JP5429731B2 - Phosphor production method, phosphor-containing composition, light emitting device, image display device, and illumination device - Google Patents

Description

  The present invention relates to a method for producing a phosphor, a phosphor-containing composition and a light emitting device using the phosphor, and an image display device and an illumination device using the light emitting device.

  Phosphors are used in fluorescent lamps, fluorescent display tubes (VFD), field emission displays (FED), plasma display panels (PDP), cathode ray tubes (CRT), white light emitting diodes (LEDs) and the like. In any of these applications, in order to make the phosphor emit light, it is necessary to supply the phosphor with energy for exciting the phosphor, and the phosphor is not limited to vacuum ultraviolet rays, ultraviolet rays, visible rays, electron beams, etc. When excited by an excitation source having high energy, it emits ultraviolet rays, visible rays, and infrared rays.

In recent years, in place of conventional phosphors such as silicate phosphor, phosphate phosphor, aluminate phosphor, borate phosphor, sulfide phosphor, oxysulfide phosphor, etc. Many new materials have been synthesized for nitrides. Particularly recently, phosphors having excellent characteristics such as multi-element nitrides and oxynitrides exhibiting high-luminance emission and little deterioration during use, for example, Ca-α-sialon activated Eu ²⁺ ions. Li-α-sialon, (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Ce, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, (Sr, Ca, Mg) AlSiN ₃ : Eu, (Sr, Ca, Mg) AlSiN ₃ : Ce and the like have been developed.

  The phosphors of such multi-element nitrides and oxynitrides (hereinafter sometimes referred to as “(acid) nitrides”) are nitrides or oxides of the respective metal elements constituting the phosphor. The raw material powder is produced by a so-called solid phase method in which raw material powder is mixed at a predetermined ratio and the raw material mixed powder is fired in nitrogen gas or ammonia gas.

  However, in the case of the solid phase method, since the raw material powder used has low reactivity, the phosphor is fired in a compression-molded state in order to promote the solid phase reaction between the raw material mixed powders during firing. Is manufactured in a very hard sintered state. Therefore, it is necessary to pulverize the obtained sintered body to a fine powder state suitable for the intended use of the phosphor. However, when a phosphor made of a hard sintered body is pulverized using a jaw crusher or a ball mill, a large number of defects are generated in the crystal matrix of the phosphor, which may significantly reduce the emission intensity of the phosphor. It was.

  In addition, although a method of firing in a powder state without compression molding has been attempted, in this case, firing at a low temperature does not promote a solid-phase reaction between the raw material powders, and the target phosphor is not generated. Therefore, it is necessary to synthesize the phosphor at a high temperature of 1800 ° C. or higher. However, when firing at such a high temperature, there is a possibility that a decomposition reaction accompanied by desorption of nitrogen from the nitride raw material may occur. In addition, in order to suppress the decomposition reaction, it is necessary to perform firing in a nitrogen gas atmosphere of 5 atm or higher, which not only requires high firing energy, but also requires a very expensive high-temperature high-pressure firing furnace, It is a cause of increasing the manufacturing cost of the body.

Furthermore, in the case of a phosphor containing an alkaline earth metal, a divalent metal nitride such as calcium nitride (Ca ₃ N ₂ ) or strontium nitride (Sr ₃ N ₂ ) is used as a raw material. Valent metal nitrides are unstable in a moisture-containing atmosphere, and easily react with moisture in the atmosphere to be hydrolyzed to generate hydroxides, and thus contain a large amount of hydroxides. When a divalent metal nitride containing a large amount of hydroxide is used as a raw material in this way, the oxygen concentration in the obtained phosphor is increased, which may adversely affect the phosphor characteristics. In addition, since calcium nitride and strontium nitride are very active and explosively burn in contact with water, handling with sufficient care is necessary.

  For this reason, a new production method that replaces the solid phase method has been demanded. In recent years, Patent Literature 1, Patent Literature 2, and the like have reported on a method for producing a nitride phosphor using a metal or an alloy as a starting material. Has been.

Patent Document 1 discloses an example of a method for producing an aluminum nitride-based phosphor, which describes that transition elements, rare earth elements, aluminum, and alloys thereof can be used as raw materials.
However, an example using an alloy as a raw material is not described, and it is characterized by using Al metal as an Al source. In addition, since the combustion synthesis method is used to ignite the raw material and instantaneously raise the temperature to a high temperature (3000 K), the activation elements cannot be uniformly distributed, and it is difficult to obtain a high-quality phosphor. It is guessed. Moreover, there is no description regarding the (acid) nitride phosphor containing an alkaline earth element obtained from the alloy raw material or the (acid) nitride phosphor further containing silicon.

Patent Document 2 discloses a phosphor manufacturing method in which an alloy containing two or more metal elements constituting a phosphor is prepared, and the alloy powder is heated and nitrided in a nitrogen-containing atmosphere. In the case of a phosphor containing silicon and an alkaline earth metal, since the melting point of Si is as high as the boiling point of the alkaline earth metal, the Si metal or the master alloy containing Si is first melted, It is described that it is preferable to prepare a raw material alloy by adding an alkaline earth metal.
However, in the method of Patent Document 2, since there is a very large rapid heat generation when nitriding the raw material alloy powder, there is a possibility that the raw material alloy powder melts and the ingress of nitrogen is inhibited and nitriding does not proceed sufficiently. is there. Further, there is a possibility that silicon is separated when melted, and the separated silicon is blackened because it is difficult to nitride, and there is a possibility that a desired phosphor cannot be obtained. Further, it is described that it is preferable to gradually nitride the surface of the alloy powder while dissipating the heat accompanying the nitriding reaction in order to prevent melting of the raw material alloy powder and rapid heat generation. Since it is necessary to slow the rate of temperature rise at a temperature around the melting point of the alloy or to reduce the amount of the raw material alloy, the heating time becomes long and productivity may be reduced.
JP 2005-54182 A International publication pamphlet WO2007 / 135975

  The object of the present invention is to solve the problems of conventional solid-phase methods and phosphor manufacturing methods using alloys as raw materials, and to produce phosphors that exhibit high-luminance emission and little deterioration during use safely and efficiently. It is to provide a way to do.

As a result of intensive studies in view of this point, the present inventors, as a result, in a method for producing an (acid) nitride phosphor containing an activating element M1, a divalent metal element M2, and a tetravalent metal element M4, The inventors have found that the above object can be achieved by using an alloy containing an activating element M1 and a divalent metal element M2 and a nitride of a tetravalent metal element M4 as raw materials, and completed the present invention. .
The gist of the present invention is the following (1) to ( 16 ).

(1) In the method of the activation element M1,2 divalent metal elements M2, 3 trivalent metal elements M3, and a nitride containing tetravalent metal elements M4 or oxynitride phosphor, as a raw material, at least A phosphor manufacturing method using an alloy containing an activation element M1 and a divalent metal element M2 and a nitride of a tetravalent metal element M4 and heating the raw material in an atmosphere containing a nitrogen element. The activation element M1 contains Eu and / or Ce, and 50 mol% or more of the divalent metal element M2 is Ca and / or Sr, and 50 mol% or more of the trivalent metal element M3 is Al. And 50% by mole or more of the tetravalent metal element M4 is Si .

( 2 ) The active element M1 is selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, and Eu and / or Ce. at least one element as essential elements, tetravalent metal elements M4 is Si, Ge, Sn, Ti, Zr, and selected from the group consisting of Hf, at least one element as essential elements of Si (1 ) The method for producing a phosphor according to (1 ) .

( 3 ) The trivalent metal element M3 is one or more elements selected from the group consisting of Al, Ga, In, and Sc and having Al as an essential element (1) or (2 ) Phosphor manufacturing method.

( 4 ) An active element M1, an alloy containing a valent metal element M2, and a trivalent metal element M3 and a nitride of a tetravalent metal element M4 are used as raw materials ( 1 ) to method for manufacturing the phosphor according to any one of (3).

( 5 ) As raw materials, an active element M1, an alloy containing a valent metal element M2, and a trivalent metal element M3, an alloy containing a divalent metal element M2 and a tetravalent metal element M4, The method for producing a phosphor according to any one of ( 1 ) to ( 3 ) , wherein a nitride of a tetravalent metal element M4 is used.

( 6 ) As raw materials, an active element M1, an alloy containing a divalent metal element M2, and a tetravalent metal element M4, an alloy containing a divalent metal element M2 and a trivalent metal element M3, The method for producing a phosphor according to any one of ( 1 ) to ( 3 ) , wherein a nitride of a tetravalent metal element M4 is used.

(7) The method for producing a phosphor according to any one of _{the weight-average} median diameter _{D 50} of the alloy (1), characterized in that at 200μm or less (6).

(8) as a nitride of tetravalent metal elements M4, the production method of the phosphor according to any one of (1), characterized by using a powder weight median diameter D ₅₀ is 100μm or less (7) .

( 9 ) The method for producing a phosphor according to any one of ( 1 ) to ( 8 ), wherein the nitride or oxynitride phosphor is a phosphor represented by the following general formula [1]: .
_{M1 a M2 b M3 c M4 d} N e O f [1]
(Wherein M1 is an activator element, M2 is a divalent metal element, M3 is a trivalent metal element, M4 is a tetravalent metal element, and a, b, c, e, Each f is a value within the following range.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5)

( 10 ) A phosphor-containing composition comprising a phosphor produced by the method according to any one of (1) to ( 9 ) and a liquid medium.

( 11 ) A first illuminant and a second illuminant that emits visible light when irradiated with light from the first illuminant, wherein the second illuminant comprises (1) to ( 9 ). A light-emitting device comprising one or more phosphors produced by the method according to any one of the above as the first phosphor.

(12) said second luminous body, one or more different fluorophores of said first peak emission wavelength and the phosphor, according to characterized in that it contains as the second phosphor (11) Light-emitting device.

