B), green (G), and red (R) phosphors and not containing the deep red (DR) phosphor. Without the deep red (DR) phosphor, it is confirmed that the light emission intensity (light emission efficiency) decreases and that the average color rendering index (Ra) is approximately 92.
The blue, green, red, and deep red phosphors are dispersed into the transparent resin layer 7 in the form of, for example, a mixture. A mixing ratio of each of the phosphors is appropriately set in accordance with chromaticity of required white light. A phosphor other than the blue, green, red, and deep red phosphors may be added as needed.
In order to obtain a high-quality white light emission from the light emitting portion 9, it is preferable to set the mixing ratio of the phosphors such that the ratio of the blue phosphor is 20 to 35 percent by mass, the ratio of the green phosphor is 1 to 10 percent by mass, the ratio of the red phosphor is 0.4 to 70 percent by mass, and the ratio of the deep red phosphor is 3 to 25 percent by mass (the total ratio of the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor is 100 percent by mass).
Further, it is preferable that the blue, green, red, and deep red phosphors each have an average particle diameter in a range of 10 µm or more and 80 µm or less. The average particle diameter in this case refers to a median (50% value) in particle size distribution. The absorption efficiency of the ultraviolet light or the violet light emitted from the LED chip 2 can be enhanced by setting the average particle diameter of each of the blue, green, red, and deep red phosphors to a range of 10 to 80 µm. Accordingly, the luminance of the white LED lamp 1 can be further enhanced. It is more preferable to set the average particle diameter of each phosphor to a range of 20 to 70 µm.
In order to enhance uniformity of the dispersion state of the blue, green, red, and deep red phosphors in the transparent resin layer 7, the blue, green, red, and deep red phosphors may be integrated with one another in advance using a binder such as an inorganic binder and an organic binder, and may be dispersed into the transparent resin layer 7 in such an integrated state.
Examples of the inorganic binder include micronized alkaline-earth borate, and examples of the organic binder to be used include transparent resins such as an acrylic resin and a silicone resin. Through the integration process using the binder, the phosphors are randomly bound to one another to have a larger particle diameter.
As a result, non-uniformity of the dispersion state caused by, for example, a difference in sedimentation rate among the phosphors in the transparent resin layer 7 can be resolved, and hence the reproducibility of the white light and the uniformity of light emission can be enhanced.
The white LED lamp 1 of the present embodiment has excellent lamp characteristics such as luminance characteristics, color rendering properties, and color reproducibility. Accordingly, the white LED lamp 1 is suitably used as light sources of lighting apparatuses such as in-vehicle lamps, signaling equipment, various switches, and general lighting (illumination devices).
A lighting apparatus according to the embodiment of the present invention includes one or more white LED lamps 1 as a light source thereof. The white LED lamp(s) 1 are variously arranged for use on a mounting board in accordance with a configuration of the lighting apparatus to which the white LED lamp(s) 1 are applied. The lighting apparatus including the white LED lamp(s) 1 of the present embodiment provides high-quality lighting as an alternative to a conventional fluorescent lamp.

Examples
Next, concrete examples of the present invention and evaluation results thereof will be described hereunder.

(Examples 1 to 27)
The following various phosphors were prepared:
- for the blue phosphor (B), a Eu-activated alkaline-earth chlorophosphate ((Sr_{0.95}, Ba_{0.043}, Eu_{0.007})_5(PO_4)_3 · Cl) phosphor (hereinafter, abbreviated to "B1" in Table 1) having an average particle diameter of 12 µm;
- for the green phosphor (G), a Eu and Mn-activated alkaline-earth silicate ((Sr_{1.48}, Ba_{0.32}, Mg_{0.095}, Eu_{0.1}, Mn_{0.005})_2SiO_4) phosphor (hereinafter, abbreviated to "G1" in Table 1) having an average particle diameter of 15 µm;
- for another green phosphor, a europium-activated aluminate ((Ba_{0.95}, Eu_{0.05})(Mg_{0.7}Mn_{0.3})Al_{10}O_{17}) phosphor (hereinafter, abbreviated to "G2" in Table 1) having an average particle diameter of 15 µm;
- for still another green phosphor, a europium-activated SiAlON ((Sr_{2.7}, Eu_{0.3}) Si_{13}Al_3O_2N_{21}) phosphor (hereinafter, abbreviated to "G3" in Table 1) having an average particle diameter of 15 µm; and
- for the red phosphor (R), a Eu-activated SiAlON phosphor and a europium-activated CASN phosphor each having an average particle diameter of 12 µm and having a composition shown in Table 1.