( 13 ) The first light emitter has a light emission peak in a wavelength range of 420 nm to 500 nm, and the second light emitter emits light in a wavelength range of 500 nm to 570 nm as the second phosphor. The light-emitting device according to ( 12 ), comprising at least one kind of phosphor having a peak.

( 14 ) The first light emitter has a light emission peak in a wavelength range of 300 nm to 420 nm, and the second light emitter emits light in a wavelength range of 420 nm to 500 nm as the second phosphor. The light-emitting device according to ( 12 ), comprising at least one phosphor having a peak and at least one phosphor having an emission peak in a wavelength range of 500 nm to 570 nm.

( 15 ) An image display device comprising the light-emitting device according to any one of ( 11 ) to ( 14 ) as a light source.

( 16 ) An illumination device comprising the light-emitting device according to any one of ( 11 ) to ( 14 ) as a light source.

  According to the method for manufacturing a phosphor of the present invention, it is possible to provide a phosphor that exhibits high-luminance light emission and has little deterioration during use in a safe and efficient manner. In particular, since it is not necessary to slow down the temperature rising rate at the time of manufacturing the phosphor or to reduce the amount of the raw material alloy, productivity can be improved.

  By the manufacturing method of the present invention, it is suitably used for fluorescent lamps, fluorescent display tubes (VFD), field emission displays (FED), plasma display panels (PDP), cathode ray tubes (CRT), white light emitting diodes (LEDs), etc. Useful phosphors are advantageously provided industrially.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

  In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

Further, in the phosphor composition formula in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed by separating them with commas (,), it indicates that one or more of the listed elements may be contained in any combination and composition. For example, the composition formula “(Ba, Sr, Ca) Al ₂ O ₄ : Eu” has “BaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “CaAl ₂ O ₄ : Eu”. If: the _{"Ba 1-x Sr x Al 2} O 4 Eu ": the _{"Ba 1-x Ca x Al 2} O 4 Eu ": a _{"Sr 1-x Ca x Al 2} O 4 Eu " _{"Ba 1-x-y Sr x} Ca y Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <X + y <1).

[Composition of phosphor]
The phosphor manufactured according to the present invention (hereinafter referred to as “phosphor of the present invention”) includes an activating element M1, a bivalent metal element M2, and a tetravalent metal element M4 (acid) nitride. Examples include phosphors.

  Examples of the activating element M1 include various light-emitting ions that can be contained in a crystal matrix constituting a phosphor having nitride or oxynitride as a matrix. Examples of the activating element M1 include Cr, Mn, and Fe. It is possible to manufacture a phosphor having high light emission characteristics by including one or more elements selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. This is possible and preferable. Further, the activator element M1 preferably contains one or more of Mn, Ce, Pr and Eu, and particularly contains Ce and / or Eu so that a high-luminance phosphor can be obtained. preferable. Moreover, in order to give various functions, such as raising a brightness | luminance and providing luminous property, as an activator element M1, you may contain 1 type or multiple types of coactivators other than Ce and / or Eu. .

  The divalent metal element M2 preferably includes at least an alkaline earth metal element, and specifically includes one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. This is preferable because a phosphor having high emission characteristics can be obtained. The production method of the present invention can be suitably used particularly for phosphors containing Ca.

  The tetravalent metal element M4 preferably contains one or more elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf because a phosphor with high emission characteristics can be obtained. The production method of the present invention can be suitably used particularly for a phosphor containing Si.

Specific examples of such phosphors include, for example, (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, (Ca, Sr, Ba). ) ₂ Si ₅ N ₈ : Ce, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Ce, and the like.

  In addition, as the phosphor of the present invention, an (acid) nitride phosphor containing an activating element M1, a bivalent metal element M2, a tetravalent metal element M4, and further containing a trivalent metal element M3 is used. It can also be mentioned.

  The trivalent metal element M3 is preferably one or more elements selected from the group consisting of Al, Ga, In, and Sc because a phosphor with high emission characteristics can be obtained.

  As the phosphor of the present invention, an (oxy) nitride phosphor represented by the following general formula [1] is particularly preferable because it is a high-luminance and stable phosphor.

_{M1 a M2 b M3 c M4 d} N e O f [1]
(However, a, b, c, e, and f are values in the following ranges, respectively.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5)

  In the general formula [1], as the activator element M1, various light-emitting ions that can be contained in a crystal matrix constituting a phosphor having nitride or oxynitride as a matrix can be used. When one or more elements selected from the group consisting of Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb are used, a phosphor having high emission characteristics is manufactured. Is possible and preferable. The activator element M1 preferably contains one or more of Mn, Ce, Pr and Eu, and in particular, it contains Ce and / or Eu to obtain a phosphor exhibiting high luminance red light emission. Is more preferable. Moreover, in order to give various functions, such as raising a brightness | luminance and providing luminous property, as an activator element M1, you may contain 1 type or multiple types of coactivators other than Ce and / or Eu. .

  Various divalent, trivalent, and tetravalent metal elements can be used as elements other than the activator element M1, but the divalent metal element M2 is made of Mg, Ca, Sr, Ba, and Zn. One or more elements selected from the group consisting of trivalent metal element M3 selected from the group consisting of Al, Ga, In, and Sc, and the tetravalent metal element M4 selected from Si, Ge, Sn, Ti , Zr, and Hf are preferably one or more elements selected from the group consisting of Hf, because a phosphor with high emission characteristics can be obtained.

  In addition, it is preferable to adjust the composition so that 50 mol% or more of the divalent metal element M2 is Ca and / or Sr because a phosphor with high emission characteristics can be obtained. In particular, 80 mol% or more of M2 is more preferably Ca and / or Sr, more preferably 90 mol% or more of M2 is Ca and / or Sr, and all of M2 is Ca and / or Sr. Most preferably.

  Further, it is preferable to adjust the composition so that 50 mol% or more of the trivalent metal element M3 is Al because a phosphor with high emission characteristics can be obtained. In particular, 80 mol% or more of M3 is preferably Al, more preferably 90 mol% or more of M3 is Al, and most preferably all M3 is Al.

  Further, it is preferable to adjust the composition so that 50 mol% or more of the tetravalent metal element M4 is Si because a phosphor with high emission characteristics can be obtained. In particular, 80 mol% or more of M4 is preferably Si, more preferably 90 mol% or more of M4 is Si, and most preferably all M4 is Si.

  In particular, 50 mol% or more of the divalent metal element M2 is Ca and / or Sr, 50 mol% or more of the trivalent metal element M3 is Al, and 50 of the tetravalent metal element M4. It is preferable to make Si at least mol% because a phosphor having particularly high emission characteristics can be produced.

  In addition, the reason why the numerical range of a to f in the general formula [1] is preferable is as follows.

  When a is smaller than 0.00001, sufficient light emission intensity tends to be not obtained, and when a is larger than 0.15, concentration quenching increases and the light emission intensity tends to decrease. Accordingly, the raw materials are mixed so that a is in the range of 0.00001 ≦ a ≦ 0.15. For the same reason, 0.0001 ≦ a ≦ 0.1 is preferable, 0.001 ≦ a ≦ 0.05 is more preferable, 0.002 ≦ a ≦ 0.04 is further preferable, and 0.004 ≦ a ≦ 0. .02 is most preferred.

  The raw material mixture composition is adjusted so that the sum of a and b is 1 because the activating element M1 replaces the atomic position of the metal element M2 in the crystal base of the phosphor.

  When c is smaller than 0.5 or when c is larger than 1.5, a heterogeneous phase is produced during production, and the yield of the phosphor tends to be low. Therefore, the raw materials are mixed so that c is in the range of 0.5 ≦ c ≦ 1.5. From the viewpoint of emission intensity, 0.5 ≦ c ≦ 1.5 is preferable, 0.6 ≦ c ≦ 1.4 is more preferable, and 0.8 ≦ c ≦ 1.2 is most preferable.

  Whether d is smaller than 0.5 or d is larger than 1.5, a heterogeneous phase is produced during production, and the yield of the phosphor tends to be low. Accordingly, the raw materials are mixed so that d is in the range of 0.5 ≦ d ≦ 1.5. From the viewpoint of light emission intensity, 0.5 ≦ d ≦ 1.5 is preferable, 0.6 ≦ d ≦ 1.4 is more preferable, and 0.8 ≦ d ≦ 1.2 is most preferable.

  e is a coefficient indicating the nitrogen content, and e = 2/3 + c + 4d / 3 = (2 + 3c + 4d) / 3. If 0.5 ≦ c ≦ 1.5 and 0.5 ≦ d ≦ 1.5 are substituted into this equation, the range of e becomes 1.84 ≦ e ≦ 4.17. However, in the phosphor composition represented by the general formula [1], the yield of the phosphor tends to decrease when e indicating the nitrogen content is less than 2.5. Even if e exceeds 3.5, the yield of the phosphor tends to decrease. Therefore, e is usually 2.5 ≦ e ≦ 3.5.

  The oxygen in the phosphor represented by the general formula [1] may be mixed as an impurity in the raw metal, or may be introduced during a manufacturing process such as a pulverization process or a nitriding process. The ratio of oxygen, f, is preferably 0 ≦ f ≦ 0.5 within a range in which a decrease in the light emission characteristics of the phosphor is acceptable.

Oxygen contained in the phosphor of the present invention may be mixed as an impurity in the raw metal, or mixed during a manufacturing process such as a pulverization process or a nitriding process.
The oxygen content is usually 5% by weight or less, preferably 2% by weight or less, and most preferably 1% by weight or less as long as the reduction in the light emission characteristics of the phosphor is acceptable.

As specific examples of the phosphor composition of the present invention, (Sr, Ca, Mg) AlSiN ₃ : Eu, (Sr, Ca, Mg) AlSiN ₃ : Ce, (Sr, Ca) ₂ Si ₅ N ₈ : Eu , (Sr, Ca) ₂ Si ₅ N ₈ : Ce and the like.