Further, for the deep red phosphor (DR), manganese-activated magnesium fluorogermanate phosphors each having an average particle diameter of 12 µm and having respective compositions shown in Table 1 were prepared. The particle diameter of each phosphor was measured by laser diffractometry using a laser diffraction particle size analyzer.
Each phosphor was mixed with a silicone resin at a mixing ratio of 30 percent by mass, whereby slurry of each phosphor was prepared, respectively. The blue phosphor slurry, the green phosphor slurry, the red phosphor slurry, and the deep red phosphor slurry were mixed with one another at each weight ratio (percent by mass) shown in Table 1 such that emission chromaticity of the white LED lamp fell within a range of (x = 0.29 to 0.34, y = 0.29 to 0.34) and that a color temperature of an electric bulb color was 2,800 K, whereby each mixture phosphor was prepared.
Next, a silicone resin not containing a phosphor was dropped onto the LED chip (emission peak wavelength: 399 nm, size: 300 x 300 µm) 2 of the white LED lamp 1 having the configuration illustrated in Fig. 2, and the above-mentioned mixture slurry containing the phosphors was further dropped thereon. Then, the silicone resin was cured through heat treatment at 140°C. In this way, the white LED lamp 1 according to each example was prepared. The prepared white LED lamp was subjected to characteristic evaluation to be described later.

(Comparative Example 1)
Comparative Example 1 is similar to Example 1, except that the manganese-activated magnesium fluorogermanate phosphor as the deep red phosphor was not contained, a conventional europium-activated was used as the red phosphor (R), and that the mixing ratio of the B, G, and R phosphors was adjusted as shown in Table 1. The white LED lamp 1 according to such Comparative Example 1 was prepared so as to have a configuration similar to that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.

(Comparative Example 2)
Comparative Example 2 is similar to Example 1, except that a conventional europium- activated lanthanum oxysulfide was used as the red phosphor (R), and that the mixing ratio of the B, G, and R phosphors was adjusted as shown in Table 1. The white LED lamp 1 according to such Comparative Example 2 was prepared so as to have a configuration similar to that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.

(Comparative Example 3)
The same manufacturing process as in Example 1 was repeated except that the SiAlON phosphor in which a content ratio of strontium (Sr) was set to be excessively large was used as the red phosphor (R), thereby to manufacture a white LED lamp 1 according to Comparative Example 3 having the same configuration as that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.

(Comparative Example 4)
The same manufacturing process as in Example 1 was repeated except that the SiAlON phosphor in which a strontium (Sr) was not contained was used as the red phosphor (R), thereby to manufacture a white LED lamp 1 according to Comparative Example 4 having the same configuration as that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.

(Comparative Example 5)
The same manufacturing process as in Example 1 was repeated except that the manganese- activated magnesium fluorogermanate phosphor in which a content ratio of manganese (Mn) to Ge was set to be excessively small was used as the deep red phosphor (DR), thereby to manufacture a white LED lamp 1 according to Comparative Example 5 having the same configuration as that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.

(Comparative Example 6)
The same manufacturing process as in Example 1 was repeated except that the manganese- activated magnesium fluorogermanate phosphor in which a content ratio of manganese (Mn) to Ge was set to be excessively large was used as the deep red phosphor (DR), thereby to manufacture a white LED lamp 1 according to Comparative Example 6 having the same configuration as that illustrated in Fig. 2. The prepared white LED lamp 1 was subjected to the characteristic evaluation to be described later.
A current of 20 mA was caused to flow through the white LED lamp prepared as described above according to each of Examples 1 to 27 and Comparative Examples 1 to 6, and the white LED lamp was lighted. Then, the luminance (light emission efficiency) and the average color rendering index Ra of each white LED lamp were measured.