[Phosphor production method]
The method for producing a phosphor of the present invention includes an activator element as a raw material when producing an (acid) nitride phosphor containing an activator element M1, a divalent metal element M2, and a tetravalent metal element M4. An alloy containing M1 and a divalent metal element M2 and a nitride of a tetravalent metal element M4 are used, and the raw material is heated in an atmosphere containing a nitrogen element.

Further, when producing an (acid) nitride phosphor containing the activating element M1, the divalent metal element M2, the trivalent metal element M3, and the tetravalent metal element M4, the following (i) (Iii) is used, and the raw material is heated in an atmosphere containing nitrogen element.
(I) A combination of an active element M1, an alloy containing a divalent metal element M2 and a trivalent metal element M3 and a nitride of a tetravalent metal element M4 (ii) an active element M1, 2 A combination of an alloy containing the metal element M2 and the trivalent metal element M3, an alloy containing the divalent metal element M2 and the tetravalent metal element M4, and a nitride of the tetravalent metal element M4 (Iii) activating element M1, alloy containing bivalent metal element M2 and tetravalent metal element M4, alloy containing divalent metal element M2 and trivalent metal element M3, and tetravalent metal element Combination with metal element M4 nitride

  Hereinafter, although the manufacturing method of the phosphor represented by the general formula [1], which is an embodiment of the present invention, will be specifically described, the phosphor manufactured by the manufacturing method of the phosphor of the present invention is: The phosphor is not limited to the phosphor represented by the general formula [1].

  The phosphor represented by the general formula [1] is an (oxy) nitride phosphor including an activating element M1, a divalent metal element M2, a trivalent metal element M3, and a tetravalent metal element M4. Since it exists, it can manufacture using the raw material of said (i)-(iii).

As the nitride of the tetravalent metal element M4 used in the raw materials (i) to (iii), a nitride of Si, Ge, Sn, Ti, Zr, or Hf, or a mixture thereof can be used. Since nitrogen is a trivalent element, specifically, (Si, Ge, Sn, Ti, Zr, Hf) ₃ N ₄ is used, preferably (Si, Ge) ₃ N ₄ , particularly preferably Si _3. N ₄ is used.

(M1 _a M2 _b ) M3 _c may be mentioned as an alloy containing the activating element M1, the divalent metal element M2, and the trivalent metal element M3 used in the raw material (i). ((Ce, Eu) _a (Mg, Ca, Sr, Ba, Zn) _b ) (Al, Ga, In, Sc) _c , and (Eu _a Ca _b ) Al _c , (Eu _a (Ca, Sr) _b ) Al _c , (Ce _a Ca _b ) Al _c , ( _{C a} (Ca, Sr) _b ) Al _c (where a, b, and c are each represented by the general formula [1 ] Is synonymous with

The alloy (M1 _a M2 _b ) M3 _c used as the raw material (i) and the use ratio of the M4 nitride are the same as those in the general formula [M1, M2, M3, M4 contained in the raw material used]. 1] is preferably used at such a ratio as to satisfy. However, even if it is not exactly the same as the composition in the general formula [1], it may be different by about ± 5%.

Two kinds of alloys used in the raw material (ii), an alloy containing an activating element M1, a divalent metal element M2, and a trivalent metal element M3, a divalent metal element M2 and a tetravalent metal element Preferred examples of the alloy containing M4 include M3 _2c (M1 _a M2 _b ) and M2 _2b M4 _d .

M3 _2c (M1 _a M2 _b ) is preferably (Al, Ga, In, Sc) _2c ((Ce, Eu) _a (Mg, Ca, Sr, Ba, Zn) _b ), particularly preferably. _{is, Al 2c (Eu a Ca b} ), Al 2c (Eu a (Ca, Sr) b), Al 2c (Ce a Ca b), Al 2c (Ce a (Ca, Sr) b) may be mentioned (wherein A, b, and c are as defined in the general formula [1]).

Further, as M2 _2b M4 _d , (Mg, Ca, Sr, Ba, Zn) _2b (Si, Ge, Sn, Ti, Zr, Hf) _d is preferable, and (Ca, Sr) is particularly preferable. _2b (Si, Ge) _d , Ca _2b (Si, Ge) _d , and Ca _2b Si _d (where b and d are as defined in the general formula [1]).

The alloy M3 _2c (M1 _a M2 _b ) and M2 _2b M4 _d used as the raw material (ii) and the use ratio of the nitride of M4 are such that the total amount of M1, M2, M3, and M4 contained in the raw material used is It is preferable to use them at a ratio satisfying the general formula [1]. However, even if it is not exactly the same as the composition in the general formula [1], it may be different by about ± 5%.

Two kinds of alloys used in the above raw material (iii), an alloy containing an activating element M1, a bivalent metal element M2, and a tetravalent metal element M4, a divalent metal element M2 and a trivalent metal element Examples of the alloy containing M3 include (M1 _a M2 _b ) ₂ M4 _d and M2 _b M3 _2c .

(M1 _a M2 _b ) ₂ M4 _d is preferably ((Ce, Eu) _a (Mg, Ca, Sr, Ba, Zn) _b ) ₂ (Si, Ge, Sn, Ti, Zr, Hf) _d . particularly _{preferably, (Eu a (Ca, Sr} ) b) 2 Si d, (Ce a (Ca, Sr) b) 2 Si d, (Eu a Ca b) 2 Si d, (Ce a Ca _b ) ₂ Si _d (wherein a, b and d have the same meanings as in the general formula [1]).

_As the M2 b _{M3 2c, preferably, (Mg, Ca, Sr,} Ba, Zn) b (Al, Ga, In, Sc) 2c and the like, particularly _{preferably, (Ca, Sr) b Al} 2c , And Ca _b Al _2c (where b and c are as defined in the general formula [1]).

The alloy (M1 _a M2 _b ) ₂ M4 _d and M2 _b M3 _2c used as the raw material (iii) and the use ratio of the nitride of M4 are the total amount of M1, M2, M3 and M4 contained in the raw material used These are preferably used in such a ratio that satisfies the general formula [1]. However, even if it is not exactly the same as the composition in the general formula [1], it may be different by about ± 5%.

For example, when the phosphor represented by the general formula [1] is CaAlSiN ₃ : Eu (that is, (Ca, Eu) AlSiN ₃ ), the following raw materials and proportions (molar ratio) are used. Is preferred.
For raw material (i) ⇒ (Eu, Ca) Al: Si ₃ N ₄ = 1: 1/3
In the case of the raw material (ii) ⇒ Al ₂ (Eu, Ca): Ca ₂ Si: Si ₃ N ₄
= 1/2: 1/4: 1/4
In the case of the raw material (iii) ⇒ (Eu, Ca) ₂ Si: CaAl ₂ : Si ₃ N ₄
= 1/4: 1/2: 1/4

  As an alloy used as a raw material, an alloy having an arbitrary shape such as a lump or powder can be used, but a powder is preferably used because of its high reactivity.

Weight-average median diameter D ₅₀ of the alloy powder used as a raw material, may be selected to suitable particle size by the activity of the metal elements constituting the alloy powder, usually, 200 [mu] m or less, preferably 100μm or less, more preferably Is 80 μm or less, particularly preferably 60 μm or less, 0.1 μm or more, preferably 0.5 μm or more, particularly preferably 1 μm or more.
However, if the alloy powder used as a raw material contains Sr has a high reactivity with atmospheric gas, the lower limit of the weight-average median diameter D ₅₀ of the alloy powder, usually 5μm or more, preferably 8μm or more, more preferably It is desirable that the thickness is 10 μm or more, particularly preferably 13 μm or more.
If the particle size of the raw material alloy powder is smaller than the range of the weight-average median diameter D ₅₀ of the aforementioned heat generation rate during the reaction such as nitriding becomes large, it may become difficult to control the reaction. On the other hand, when the weight median diameter D ₅₀ is larger than the above range, the reaction such as nitriding inside the alloy particles may be insufficient.

  The ratio of alloy particles having a particle size of 10 μm or less contained in the alloy powder is preferably 80% by weight or less, and the ratio of alloy particles having a particle size of 45 μm or more is preferably 40% by weight or less.

Further, the value of QD of the raw material alloy powder is not particularly limited, but is usually 0.59 or less. Here, QD is defined as QD = (D ₇₅ −D ₂₅ ) / (D ₇₅ + D ₂₅ ), where the particle size values when the integrated values are 25% and 75% are expressed as D ₂₅ and D ₇₅ , respectively. To do. A small QD value means a narrow particle size distribution.

  On the other hand, as the nitride of the tetravalent metal element M4 used as a raw material, it is usually preferable to use a powdered one.

M4 nitride weight median diameter D ₅₀ of the powder, unless there is no problem in mixing or reaction with other alloy materials is not particularly limited but usually 100μm or less, particularly preferably 80μm or less, more preferably is 60μm or less . It is preferable that _{the weight-average} median diameter _{D 50} of the raw material M4 nitride is 0.01μm or more, and more preferably 0.05μm or more.

{Manufacture of raw material alloys}
The raw material alloy described above can be manufactured by mixing a metal as a raw material or an alloy thereof, and melting and alloying it.
For the production of the raw material alloy, a metal corresponding to the element contained in the phosphor of the present invention, an alloy containing the metal, or the like can be used. Moreover, only 1 type may be used for the raw material corresponding to the element which the fluorescent substance of this invention contains, respectively, and 2 or more types may be used together by arbitrary combinations and a ratio. However, among the raw materials, it is preferable to use Eu metal or Ce metal as the Eu raw material or Ce raw material used as the raw material of the activation element M1. This is because it is easy to obtain raw materials.

<Purity of metal for raw material alloy production>
As for the purity of the metal used for the production of the raw material alloy, impurities are usually 1 mol% or less, preferably 0.5 mol% or less as the metal raw material of the activator element M1 from the viewpoint of the light emission characteristics of the synthesized phosphor More preferably, it is preferable to use a metal purified to 0.1% or less. As described above, when Eu is used as the activation element M1, it is preferable to use Eu metal as the Eu raw material. As raw materials for elements other than the activation element M1, divalent, trivalent and tetravalent metals are used. For the same reason, the concentration of impurities contained is preferably 0.1 mol% or less. It is preferable to use a high-purity metal raw material of 0.01 mol% or less from the viewpoint that a phosphor with high emission characteristics can be produced.