Note that the average color rendering index Ra was measured in conformity with Japanese Industrial Standards (JIS Z 8726-1990: Method of specifying color rendering properties of light sources). In addition, the light emission characteristics (the luminance, the light emission efficiency) of each white LED lamp were measured by using a compact array spectrometer CAS 140 produced by Instrument Systems and an MCPD apparatus produced by Otsuka Electronics Co., Ltd. These measurement results are shown in Table 1 hereunder.

[Table 1]
Sample No. | Blue Phosphor (B) | Green Phosphor (G) | Red Phosphor (R) | Deep Red Phosphor (DR) | Average Color Rendering Index (Ra) | Light Emission Efficiency (Im/W)
Phosphor Composition | Mixing Ratio | Phosphor Composition | Mixing Ratio | Phosphor Composition | Mixing Ratio | Phosphor Composition | Mixing Ratio
comparative Example 1 | B1 | 36% | G1 | 5% | (La_{0.885}Eu_{0.115})_2O_2S | 59% | - | 0% | 92 | 60
Comparative Example 2 | B1 | 29% | G1 | 4% | (La_{0.885}Eu_{0.115})_2O_2S | 47% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 93 | 60
Comparative Fxample 3 | B1 | 29% | G1 | 4% | (Sr_{2.997}EU_{0.005})Si_7Al_3ON_{13} | 47% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 93 | 58
Comparative Example 4 | B1 | 29% | G1 | 4% | Eu_{0.1}Si_7Al_3ON_{13} | 47% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 91 | 55
Comparative Example 5 | B1 | 29% | G1 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 47% | 3.5MgO· 0.5MgF_2· (Ge_{0.9995}Mn_{0.0005})O_2 | 20% | 92 | 60
Comparative Example 6 | B1 | 29% | G1 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 47% | 3.5MgO· 0.5MgF_2· (Ge_{0.3}Mn_{0.7})O_2 | 20% | 92 | 59
Example 1 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 68
Example 2 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 59% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{001})O_2 | 10% | 96 | 67
Example 3 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 54% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 15% | 97 | 65
Example 4 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 49% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 98 | 65
Example 5 | B1 | 29% | G1 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 62% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 67
Example 6 | B1 | 29% | G1 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 57% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 10% | 96 | 67
Example 7 | B1 | 25% | G1 | 6% | (Sr_{1.4}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.6}Mn_{0.4})O_2 | 5% | 96 | 68
Example 8 | B1 | 25% | G2 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 68
Example 9 | B1 | 25% | G2 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 59% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 10% | 96 | 68
Example 10 | B1 | 25% | G2 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 54% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 15% | 97 | 67
Example 11 | B1 | 25% | G2 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 49% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 98 | 66
Example 12 | B1 | 29% | G2 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 62% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 67
Example 13 | B1 | 29% | G2 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 57% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 10% | 96 | 66
Example 14 | B1 | 25% | G2 | 6% | (Sr_{1.4}Eu_{0.6})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.6}Mn_{0.4})O_2 | 5% | 96 | 67
Example 15 | B1 | 25% | G3 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 68
Example 16 | B1 | 25% | G3 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 59% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 10% | 96 | 67
Example 17 | B1 | 25% | G3 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 54% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 15% | 97 | 66
Example 18 | B1 | 25% | G3 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 49% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 20% | 98 | 65
Example 19 | B1 | 29% | G3 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 62% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 68
Example 20 | B1 | 29% | G3 | 4% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 57% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 10% | 96 | 68
Example 21 | B1 | 25% | G3 | 6% | (Sr_{1.4}Eu_{0.6})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.6}Mn_{0.4})O_2 | 5% | 96 | 67
Example 22 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 66
Example 23 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 97 | 64
Example 24 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.4MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 66
Example 25 | B1 | 25% | G1 | 6% | (Sr_{1.6}Eu_{0.4})Si_7Al_3ON_{13} | 64% | 3.8MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 65
Example 26 | B1 | 25% | G1 | 6% | (Ca_{0.95}Eu_{0.05})AlSiN_3 | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 96 | 64
Example 27 | B1 | 25% | G1 | 6% | (Sr_{0.45}Ca_{0.50}Eu_{0.05})AlSiN_3 | 64% | 3.5MgO· 0.5MgF_2· (Ge_{0.99}Mn_{0.01})O_2 | 5% | 95 | 65
B1 : Composition (Sr_{0.95}Ba_{0.043}Eu_0._{007})_5(PO_4)_3Cl G1 : Composition (Sr_{1.48}Ba_{0.32}Mg_{0.095}Mn_{0.005}EU_{0.1})SiO_4 G2 : Composition (Ba_{0.95}Eu_{0.05})(Mg_{0.7}Mn_{0.3})Al_{10}O_{17} G3 : Composition (Sr_{2.7}Eu_{0.3})Si_{13}Al_3O_2N_{21}
As is apparent from the results shown in Table 1, with regard to the white LED lamps according to each of Examples 1 to 27, in which the deep red phosphor having a predetermined composition and having the main emission peak in a longer wavelength region than the main emission peak of the red phosphor having a predetermined composition was further added and both the red phosphor and the deep red phosphor were used together, it was confirmed that both the light emission efficiency and the color rendering properties were excellent in comparison with those of Comparative Examples 1 to 6.