<Shape of metal for raw material alloy production>
Although there is no restriction | limiting in the shape of the metal for raw material alloy manufacture, Usually, the particle | grain or lump shape of diameter several millimeters to several dozen mm is used.
When an alkaline earth metal element is used as the divalent metal element M2, the raw material may be any shape such as granular or massive, but it is preferable to select an appropriate shape according to the chemical properties of the raw material. For example, Ca is stable in the atmosphere in either a granular form or a lump, and can be used. However, since Sr is chemically more active, it is preferable to use a lump raw material.

<Melting of metal for manufacturing raw material alloys>
There are no particular restrictions on the method for melting the metal for manufacturing the raw material alloy, but usually a resistance heating method, an electron beam method, an arc melting method, and a high frequency induction heating method (hereinafter sometimes referred to as “high frequency melting method”). Etc. can be used. Moreover, it can also carry out combining 2 or more types of these methods. Among these, the arc melting method and the high frequency melting method are preferable, and the high frequency melting method is particularly preferable.

  In the present invention, the melting order of the metal for producing the raw material alloy is not particularly limited, but it is usually preferable to first melt the metal having a large amount or the melting point.

Examples of the crucible material that can be used at the time of melting include alumina, magnesia, calcia, graphite, and molybdenum.
The atmosphere at the time of melting the raw material alloy manufacturing metal is preferably an inert atmosphere, and an argon atmosphere is particularly preferable. At this time, only one kind of inert gas may be used, or two or more kinds may be used in any combination and ratio.
Further, the pressure is usually preferably 1 × 10 ³ Pa or more and 1 × 10 ⁵ Pa or less, and it is desirable that the pressure is not more than atmospheric pressure from the viewpoint of safety.

  In addition, about the metal element lost by volatilization, reaction with the material of a crucible, etc. at the time of melting | dissolving, you may weigh and add beforehand beforehand as needed.

<Casting of molten metal>
A raw material alloy is obtained by melting the metal for manufacturing the raw material alloy. Although this raw material alloy is usually obtained as a molten alloy, there are many technical problems in producing a phosphor directly from this molten alloy. Therefore, it is preferable to obtain a solidified body (hereinafter referred to as “alloy lump” as appropriate) through a casting process in which the molten alloy is poured into a mold and molded.

  However, in this casting process, segregation occurs due to the cooling rate of the molten metal, and a composition that has a uniform composition in the molten state may have an uneven composition distribution. Therefore, it is desirable that the cooling rate be as fast as possible. The mold is preferably made of a material having good thermal conductivity such as copper, and preferably has a shape in which heat is easily dissipated. It is also preferable to devise cooling the mold by means such as water cooling if necessary.

  By such a device, for example, it is preferable to use a mold having a large bottom area with respect to the thickness and solidify as soon as possible after pouring the molten metal into the mold.

  Also, since the degree of segregation varies depending on the composition of the alloy, it is necessary to prevent segregation by collecting samples from several places of the obtained solidified body by using necessary analytical means such as ICP emission spectroscopy. It is preferable to set a proper cooling rate.

  The atmosphere during casting is preferably an inert gas atmosphere, and an argon atmosphere is particularly preferable. At this time, only one kind of inert gas may be used, or two or more kinds may be used in any combination and ratio.

<Crushing of alloy lump>
Prior to the nitriding step by heating, the raw material alloy is preferably powdered with a desired particle size. Therefore, the alloy lump obtained in the casting step is preferably pulverized to obtain a raw material alloy powder having a desired particle size and particle size distribution (hereinafter sometimes simply referred to as “alloy powder”). (Crushing process).
Although there is no restriction | limiting in particular in the grinding | pulverization method of an alloy lump, For example, it is possible to carry out by the dry method and the wet method using organic solvents, such as ethylene glycol, hexane, and acetone.

Hereinafter, the dry method will be described in detail as an example.
This pulverization step may be divided into a plurality of steps such as a coarse pulverization step, a medium pulverization step, and a fine pulverization step as necessary. In this case, the entire pulverization process can be pulverized using the same apparatus, but the apparatus used may be changed depending on the process.

  Here, the coarse pulverization step is a step of pulverizing so that approximately 90% by weight of the alloy powder has a particle size of 1 cm or less. Can be used. The middle pulverization step is a step of pulverizing so that approximately 90% by weight of the alloy powder has a particle size of 1 mm or less, and a pulverizer such as a cone crusher, a crushing roll, a hammer mill, or a disk mill can be used. . The fine pulverization step is a step of pulverizing the alloy powder so as to have a weight median diameter, which will be described later. Can be used.

  Among these, from the viewpoint of preventing impurities from being mixed, it is preferable to use a jet mill in the final pulverization step. In order to use a jet mill, the alloy lump is preferably pulverized in advance until the particle size is about 2 mm or less. In the jet mill, the particles are pulverized mainly by using the expansion energy of the fluid injected from the nozzle original pressure to the atmospheric pressure. Therefore, the particle size can be controlled by the pulverization pressure, and contamination of impurities can be prevented. Is possible. Although the pulverization pressure varies depending on the apparatus, it is usually in the range of 0.01 MPa or more and 2 MPa or less in gauge pressure. Among them, 0.05 MPa or more and less than 0.4 MPa is preferable, and 0.1 MPa or more and 0.3 MPa or less. Is more preferable. If the gauge pressure is too low, the particle size of the obtained particles may be too large, and if it is too high, the particle size of the obtained particles may be too small.

  Moreover, when there is little quantity of an alloy lump, you may grind | pulverize using a mortar.

  Furthermore, in any case, it is necessary to appropriately select the relationship between the material of the pulverizer and the object to be crushed so that impurities such as iron do not enter during the pulverization process. For example, the powder contact portion is preferably subjected to ceramic lining, and among ceramics, it is preferable to be lined with alumina, silicon nitride, tungsten carbide, zirconia, or the like.

  In order to prevent oxidation of the alloy powder, the pulverization step is preferably performed in an inert gas atmosphere. Although there is no restriction | limiting in particular in the kind of inert gas, Usually, 1 type single atmosphere or 2 or more types mixed atmosphere can be used among gases, such as nitrogen, argon, and helium. Among these, a nitrogen atmosphere is particularly preferable from the viewpoint of economy.

Further, the oxygen concentration in the atmosphere is not limited as long as the oxidation of the alloy powder can be prevented, but it is usually preferably 10% by volume or less, particularly preferably 5% by volume or less. Moreover, as a minimum of oxygen concentration, it is about 10 ppm normally. By setting the oxygen concentration within a specific range, it is considered that an oxide film is formed on the surface of the alloy during pulverization and stabilized. However, when the pulverization step is performed in an atmosphere having an oxygen concentration higher than 5% by volume, dust may explode during the pulverization. Therefore, it is preferable to provide equipment that does not generate dust.
In addition, you may cool as needed so that the temperature of an alloy powder may not rise during a grinding | pulverization process.

<Classification of alloy powder>
The alloy powder obtained as described above is obtained by using, for example, a sieving device using a mesh such as a vibratory screen or a shifter; an inertia classifier such as an air separator; a centrifuge such as a cyclone, etc. After adjusting to the desired weight median diameter D ₅₀ and particle size distribution (classification step), it is preferably used for the subsequent steps.
In adjusting the particle size distribution, the coarse particles are preferably classified and recycled to a pulverizer, and the classification and / or recycling is more preferably continuous.

  This classification step is also preferably performed in an inert gas atmosphere. Although there is no restriction | limiting in particular in the kind of inert gas, Usually, 1 type single atmospheres, such as nitrogen, argon, helium, or 2 or more types of mixed atmospheres are used, and nitrogen atmosphere is especially preferable from a viewpoint of economical efficiency. For the same reason as in the pulverization step, the oxygen concentration in the inert gas atmosphere is preferably 10% by volume or less, particularly preferably 5% by volume or less.

{Raw material mixing process}
The phosphor of the present invention can be produced by nitriding the aforementioned raw material alloy powder and M4 nitride, but it is preferable to mix the raw material alloy powder and the M4 nitride powder before nitriding. As a mixer used for mixing, a horizontal cylindrical mixer, a double cone mixer, a V blender, a ribbon blender, a paddle blender, a conical screw, a high-speed fluid mixer, or the like may be used. it can. Moreover, you may mix using a mortar and a pestle.

  The mixing is preferably performed in an inert gas atmosphere in order to prevent oxidation of the raw material alloy. Although there is no restriction | limiting in particular in the kind of inert gas, Usually, you may mix only 1 type or 2 types or more among gases, such as nitrogen, argon, and helium, by arbitrary combinations and a ratio.

  The oxygen concentration in the inert gas atmosphere at the time of mixing is not limited as long as oxidation of the raw material alloy can be prevented, but is usually 10% by volume or less, and particularly preferably 5% by volume or less. Moreover, as a minimum of oxygen concentration, it is about 10 ppm normally. By setting the oxygen concentration in a specific range, it is considered that an oxide film is formed on the surface of the alloy during mixing and is stabilized. When the mixing step is performed in an atmosphere having an oxygen concentration higher than 5% by volume, dust may explode during mixing. Therefore, it is preferable to provide equipment that does not generate dust.

{Nitriding of raw materials}
The phosphor of the present invention can be manufactured by heating and nitriding the above-mentioned raw material alloy and M4 nitride in an atmosphere containing nitrogen element.

For example, first, raw material alloy powder and M4 nitride powder are filled in a crucible or tray. Examples of the material for the crucible or tray used here include boron nitride, silicon nitride, aluminum nitride, and tungsten. Boron nitride is preferable because of its excellent corrosion resistance.
After putting the crucible or tray filled with the alloy powder in a heating furnace capable of controlling the atmosphere, a gas containing nitrogen is circulated to sufficiently replace the inside of the system with the nitrogen-containing gas. If necessary, a nitrogen-containing gas may be circulated after the system is evacuated.

  Examples of the nitrogen-containing gas used in the nitriding treatment include a gas containing nitrogen, such as nitrogen, ammonia, or a mixed gas of nitrogen and hydrogen. The oxygen concentration in the system affects the oxygen content of the phosphor to be produced, and if the content is too high, high light emission cannot be obtained. Therefore, the oxygen concentration in the nitriding atmosphere is preferably as low as possible, usually 1000 ppm or less, Preferably it is 100 ppm or less, More preferably, it is 10 ppm or less. Further, if necessary, an oxygen getter such as carbon or molybdenum may be placed in the in-system heating portion to lower the oxygen concentration.

  The nitriding treatment is performed by heating in a state in which the nitrogen-containing gas is filled or in a flow state, and the pressure may be any state of reduced pressure, atmospheric pressure or increased pressure rather than atmospheric pressure. The pressure of the nitrogen-containing gas is at least a gauge pressure, and is usually 0.0001 MPa or more, preferably 0.01 MPa or more, and particularly preferably 0.05 MPa or more. If the pressure is less than atmospheric pressure, if the heating furnace has poor sealing properties, a large amount of oxygen may be mixed and a phosphor having high characteristics may not be obtained. The pressure of the nitrogen-containing gas is at least a gauge pressure, preferably 100 MPa or less, preferably 10 MPa or less, particularly preferably 5 MPa or less, but most preferably 1 MPa or less from the viewpoint of safety.

  When using a raw material alloy containing Sr, the pressure of the nitrogen-containing gas is at least a gauge pressure, preferably 1 MPa or more, and most preferably 10 MPa or more and 200 MPa or less.

  The heating temperature for nitriding the raw material is usually 800 ° C. or higher, preferably 1000 ° C. or higher, more preferably 1200 ° C. or higher, and usually 2200 ° C. or lower, preferably 2100 ° C. or lower, more preferably 2000 ° C. or lower. To do. When the heating temperature is lower than 800 ° C., the time required for the nitriding treatment becomes very long, which is not preferable. On the other hand, when the heating temperature is higher than 2200 ° C., the generated nitride volatilizes or decomposes, the chemical composition of the obtained phosphor shifts, and a phosphor with high characteristics cannot be obtained, and the reproducibility is also poor. There is a risk.

  The heating time (holding time at the maximum temperature) during the nitriding treatment may be a time required for the reaction between the raw material and nitrogen, but is usually 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more, and still more preferably Is 60 minutes or longer. When the heating time is shorter than 1 minute, the nitriding reaction is not completed and a phosphor having high characteristics cannot be obtained. The upper limit of the heating time is determined from the viewpoint of production efficiency, and is usually 24 hours or less.

  Further, the rate of temperature increase during the nitriding treatment is not limited and may be appropriately selected from the viewpoint of productivity and the like, and it is not necessary to increase the temperature particularly slowly before and after the melting point of the raw material alloy as in the conventional method. The heating rate is usually 10 ° C./hour or more, preferably 100 ° C./hour or more, more preferably 200 ° C./hour or more, and usually 1000 ° C./hour or less, preferably 900 ° C./hour or less. . Even in the temperature range before and after the melting point of the raw material alloy, the temperature rising rate can be 200 ° C./hour or more.

In the nitriding treatment, the target phosphor previously produced, for example, the phosphor represented by the general formula [1] may be added as a seed crystal to the nitriding treatment. Good.
In this case, the weight median diameter D ₅₀ of the seed crystal is not particularly limited as long as mixing with other raw materials is not hindered, but is preferably easy to mix with other raw materials, for example, raw material alloy powder or M4 nitriding It is preferable that it is about the same as the product powder. Usually, the weight median diameter D ₅₀ of the seed crystal is preferably 200 μm or less, more preferably 100 μm or less, particularly preferably 80 μm or less, further preferably 60 μm or less, and preferably 0.1 μm or more. More preferably, it is 0.5 μm or more.

  The mixing ratio of the seed crystal to the entire raw material (excluding the seed crystal) is usually preferably 1% by weight to 50% by weight. This suppresses the rate of heat generation per unit volume during nitriding, and as a result, the generated heat causes melting of the raw material, phase separation, or decomposition of the nitride, resulting in a deterioration in the properties of the obtained phosphor. Can be suppressed. It also has the effect of promoting crystal grain growth.

  Further, in the nitriding treatment step, a flux may coexist in the reaction system from the viewpoint of growing a good crystal.

{Reheating treatment}
The (oxy) nitride phosphor obtained by the nitriding treatment of the raw material described above may be subjected to particle growth by reheating as necessary for the purpose of obtaining high light emission (reheating treatment). ).

  The heating conditions for the reheating treatment are preferably 1200 ° C. or higher and 2200 ° C. or lower. If this temperature is less than 1200 ° C., the effect of growing particles is small even if reheating is performed. On the other hand, when heating at a temperature exceeding 2200 ° C., not only wasteful heating energy is consumed, but also the phosphor is decomposed, and the target fluorescence must be obtained unless the pressure of nitrogen, which is part of the atmospheric gas, is very high. The body cannot be manufactured. For the same reason, the reheating temperature is preferably 1300 ° C. or higher, more preferably 1400 ° C. or higher, and most preferably 1500 ° C. or higher. Moreover, 2100 degrees C or less is preferable, 2000 degrees C or less is more preferable, and 1900 degrees C or less is the most preferable.

  The atmosphere for the reheating treatment is basically an inert atmosphere such as a nitrogen-containing gas or a reducing atmosphere. The oxygen concentration in the atmosphere is usually 1000 ppm or less, preferably 100 ppm or less, more preferably 10 ppm or less. If reheating treatment is performed in an oxidizing atmosphere such as in an oxygen-containing gas or in the air where the oxygen concentration exceeds 1000 ppm, the phosphor is oxidized and the target phosphor cannot be obtained. However, it is preferable to use an atmosphere containing a trace amount of oxygen of about 0.1 ppm to 10 ppm because phosphors can be synthesized at a relatively low temperature.

  The pressure during the reheating treatment is preferably set to a pressure equal to or higher than atmospheric pressure in order to prevent oxygen from being mixed in the atmosphere. If the pressure is less than atmospheric pressure, as in the heating process during nitriding, there is a possibility that a large amount of oxygen is mixed and a high-quality phosphor cannot be obtained if the heating furnace is poorly sealed.

  The heating time (retention time at the maximum temperature) during the reheating treatment is usually 1 minute or more and 100 hours or less. If the holding time is too short, the particle growth does not proceed sufficiently, and if the holding time is too long, not only is unnecessary heating energy consumed, but nitrogen is desorbed from the surface of the phosphor and the emission characteristics are reduced. There is a tendency to decrease. For the same reason, the holding time is preferably 10 minutes or longer, more preferably 30 minutes or longer, preferably 24 hours or shorter, more preferably 12 hours or shorter.

{Other processes}
In the method for producing the phosphor of the present invention, it may have a step other than the above, for example, a pulverization step, a classification step, a washing step, a drying step, a surface treatment step, and other post-treatment steps at an arbitrary timing. .

<Crushing process>
In the pulverization step, mechanical force is applied to the aggregated phosphors due to particle growth and sintering during nitriding, and pulverization is performed. For example, a method such as pulverization with an air current such as a jet mill or pulverization with a medium such as a ball mill or a bead mill can be used.

<Classification process>
The phosphor powder obtained by pulverization as necessary can be adjusted to a desired particle size distribution by performing a classification step. For classification, for example, a sieving apparatus using a mesh such as a vibratory screen or a shifter, an inertia classifier such as an air separator or a water tank apparatus, or a centrifugal classifier such as a cyclone can be used.

<Washing process>
In the cleaning step, the phosphor is cleaned using a neutral or acidic solution (hereinafter sometimes referred to as “cleaning medium”). In addition, it is preferable to perform the washing step after the above-described pulverization step, because the characteristics of the phosphor tend to be improved.
As a neutral solution used here, it is preferable to use demineralized water or distilled water. As the acidic solution, an aqueous solution in which one or more mineral acids such as hydrochloric acid and sulfuric acid are diluted can be used. The concentration of the acid in the acid aqueous solution is usually preferably from 0.1 mol / l to 5 mol / l. When an acidic aqueous solution is used, it is preferable in terms of efficiency of reducing the amount of dissolved ions of the phosphor. However, if the acid concentration of the acid aqueous solution used for this cleaning is too high, the phosphor surface may be dissolved. The effect used may not be obtained sufficiently.
Moreover, only 1 type may be used for a washing | cleaning medium, and you may wash | clean using 2 or more types by arbitrary combinations and a ratio.

  Moreover, you may perform a washing | cleaning process in multiple times. When performing multiple washing steps, washing with water and washing with an acidic solution may be performed in combination, but in that case, washing with an acidic solution is performed in order to prevent acid from adhering to the phosphor. Thereafter, it is preferable to perform washing with water. Further, after washing with water, washing with an acidic solution may be performed, followed by washing with water.

  Moreover, when performing the washing | cleaning process in multiple times, you may perform the above-mentioned grinding | pulverization process and classification process between washing | cleaning processes.

<Drying process>
After the washing, the phosphor is preferably dried until it is free of attached moisture and used. As an example of specific operation, the phosphor slurry that has been washed may be dehydrated with a centrifugal separator or the like, and the obtained dehydrated cake may be filled in a drying tray. Then, it dries in the temperature range of 100 ° C. to 200 ° C. until the water content becomes 0.1% by weight or less. The obtained dried cake is passed through a sieve or the like and lightly crushed to obtain a phosphor.