The average color rendering index Ra of each example was 96 to 98 Ra, and hence, it was confirmed that the color rendering properties were considerably improved in comparison with those of each comparative example.
In contrast, with regard to the white LED lamp according to Comparative Example 1, which did not contain a manganese-activated magnesium fluorogermanate phosphor and contained only the conventional BGR phosphor, both the light emission efficiency and the color rendering properties were decreased in comparison with those of the present examples.
In case of Comparative Example 3 in which the amount of Sr in the red phosphor was set to excessively large, and in case of Comparative Example 4 in which the SiAlON phosphor containing no Sr was used, the light emission efficiency was remarkably lowered.
With regard to the white LED lamp according to Comparative Example 5, which contained the deep red phosphor in which the content ratio of Mn to Ge was set to be excessively small, a small improvement effect of the color rendering properties was found to some extent, but improvement effect of the light emission efficiency was found to be small.
In addition, with regard to the white LED lamp according to Comparative Example 6, which contained the deep red phosphor in which the content ratio of Mn to Ge was set to be excessively large, it was confirmed that a small improvement effect of the color rendering properties was found to some extent, but the light emission efficiency was considerably decreased.

Industrial Applicability
In a white light emitting lamp according to the present invention, a deep red phosphor having a main emission peak in a longer wavelength region than a main emission peak of a red phosphor is further added, and both the red phosphor and the deep red phosphor are used together. Hence, luminance characteristics (light emission efficiency) and color rendering properties can be both enhanced. Such a white light emitting lamp having both the high color rendering properties and the high luminance can be suitably used for lighting and other such purposes.

Description of Symbols
1 ... white LED lamp, 2 ... LED chip, 3 ... wiring board, 4 ... frame body, 5 ... bonding wire, 6 ... metal wiring layer, 7 ... transparent resin layer, 7A ... first transparent resin layer, 7B ... second transparent resin layer, 8 ... BGR-DR phosphor, 9 ... light emitting portion
1. A white light emitting lamp comprising:
a semiconductor light emitting element which is placed on a board and emits ultraviolet light or blue light; and
a light emitting portion that is formed so as to cover a light emitting surface of the semiconductor light emitting element, the light emitting portion containing a blue phosphor, a green phosphor, a red phosphor and a deep red phosphor that are excited by the light emitted from the semiconductor light emitting element to respectively emit blue light, green light, red light and a deep red light,
the white light emitting lamp emitting white light by mixing light emission colors from the blue phosphor, the green phosphor, the red phosphor and a deep red phosphor with one another,
wherein the deep red phosphor has a main emission peak in a longer wavelength region than a main emission peak of the red phosphor,
said red phosphor comprises at least one component selected from: a europium-activated SiAlON phosphor having a composition expressed by a general formula of:
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (1)
in which x, α, β, γ, δ and ω satisfy the following relations 0 < x < 1, 0 < α ≦ 3, 5 ≦ β ≦ 9, 1 ≦ γ ≦ 5, 0.5 ≦ δ ≦ 2 and 5 ≦ ω ≦ 15; and
a europium-activated CASN phosphor having a composition expressed by a general formula of:
(Sr_{1-x-y}, Ca_x Eu_y) Al Si N_3 (2)
in which x and y satisfy the following relations 0<x<1, 0<y<0.2, 0 < x+y < 1 ; and
wherein said deep red phosphor comprises a manganese-activated magnesium fluorogermanate phosphor having a composition expressed by a general formula of:
α MgO · β MgF_2 · (Ge_{1-x}, Mn_x)O_2 (3)
in which α, β and x satisfy the following relations 3.0 ≦ α ≦ 4.0, 0.4 ≦ β ≦ 0.6, 0.001 ≦ x ≦ 0.5.
2. The white light emitting lamp according to claim 1, wherein
the blue phosphor is made of a europium-activated alkaline-earth chlorophosphate phosphor having a composition expressed by a general formula:
(Sr_{1-x-y-z}, Ba_x, Ca_y, Eu_z)_5 (PO_4)_3Cl (4)
in which x, y, and z are numbers that respectively satisfy 0 ≤ x < 0.5, 0 ≤ y < 0.1, and 0.005 ≤ z < 0.1.
3. The white light emitting lamp according to claim 1 or 2, wherein the green phosphor is made of at least one of:
a europium and manganese-activated aluminate phosphor having a composition expressed by a general formula:
(Ba_{1-x-y-z}, Sr_x, Ca_y, Eu_z)(Mg_{1-u}Mn_u)Al_{10}O_{17} (5)
(where x, y, z, and u are numbers that respectively satisfy 0 ≤ x < 0.2, 0 ≤ y < 0.1, 0.005 < z < 0.5, and 0.1 < u < 0.5);
a europium and manganese-activated silicate phosphor having a composition expressed by a general formula:
(Sr_{1-x-y-z-u}, Ba_x, Mg_y, Eu_z, Mn_u)_2SiO_4 ... (6)
(where x, y, z, and u are numbers that respectively satisfy 0.1 ≤ x ≤ 0.35, 0.025 ≤ y ≤ 0.105, 0.025 ≤ z ≤ 0.25, and 0.0005 ≤ u ≤ 0.02); and
a europium-activated SiAlON phosphor having a composition expressed by a general formula of
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω, (7)
(where x, α, β, γ, δ and ω satisfy the following relations 0 < x < 1,
0 < α ≦ 3,12 ≦ β ≦ 14, 2 ≦ γ ≦ 3.5, 1 ≦ δ ≦ 3 and 20 ≦ ω ≦ 22).
4. The white light emitting lamp according to any one of claim 1 to claim 3, wherein the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor each have an average particle diameter in a range of 10 µm or more and 80 µm or less.
5. The white light emitting lamp according to any one of claim 1 to claim 4, wherein the light emitting portion includes a transparent resin layer that is formed so as to cover the light emitting surface of the semiconductor light emitting element and the transparent resin layer contains the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor.
6. The white light emitting lamp according to any one of claim 1 to claim 4, wherein the light emitting portion includes:
a first transparent resin layer that is formed so as to cover the light emitting surface of the semiconductor light emitting element and does not contain the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor; and
a second transparent resin layer that is formed so as to cover the first transparent resin layer and contains the blue phosphor, the green phosphor, the red phosphor, and the deep red phosphor.
7. The white light emitting lamp according to any one of claim 1 to claim 6, wherein the semiconductor light emitting element is a light emitting diode or a laser diode that emits light having a peak wavelength in a range of 370 nm or more and 470 nm or less.