<Surface treatment process>
Moreover, you may surface-treat with respect to the obtained fluorescent substance. Examples of the surface treatment include a treatment in which fine particles such as silica, alumina, and calcium phosphate are attached to the surface of the phosphor as a thin layer. Thereby, the powder characteristics (aggregation state, dispersibility in solution, sedimentation behavior, etc.) of the phosphor can be improved.

<Other post-processing steps>
In addition, post-treatment after heat treatment is generally known for known phosphors such as phosphors used in cathode ray tubes, plasma display panels, fluorescent lamps, fluorescent display tubes, X-ray intensifying screens, and the like. The technology can be used, and can be selected and applied as appropriate according to the purpose and application.

[Characteristics of phosphor]
<Luminescent color>
The emission color of the phosphor of the present invention can be set to a desired emission color such as blue, blue-green, green, yellow-green, yellow, orange, and red by adjusting the chemical composition and the like.

<Emission spectrum>
For example, the phosphor represented by the general formula [1] in which M1 is Eu preferably has the following characteristics when an emission spectrum is measured in view of the use as an orange or red light-emitting phosphor. .

  First, the phosphor represented by the general formula [1] in which M1 is Eu (hereinafter sometimes referred to as “the phosphor of the present invention [1]”) has an emission spectrum when excited with light having a wavelength of 465 nm. The peak wavelength λp (nm) is usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. If this emission peak wavelength λp is too short, it tends to be yellowish, while if it is too long, it tends to be dark reddish, and there is a possibility that the characteristics as orange or red light may deteriorate. It is not preferable.

  In addition, the phosphor [1] of the present invention has a full width at half maximum (hereinafter abbreviated as “FWHM” where appropriate) in the emission spectrum when excited with light having a wavelength of 465 nm. It is preferably larger, especially 70 nm or more, and usually less than 150 nm, especially 120 nm or less. If the full width at half maximum FWHM is too narrow, the emission intensity may decrease, and if it is too wide, the color purity may decrease.

  In order to excite the phosphor [1] of the present invention with light having a peak wavelength of 465 nm, for example, a GaN-based light emitting diode can be used. In addition, the measurement of the emission spectrum of the phosphor [1] of the present invention is performed, for example, with a fluorescence measuring apparatus (Japan) having a 150 W xenon lamp as an excitation light source and a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus. (Manufactured by Spectroscopic Co., Ltd.) or the like. The emission peak wavelength and the half width of the emission peak can be calculated from the obtained emission spectrum.

The excitation spectrum of the phosphor [1] of the present invention is not limited. For example, the excitation spectrum at an emission wavelength of 650 nm is usually 250 nm or more, preferably 300 nm or more, and usually 600 nm or less, preferably 550 nm or less. Visible light is emitted when excited by light.
Since the phosphor [1] of the present invention can absorb light in a wide wavelength range as described above, it is presumed that the phosphor [1] can emit light with higher luminance than the conventional phosphor.
The excitation spectrum of the phosphor [1] of the present invention can be measured using, for example, the same measuring apparatus as mentioned in the section of the emission spectrum measuring method.

<Weight average median diameter _{D 50>}
The phosphor of the present invention has a weight median diameter D ₅₀ of usually 3 μm or more, especially 5 μm or more, preferably 10 μm or more, and usually 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less. When the weight median diameter D ₅₀ is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter D ₅₀ is too large, there is a tendency that coating unevenness, blockage of a dispenser, etc. occur.
For the same reason, the phosphor of the present invention preferably has as small a content of coarse particles having a particle size of 100 μm or more as possible, and more preferably has a content of coarse particles having a particle size of 50 μm or more as small as possible. The content of is preferably substantially zero.
The weight-average median diameter D ₅₀ of the phosphor in the present invention, for example, can be measured using a device such as a laser diffraction / scattering particle size distribution measuring apparatus.

<Temperature characteristics>
The phosphor of the present invention also has excellent temperature characteristics. Specifically, the ratio of the emission peak intensity value in the emission spectrum diagram at 150 ° C. to the emission peak intensity value in the emission spectrum diagram at 25 ° C. when light having a peak at a wavelength of 455 nm is normally 55 % Or more, preferably 60% or more, particularly preferably 70% or more.
Further, since the emission intensity of ordinary phosphors decreases with increasing temperature, it is unlikely that the ratio exceeds 100%, but it may exceed 100% for some reason. However, if it exceeds 150%, the color shift tends to occur due to a temperature change.

  The phosphor of the present invention is excellent in temperature characteristics not only with respect to the emission peak intensity but also in terms of luminance. Specifically, the ratio of the luminance at 150 ° C. to the luminance at 25 ° C. when irradiated with light having a peak at a wavelength of 455 nm is usually 55% or more, preferably 60% or more, particularly preferably 70%. That's it.

<Others>
The phosphor of the present invention is more preferable as its internal quantum efficiency is higher. The value is usually 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more. If the internal quantum efficiency is low, the light emission efficiency tends to decrease, which is not preferable.
The phosphor of the present invention is preferably as its absorption efficiency is high. The value is usually 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more. If the absorption efficiency is low, the light emission efficiency tends to decrease, which is not preferable.

[Use of phosphor]
The phosphor of the present invention can be suitably used for various light emitting devices by taking advantage of its high luminance and high color rendering properties. For example, when the phosphor of the present invention is an orange or red phosphor, a high color rendering white light emitting device can be realized by combining a green phosphor, a blue phosphor, and the like. The light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.

[Phosphor-containing composition]
The phosphor of the present invention can be used by mixing with a liquid medium. In particular, when the phosphor is used for an application such as a light emitting device, it is preferably used in a form dispersed in a liquid medium. A phosphor dispersed in a liquid medium is appropriately referred to as “the phosphor-containing composition of the present invention”.

  The phosphor-containing composition of the present invention contains one or more phosphors obtained by the production method of the present invention. Furthermore, the phosphor-containing composition of the present invention may contain a phosphor other than the phosphor obtained by the production method of the present invention unless the effects of the present invention are significantly impaired. When two or more kinds of phosphors are contained, the combination and ratio can be appropriately selected depending on the purpose.

  The liquid medium used in the phosphor-containing composition of the present invention is not particularly limited as long as the performance of the phosphor is not impaired within the intended range. For example, any inorganic material and / or organic material may be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause an undesirable reaction. it can.

  Examples of the inorganic material include a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or an inorganic material (for example, having a siloxane bond). Inorganic material).

  Examples of organic materials include thermoplastic resins, thermosetting resins, and photocurable resins. Specific examples include methacrylic resins such as polymethylmethacrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; polyvinyl alcohols; Cellulose-based resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

  Among these, when using a phosphor for a high-power light-emitting device such as illumination, it is preferable to use a silicon-containing compound for the purpose of heat resistance and light resistance.

  The silicon-containing compound refers to a compound having a silicon atom in the molecule, for example, an organic material (silicone material) such as polyorganosiloxane, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, and borosilicate. And glass materials such as phosphosilicate and alkali silicate. Among these, silicone materials are preferable from the viewpoint of ease of handling.

The silicone material generally refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the following formula and / or a mixture thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D
(R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q
In the above formula, R ¹ to R ⁶ may be the same or different and are selected from the group consisting of an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are numbers that are 0 or more and less than 1, and satisfy M + D + T + Q = 1.

  When used for sealing a semiconductor light emitting device, the silicone material can be used after being sealed with a liquid silicone material and then cured by heat or light.

  When silicone materials are classified according to the curing mechanism, silicone materials such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide vulcanization type can be generally cited. Among these, addition polymerization curing type (addition type silicone material), condensation curing type (condensation type silicone material), and ultraviolet curing type are preferable.

  The content of the phosphor and the liquid medium in the phosphor-containing composition of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but the liquid medium is based on the entire phosphor-containing composition of the present invention. The amount is usually 50% by weight or more, preferably 75% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less. Further, the phosphor is usually 1% by weight or more, preferably 5% by weight or more, and usually 50% by weight or less, preferably 25% by weight or less, based on the entire phosphor-containing composition of the present invention. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium and a phosphor. On the other hand, when there is too little liquid medium, there is no fluidity and it may be difficult to handle.

  The liquid medium mainly serves as a binder in the phosphor-containing composition of the present invention. The liquid medium may be used alone or in combination of two or more in any combination and ratio. For example, when a silicon-containing compound is used for the purpose of heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin may be contained to the extent that the durability of the silicon-containing compound is not impaired. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the total amount of the liquid medium as the binder.

  In addition, the phosphor-containing composition of the present invention can appropriately contain other components depending on its use and the like. Examples of other components include a diffusing agent, a thickener, a bulking agent, an interference agent, and an ultraviolet ray preventing agent. Specifically, silica-based fine powder such as Aerosil, alumina powder and the like can be mentioned. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

  According to the phosphor-containing composition of the present invention, the phosphor of the present invention can be easily fixed at a desired position. For example, when the phosphor-containing composition of the present invention is used in the production of a light-emitting device, the phosphor-containing composition of the present invention is molded at a desired position and the liquid medium is cured. The phosphor can be sealed, and the phosphor of the present invention can be easily fixed at a desired position.

[Light emitting device]
Next, the light emitting device of the present invention will be described.
The light-emitting device of the present invention (hereinafter referred to as “light-emitting device” as appropriate) includes a first light-emitting body (excitation light source), and a second light-emitting body that emits visible light when irradiated with light from the first light-emitting body. The second light emitter contains, as the first phosphor, one or more of the phosphors of the present invention obtained by the above-described production method of the present invention.

  For example, the phosphor [1] represented by the general formula [1] in which M1 is Eu, as described above, is a phosphor that emits orange or red light when irradiated with light from an excitation light source. Suitable for the light emitting device of the invention. In the light emitting device of the present invention, any one of the phosphors of the present invention may be used alone, or two or more of them may be contained in any combination and ratio.

Specifically, the light-emitting device of the present invention uses an excitation light source as will be described later as the first light emitter, adjusts the type and proportion of the phosphor used as the second light emitter, and is a known device configuration By arbitrarily taking, a light emitting device that emits light in any color can be manufactured.
For example, a white light emitting device is manufactured by combining an excitation light source that emits blue light, a phosphor that emits green fluorescence (green phosphor), and a phosphor that emits orange or red fluorescence (orange or red phosphor). be able to. The emission color in this case can be changed to a desired emission color by adjusting the emission wavelength of the phosphor to be used. For example, a so-called pseudo white color (for example, a blue light emitting diode (hereinafter referred to as a light emitting diode as appropriate) It is also possible to obtain an emission spectrum similar to the emission spectrum of a light emitting device combining a “LED” and a phosphor emitting yellow fluorescence (yellow phosphor). Further, by combining a red phosphor with this white light emitting device, it is possible to realize a light emitting device that is extremely excellent in red color rendering and a light emitting device that emits light of a light bulb color (warm white). Also, a white light emitting device can be manufactured by combining an excitation light source that emits near-ultraviolet light with a phosphor that emits blue fluorescence (blue phosphor), a green phosphor, and a red phosphor.

  Here, the white color of the white light emitting device means all of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.

  Furthermore, if necessary, a yellow phosphor, a blue phosphor, an orange to red phosphor, another type of green phosphor, and the like are combined to adjust the type and use ratio of the phosphor and emit light in an arbitrary color. A light emitting device can also be manufactured.

  Note that the emission spectrum of the light emitting device is measured by energizing 20 mA with a color / illuminance measurement software and USB2000 series spectroscope (integral sphere specification) manufactured by Ocean Optics in a room maintained at a temperature of 25 ± 1 ° C. Can be done. Chromaticity values (x, y, z) can be calculated as chromaticity coordinates in the XYZ color system defined by JIS Z8701 from data in the wavelength region of 380 nm to 780 nm of the emission spectrum. In this case, the relational expression x + y + z = 1 holds. In the present specification, the XYZ color system may be referred to as an XY color system, and is usually expressed as (x, y).

{Configuration of light emitting device (light emitter)}
<First luminous body>
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

  The light emission wavelength of the first light emitter is not particularly limited as long as it overlaps with the absorption wavelength of the second light emitter described later, and a light emitter having a wide light emission wavelength region can be used. Usually, an illuminant having an emission wavelength from the ultraviolet region to the blue region is used, and it is particularly preferable to use an illuminant having an emission wavelength from the near ultraviolet region to the blue region.

  As a specific numerical value of the emission peak wavelength of the first illuminant, 200 nm or more is usually desirable. Among these, when near ultraviolet light is used as excitation light, it is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and a light emitting body having a peak emission wavelength of usually 420 nm or less (near ultraviolet light emitting body). ) Is desirable. When blue light is used as excitation light, it is usually 420 nm or more, preferably 430 nm or more, and a light emitter (blue light emitter) having a peak emission wavelength of usually 500 nm or less, preferably 480 nm or less is used. It is desirable. Both are from the viewpoint of color purity of the light emitting device.

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, an LED, a semiconductor laser diode (hereinafter abbreviated as “LD” as appropriate), or the like can be used. In addition, as a light-emitting body which can be used as a 1st light-emitting body, an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example. However, what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.

Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have remarkably large light output and external quantum efficiency compared to SiC-based LEDs that emit light in this region, and are extremely combined with the phosphor [1] of the present invention. This is because very bright light emission can be obtained with low power. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. The GaN-based LED or LD preferably has an Al _x Ga _y N light emitting layer, a GaN light emitting layer, or an In _x Ga _y N light emitting layer. Among GaN-based LEDs, those having an In _x Ga _y N light-emitting layer are particularly preferable because the emission intensity is very strong, and in GaN-based LEDs, the In _x Ga _y N layer and the GaN layer are also among them. A multi-quantum well structure is particularly preferable because the emission intensity is very strong.

  In the above, the value of x + y is usually in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light emitting layer, p layer, n layer, electrode, and substrate as basic components, and the light emitting layer is made of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a hetero structure sandwiched by Ga _y N layers or the like are preferable because of high light emission efficiency, and those having a hetero structure having a quantum well structure are more preferable because of high light emission efficiency.
Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio.

<Second luminous body>
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and at least the phosphor of the present invention is used as the first phosphor. A second phosphor (a red to orange phosphor, a green phosphor, a blue phosphor, a yellow phosphor, etc.), which will be described later, is contained as appropriate depending on the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

There is no restriction | limiting in particular in the composition of fluorescent substance other than the fluorescent substance of this invention used in the said 2nd light-emitting body. For example, metal oxides represented by Y ₂ O ₃ , YVO ₄ , Zn ₂ SiO ₄ , Y ₃ Al ₅ O ₁₂ , Sr ₂ SiO _4, etc., which become the crystal matrix, Sr ₂ Si ₅ N ₈ Metal nitrides typified by, etc., phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, etc. and sulfides typified by ZnS, SrS, CaS, etc., Y ₂ O ₂ S, La ₂ O ₂ S Ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ag, Cu, Au, Al, Mn, What combined the ion of metals, such as Sb, as an activator element or a coactivator element is mentioned.

Preferred examples of the crystal matrix include, for example, sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, ZnS; oxysulfides such as Y ₂ O ₂ S; (Y, Gd) ₃ Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl Aluminates such as ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O ₁₂ ; Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ ; Oxides such as SnO ₂ and Y ₂ O ₃ ; Borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ ; Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) 6 halophosphate of ₂ such as Cl; Sr ₂ P _{2 7,} it may be mentioned (La, Ce) phosphate PO _4, etc. and the like.

  However, the above-mentioned crystal matrix, activator element and coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.

  Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, as described above, phosphors that differ only in part of the structure are omitted as appropriate.

(First phosphor)
The second light emitter in the light emitting device of the present invention contains at least the above-described phosphor of the present invention as the first phosphor. Any one of the phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.
In addition to the phosphor of the present invention, a phosphor that emits fluorescence of the same color as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor. For example, when the phosphor of the present invention is a red phosphor, other types of orange or red phosphor can be used together with the phosphor of the present invention as the first phosphor.

(Second phosphor)
The second light emitter in the light emitting device of the present invention may contain one or more phosphors (that is, second phosphors) in addition to the first phosphor described above, depending on the application. . This second phosphor is a phosphor having an emission peak wavelength different from that of the first phosphor. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used.

For example, when the first phosphor is a green phosphor, a phosphor other than a green phosphor such as an orange to red phosphor, a blue phosphor, or a yellow phosphor is used as the second phosphor.
When the first phosphor is a blue phosphor, a phosphor other than a blue phosphor such as an orange to red phosphor, a green phosphor, or a yellow phosphor is used as the second phosphor.
When the first phosphor is a yellow phosphor, a phosphor other than a yellow phosphor such as an orange to red phosphor, a blue phosphor, or a green phosphor is used as the second phosphor.
When the first phosphor is an orange or red phosphor, a phosphor other than an orange or red phosphor such as a blue phosphor, a green phosphor, or a yellow phosphor is used as the second phosphor. It is done.

  The weight median diameter of the second phosphor used in the light emitting device of the present invention is usually in the range of 10 μm or more, especially 12 μm or more, and usually 30 μm or less, especially 25 μm or less. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

<Orange to red phosphor>
When an orange or red phosphor is used as the second phosphor, any orange or red phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the orange to red phosphor is usually in the wavelength range of 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred.

Such an orange to red phosphor is composed of, for example, fractured particles having a red fracture surface, and is represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that emits light in the red region. Europium activated alkaline earth silicon nitride-based phosphor, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Examples include europium activated rare earth oxychalcogenide phosphors represented by Eu.

  Furthermore, an oxynitride and / or an acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in the present invention. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu and Mn, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY _{9 (SiO 4) 6 O 2:} Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, Sr 2 BaSiO 5: Eu -activated silicate phosphors such as Eu, _{Y, Gd) 3 Al 5 O} 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce, (Mg, Ca, Sr , Ba) 2 Si 5 (N, Eu-activated oxides such as O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu , Nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn activated halophosphate phosphor such as Eu, Mn, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphor such as Eu, Mn, 3.5MgO · 0.5MgF ₂ · GeO _2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, _{a) 2 O 3: Eu,} Eu Bi, etc., Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Eu Bi, etc., Bi Tsukekatsusan sulfide phosphor (Gd, Y, Lu, La) VO ₄ : Eu, Bi activated vanadate phosphors such as Eu and Bi, SrY ₂ S ₄ : Eu and Ce activated sulfide phosphors such as Eu and Ce, CaLa ₂ S ₄ : Ce-activated sulfide phosphor such as Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Eu, Mn activated phosphor phosphor such as Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Ce phosphors such as salt phosphors, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Si _zq Ge _q O _{12 + δ} It is also possible to use an activated silicate phosphor or the like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, (La, Y) ₂ O ₂ S: Eu or containing Eu complex More preferably, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu or (La, Y) ₂ O ₂ S: Eu, or Eu (dibenzoylmethane) ₃ It preferably contains a β-diketone Eu complex such as a 1,10-phenanthroline complex or a carboxylic acid Eu complex (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Sr, Ca) AlSi (N, O) ₃ : Eu or (La, Y) ₂ O ₂ S: Eu are particularly preferred.

Of the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

  Any one of the orange to red phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.

<Green phosphor>
When a green phosphor is used as the second phosphor, any green phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and is usually 570 nm or less, particularly 540 nm or less, further 535 nm or less. It is preferable. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.