8. A white LED lighting apparatus comprising the white light emitting lamp according to any one of claim 1 to claim 7.
1. Weißes Licht emittierendes Leuchtmittel, umfassend:
ein lichtemittierendes Halbleiterelement, das auf einer Platte angeordnet ist und ultraviolettes Licht oder blaues Licht emittiert, und
einen lichtemittierenden Abschnitt, der so ausgebildet ist, dass er eine lichtemittierende Oberfläche des lichtemittierenden Halbleiterelements bedeckt, wobei der lichtemittierende Abschnitt einen blauen Leuchtstoff, einen grünen Leuchtstoff, einen roten Leuchtstoff und einen dunkelroten Leuchtstoff enthält, die durch das Licht angeregt werden, das von dem lichtemittierenden Halbleiterelement emittiert wird, so dass sie jeweils blaues Licht, grünes Licht, rotes Licht und dunkelrotes Licht emittieren,
wobei das weißes Licht emittierende Leuchtmittel durch Mischen von Lichtemissionsfarben von dem blauen Leuchtstoff, dem grünen Leuchtstoff, dem roten Leuchtstoff und dem dunkelroten Leuchtstoff weißes Licht emittiert,
wobei der dunkelrote Leuchtstoff einen Hauptemissionspeak in einem längeren Wellenlängenbereich als der Hauptemissionspeak des roten Leuchtstoffs aufweist,
wobei der rote Leuchtstoff mindestens eine Komponente umfasst, die aus einem Europium-aktivierten SiAION-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel:
(Sr_{1-x}, Eu_x)_αSi_β Al_γ O_δ N_ω (1)
dargestellt wird, worin x, α, β, γ, δ und w den folgenden Beziehungen 0 < x < 1, 0 < α ≤ 3, 5 ≤ β ≤ 9, 1 ≤ γ ≤ 5, 0,5 ≤ 2 und 5 ≤ ω ≤ 15 genügen, und
einem Europium-aktivierten CASN-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel:
(Sr_{1-x-y}, Ca_x Eu_γ) Al Si N_3 (2)
dargestellt wird, worin x und y den folgenden Beziehungen 0 < x < 1, 0 < y < 0,2, 0 < x + y < 1 genügen, ausgewählt ist, und
wobei der dunkelrote Leuchtstoff einen Mangan-aktivierten Magnesiumfluorgermanat-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel
αMgO · βMgF_2 · (Ge_{1-x}, Mnx) O_2 (3)
dargestellt wird, worin α, β und x den folgenden Beziehungen 3,0 ≤ α ≤ 4,0, 0,4 ≤ β ≤ 0,6, 0,001 ≤ x ≤ 0,5 genügen, umfasst.
2. Weißes Licht emittierendes Leuchtmittel nach Anspruch 1, bei dem
der blaue Leuchtstoff aus einem Europium-aktivierten Erdalkalichlorphosphat-Leuchtstoff, der eine Zusammensetzung aufweist, die die durch die allgemeine Formel:
(Sr_{1-x-y-z}, Ba_x, Ca_γ, Eu_z)_5(PO_4)_3Cl (4)
dargestellt wird, worin x, y und z Zahlen sind, die jeweils 0 ≤ x < 0,5, 0 ≤ y < 0,1 und 0,005 ≤ z < 0,1 genügen, hergestellt ist.
3. Weißes Licht emittierendes Leuchtmittel nach Anspruch 1 oder 2, bei dem der grüne Leuchtstoff aus mindestens einem von
einem Europium- und Mangan-aktivierten Aluminat-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel:
(Ba_{1-x-y-z}, Sr_x, Ca_y, Eu_z)(Mg_{1-u}Mn_u)Al_{10}O_{17} (5)
dargestellt wird (worin x, y, z und u Zahlen sind, die jeweils 0 ≤ x < 0,2, 0 ≤ y < 0,1, 0,005 < z < 0,5 und 0,1 < u < 0,5 genügen),
einem Europium- und Mangan-aktivierten Silikat-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel:
(Sr_{1-x-y-z-u}, Ba_x, Mg_y, Eu_z, Mn_u)_2SiO_4 (6)
dargestellt wird (worin x, y, z und u Zahlen sind, die jeweils 0,1 ≤ x ≤ 0,35, 0,025 ≤ y ≤ 0,105, 0,025 ≤ z ≤ 0,25 und 0,0005 ≤ u ≤ 0,02 genügen) und
einem Europium-aktivierten SiAlON-Leuchtstoff, der eine Zusammensetzung aufweist, die durch die allgemeine Formel:
(Sr_{1-x}, E_{Ux})_αSi_β Al_γ O_δ N_ω (7)
dargestellt wird (worin x, α, β, γ, δ und ω den folgenden Beziehungen 0 < x < 1, 0 < α ≤ 3, 12 ≤ β ≤ 14, 2 ≤ γ ≤ 3,5, 1 ≤ δ ≤ 3 und 20 ≤ ω ≤ 22 genügen), hergestellt ist.
4. Weißes Licht emittierendes Leuchtmittel nach einem der Ansprüche 1 bis 3, bei dem der blaue Leuchtstoff, der grüne Leuchtstoff, der rote Leuchtstoff und der dunkelrote Leuchtstoff jeweils einen durchschnittlichen Teilchendurchmesser in einem Bereich von 10 µm oder mehr und 80 µm oder weniger aufweisen.
5. Weißes Licht emittierendes Leuchtmittel nach einem der Ansprüche 1 bis 4, bei dem der lichtemittierende Abschnitt eine transparente Harzschicht umfasst, die so ausgebildet ist, dass sie die lichtemittierende Oberfläche des lichtemittierenden Halbleiterelements bedeckt und wobei die transparente Harzschicht den blauen Leuchtstoff, den grünen Leuchtstoff, den roten Leuchtstoff und den dunkelroten Leuchtstoff enthält.
6. Weißes Licht emittierendes Leuchtmittel nach einem der Ansprüche 1 bis 4, bei dem der lichtemittierende Abschnitt umfasst:
eine erste transparente Harzschicht, die so ausgebildet ist, dass sie die lichtemittierende Oberfläche des lichtemittierenden Halbleiterelements bedeckt und den blauen Leuchtstoff, den grünen Leuchtstoff, den roten Leuchtstoff und den dunkelroten Leuchtstoff nicht enthält, und
eine zweite transparente Harzschicht, die so ausgebildet ist, dass sie die erste transparente Harzschicht bedeckt und den blauen Leuchtstoff, den grünen Leuchtstoff, den roten Leuchtstoff und den dunkelroten Leuchtstoff enthält.
7. Weißes Licht emittierendes Leuchtmittel nach einem der Ansprüche 1 bis 6, bei dem das lichtemittierende Halbleiterelement eine Leuchtdiode oder eine Laserdiode ist, die Licht mit einer Peakwellenlänge in einem Bereich von 370 nm oder mehr und 470 nm oder weniger emittiert.
8. Weiße LED-Beleuchtungsvorrichtung, die das weißes Licht emittierende Leuchtmittel nach einem der Ansprüche 1 bis 7 umfasst.
1. Lampe d'émission de lumière blanche comprenant :
un élément d'émission de lumière à semi-conducteurs qui est placé sur une carte et qui émet une lumière ultraviolette ou une lumière bleue ; et
une portion d'émission de lumière qui est constituée de manière à recouvrir une surface d'émission de lumière de l'élément d'émission de lumière à semi-conducteurs, la portion d'émission de lumière contenant un phosphore bleu, un phosphore vert, un phosphore rouge et un phosphore rouge foncé qui sont excités par la lumière émise de l'élément d'émission de lumière à semi-conducteurs pour émettre respectivement une lumière bleue, une lumière verte, une lumière rouge et une lumière rouge foncé,
la lampe d'émission de lumière blanche émettant une lumière blanche en mélangeant des couleurs d'émission de lumière du phosphore bleu, du phosphore vert, du phosphore rouge et du phosphore rouge foncé entre elles,
dans laquelle le phosphore rouge foncé a une pointe d'émission principale dans une région de longueur d'onde plus longue que celle d'une pointe d'émission principale du phosphore rouge,
ledit phosphore rouge comprend au moins un composant sélectionné parmi : un phosphore SiAlON activé par europium ayant une composition exprimée par une formule générale de :
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (1)
où x, α, β, γ, δ et ω respectent les relations suivantes 0 < x < 1, 0 < α ≤ 3, 5 ≤ β ≤ 9, 1 ≤ γ ≤ 5, 0,5 ≤ δ ≤ 2 et 5 ≤ ω ≤ 15 ; et
un phosphore CASN activée par europium ayant une composition exprimée par une formule générale de :
(Sr_{1-x-y}, Ca_x Eu_y) Al Si N_3 (2)
où x et y respectent les relations suivantes 0 < x < 1, 0 < y < 0,2, 0 < x+y < 1 ; et
dans laquelle ledit phosphore rouge foncé comprend un phosphore de fluorogermanate de magnésium activé par manganèse ayant une composition exprimée par une formule générale de :
αMgO · βMgF_2 · (Ge_{1-x}, Mn_x)O_2 (3)
où α, β et x respectent les relations suivantes 3,0 ≤ α ≤ 4,0, 0,4 ≤ β ≤ 0,6, 0,001 ≤ x ≤ 0,5.
2. Lampe d'émission de lumière blanche selon la revendication 1, dans laquelle
le phosphore bleu est constitué d'un phosphore de chlorophosphate de terre alcaline activé par europium ayant une composition exprimée par une formule générale :
(Sr_{1-x-y-z}, Ba_x, Ca_y, Eu_z)_5 (PO_4)_3Cl (4)
où x, y et z sont des nombres respectant respectivement 0 ≤ x < 0,5, 0 ≤ y < 0,1 et 0,005 ≤ z < 0,1.
3. Lampe d'émission de lumière blanche selon la revendication 1 ou 2, dans laquelle
le phosphore vert est constitué d'au moins l'un de :
un phosphore d'aluminate activé par europium et manganèse ayant une composition exprimée par une formule générale :
(Ba_{1-x-y-z}, Sr_x, Ca_y, Eu_z) (Mg_{1-u} Mn_u) Al_{10} O_{17} (5)
(où x, y, z et u sont des nombres respectant respectivement 0 ≤ x < 0,2, 0 ≤ y < 0,1, 0,005 < z < 0,5 et 0,1 < u < 0,5);
un phosphore de silicate activé par europium et manganèse ayant une composition exprimée par une formule générale :
(Sr_{1-x-y-z-u}, Ba_x, Mg_y, Eu_z, Mn_u)_2 SiO_4 (6)
(où x, y, z et u sont des nombres respectant respectivement 0,1 ≤ x < 0,35, 0,025 ≤ y ≤ 0,105, 0,025 ≤ z ≤ 0,25 et 0,0005 ≤ u ≤ 0,02) ; et
un phosphore SiAlON activé par europium ayant une composition exprimée par une formule générale de :
(Sr_{1-x}, Eu_x)_α Si_β Al_γ O_δ N_ω (7)
(où x, α, β, γ, δ et ω respectent les relations suivantes 0 < x < 1, 0 < α ≤ 3, 12 ≤ β ≤ 14, 2 ≤ γ ≤ 3,5, 1 ≤ δ ≤ 3 et 20 ≤ ω ≤ 22).
4. Lampe d'émission de lumière blanche selon l'une quelconque des revendications 1 à 3, dans laquelle le phosphore bleu, le phosphore vert, le phosphore rouge et le phosphore rouge foncé ont chacun un diamètre moyen de particules dans une plage de 10 µm ou plus et 80 µm ou moins.
5. Lampe d'émission de lumière blanche selon l'une quelconque des revendications 1 à 4, dans laquelle la portion d'émission de lumière comprend une couche de résine transparente qui est constituée de manière à recouvrir la surface d'émission de lumière de l'élément d'émission de lumière à semi-conducteurs et la couche de résine transparente contient le phosphore bleu, le phosphore vert, le phosphore rouge et le phosphore rouge foncé.
6. Lampe d'émission de lumière blanche selon l'une quelconque des revendications 1 à 4, dans laquelle la portion d'émission de lumière comprend :
une première couche de résine transparente qui est constituée de manière à recouvrir la surface d'émission de lumière de l'élément d'émission de lumière à semi-conducteurs et qui ne contient pas le phosphore bleu, le phosphore vert, le phosphore rouge et le phosphore rouge foncé ; et
une deuxième couche de résine transparente qui est constituée de manière à recouvrir la première couche de résine transparente et qui contient le phosphore bleu, le phosphore vert, le phosphore rouge et le phosphore rouge foncé.
7. Lampe d'émission de lumière blanche selon l'une quelconque des revendications 1 à 6, dans laquelle l'élément d'émission de lumière à semi-conducteurs est une diode d'émission de lumière ou une diode laser qui émet une lumière ayant une longueur d'onde de pointe dans une plage de 370 nm ou plus et 470 nm ou moins.
8. Appareil d'éclairage à LED blanche comprenant la lampe d'émission de lumière blanche selon l'une quelconque des revendications 1 à 7.

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This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

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