As a specific example of the green phosphor, Eu activation represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fractured surface and emits light in the green region. Examples thereof include alkaline earth silicon oxynitride phosphors.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _{2. Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb activated silicate phosphor such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as Eu, Zn ₂ SiO _4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , ₃ Al ₅ O _12: Tb-activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm activated thiogallate phosphors such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, Eu activated oxynitride phosphor such as Eu activated β sialon _{, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu such as Eu Activated aluminate phosphors, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, Ce and Tb such, Tb-activated phosphate phosphor, Sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn Eu, Mn activated halosilicate phosphors such as (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu activated thioaluminate phosphors and thiogallate phosphors such as Eu, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, M ₃ S i ₆ O ₉ N ₄ : Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element). It is also possible to use Eu-activated oxynitride phosphors such as

  In addition, as the green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex. is there.

  Any one of the green phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.

<Blue phosphor>
When a blue phosphor is used as the second phosphor, any blue phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 500 nm or less, preferably 480 nm or less, more preferably 470 nm or less, still more preferably 460 nm or less. It is preferable to be in the wavelength range.

Such a blue phosphor is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape, and emits light in a blue region (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu represented by Eu. The activated barium magnesium aluminate phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ ( Cl, F): Eu-activated calcium halophosphate phosphor represented by Eu, composed of growing particles having a substantially cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu-activated alkaline earth aluminate phosphor represented by Eu, which is constituted by fractured particles having a fractured surface, rows of emission of blue-green region (Sr, Ca, Ba) Al 2 O 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: Eu -activated alkaline earth aluminate phosphor such as represented by Eu and the like.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm, BaAl ₈ O ₁₃ : Eu attached Active aluminate phosphor, Ce-activated thiogallate phosphor such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu, Mn such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn Active aluminate phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu-activated halophosphate phosphors such as Sb, BaAl ₂ Si _{2 8: Eu, (Sr, Ba} ) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate phosphor such as Eu, ZnS: Ag, ZnS : Sulfide phosphors such as Ag and Al, Y ₂ SiO ₅ : Ce activated silicate phosphors such as Ce, Tungsten phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn _{, (Sr, Ca) 10 (} PO 4) 6 · nB 2 O 3: Eu, 2SrO · 0.84P 2 O 5 · 0.16B 2 O 3: Eu such as Eu, Mn-activated borate phosphate phosphors Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu-activated halosilicate phosphor such as Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu-activated halosilicate phosphor such as Eu and EuSi ₉ Al ₁₉ ON ₃₁ , La _{1-x Ce x Al (Si} 6-z Al z) (N 10-z O z) ( here, x, and y are each 0 ≦ x Is a number satisfying 1,0 ≦ z ≦ 6.), La 1-xy Ce x Ca y Al (Si 6-z Al z) (N 10-z O z) ( here, x, y, and z Are numbers satisfying 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and 0 ≦ z ≦ 6.) Ce-activated oxynitride phosphors and the like can also be used.

  In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyralizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .

Among the above examples, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or It is preferable to contain (Ba, Ca, Mg, Sr) ₂ SiO ₄ : Eu, and (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ ( Cl, F) ₂ : Eu or (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is more preferable, and BaMgAl ₁₀ O ₁₇ : Eu, Sr ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : More preferably, Eu or Ba ₃ MgSi ₂ O ₈ : Eu is included. Of these, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu or (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu is particularly preferred for illumination and display applications.

  Any one of the blue phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.

<Yellow phosphor>
When a yellow phosphor is used as the second phosphor, any yellow phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And M ^a ₃ M ^b ₂ ^Mc ₃ O ₁₂ : Ce (where M ^a is a divalent metal element and M ^b is a trivalent metal element) , M ^c represents a tetravalent metal element.) Garnet-based phosphor having a garnet structure represented by AE ₂ M ^d O ₄ : Eu (where AE is Ba, Sr, Ca, Mg, and And at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge), etc., and oxygen of constituent elements of the phosphors of these systems Oxynitride phosphor, part of which is replaced with nitrogen, AEAlS A nitride system having a CaAlSiN ₃ structure such as i (N, O) ₃ : Ce (where AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg and Zn). Examples thereof include phosphors activated with Ce such as phosphors.

Other examples of yellow phosphors include sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. Body, Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : phosphor activated by Eu such as oxynitride-based phosphor having a sialon structure such as Eu, (M _1-A-B Eu _A Mn _B ) ₂ (BO ₃ ) _1-p (PO ₄ ) _p X (where M represents one or more elements selected from the group consisting of Ca, Sr, and Ba, and X represents F, Cl, and Represents one or more elements selected from the group consisting of Br, wherein A, B, and p are 0.001 ≦ A ≦ 0.3, 0 ≦ B ≦ 0.3, and 0 ≦ p ≦ 0.2, respectively. It is also possible to use Eu-activated or Eu / Mn co-activated halogenated borate phosphors.

Moreover, as yellow fluorescent substance, for example, brilliant sulfoflavine
FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45380), rhodamine 6G (Color Index Number) 160, etc.

  Any one of the yellow phosphors exemplified above may be used alone, or two or more thereof may be used in any combination and ratio.

<Selection of second phosphor>
As said 2nd fluorescent substance, 1 type of fluorescent substance may be used independently, and 2 or more types of fluorescent substance may be used together by arbitrary combinations and a ratio. Further, the ratio between the first phosphor and the second phosphor is also arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, the usage amount of the second phosphor, the combination and ratio of the phosphors used as the second phosphor, and the like may be arbitrarily set according to the use of the light emitting device.

  In the light emitting device of the present invention, whether or not the second phosphor (orange to red phosphor, yellow phosphor, blue phosphor, green phosphor, etc.) described above is used and its type depends on the use of the light emitting device. May be selected as appropriate. For example, when the phosphor of the present invention is a red phosphor and the light emitting device of the present invention is configured as a red light emitting device, only the first phosphor (the red phosphor of the present invention) is used. The use of the second phosphor is usually unnecessary.

  On the other hand, when the light-emitting device of the present invention is configured as a light-emitting device that emits white light, the first light-emitting body, the first phosphor (the phosphor of the present invention), and the like so as to obtain desired white light. What is necessary is just to combine a 2nd fluorescent substance appropriately. Specifically, as an example of a preferable combination of the first phosphor, the first phosphor, and the second phosphor when the light-emitting device of the present invention is configured as a white light-emitting device, for example, When the first phosphor (the phosphor of the present invention) emits orange or red light, the following combinations (1) to (2) are exemplified.

(1) A blue light-emitting body (blue LED or the like) having an emission peak in a wavelength range of 420 nm or more and 500 nm or less is used as the first light-emitting body, and an orange to red phosphor (the fluorescent light of the present invention) is used as the first phosphor. And a green phosphor having an emission peak in the wavelength range of 500 nm to 570 nm is used as the second phosphor. In this case, as the green phosphor, (Ba, Sr) ₃ Si ₆ O ₁₂ N ₂ : Eu, (Ba, Sr) ₂ SiO ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu, (Mg, Ca, Sr , Ba) One or two or more green phosphors selected from the group consisting of Si ₂ O ₂ N ₂ : Eu and β- (Si, Al) ₁₂ (O, N) ₁₆ : Eu are preferable.

(2) A near-ultraviolet illuminant (near-ultraviolet LED or the like) having an emission peak in a wavelength range of 300 nm to 420 nm is used as the first illuminant, and an orange to red phosphor (the present invention) As a second phosphor, a blue phosphor having an emission peak in a wavelength range of 420 nm to 500 nm and a green phosphor having an emission peak in a wavelength range of 500 nm to 570 nm are used in combination. To do. In this case, the blue phosphor is selected from the group consisting of (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu and (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ (Cl, F): Eu. One or more blue phosphors are preferred. As the green phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, Mn, β- (Si, Al) ₁₂ (O, N) ₁₆ : Eu, (Ca, Sr, Ba) Si ₂ N ₂ O: Eu, and (Ba, Sr) ₃ Si ₆ O ₁₂ N ₂ : One or more green phosphors selected from the group consisting of Eu Is preferred. The orange or red phosphor (such as the phosphor of the present invention) may be one or more oranges selected from the group consisting of (Sr, Ca) AlSiN ₃ : Eu and La ₂ O ₂ S: Eu. A red phosphor is preferred. Among them, a near-ultraviolet LED, BaMgAl ₁₀ O ₁₇ : Eu as a blue phosphor, (Ba, Sr) ₂ SiO ₄ : Eu, β- (Si, Al) ₁₂ (O, N) ₁₆ : Eu as a green phosphor Or (Ba, Sr) ₃ Si ₆ O ₁₂ N ₂ : Eu and (Sr, Ca) AlSiN ₃ : Eu as a red phosphor are preferably used in combination.

  In addition, the phosphor of the present invention is mixed with other phosphors (here, mixing does not necessarily mean that the phosphors need to be mixed with each other, but means that different types of phosphors are combined). ) Can be used. In particular, when phosphors are mixed in the combination described above, a preferable phosphor mixture is obtained. In addition, there is no restriction | limiting in particular in the kind and the ratio of the fluorescent substance to mix.

<Sealing material>
In the light emitting device of the present invention, the first and / or second phosphors are usually used by being dispersed in a liquid medium that is a sealing material.
Examples of the liquid medium include the same ones as described in the above-mentioned section [Phosphor-containing composition of the present invention].

  The liquid medium can contain a metal element that can be a metal oxide having a high refractive index in order to adjust the refractive index of the sealing member. Examples of metal elements that give a metal oxide having a high refractive index include Si, Al, Zr, Ti, Y, Nb, and B. These metal elements may be used alone or in combination of two or more in any combination and ratio.

  The presence form of such a metal element is not particularly limited as long as the transparency of the sealing member is not impaired. For example, a uniform glass layer may be formed as a metalloxane bond, and is present in a particulate form in the sealing member. You may do it. When present in the form of particles, the structure inside the particles may be either amorphous or crystalline, but is preferably a crystalline structure in order to provide a high refractive index. Further, the particle diameter is usually not more than the emission wavelength of the semiconductor light emitting device, preferably not more than 100 nm, more preferably not more than 50 nm, particularly preferably not more than 30 nm so as not to impair the transparency of the sealing member. For example, by mixing particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, niobium oxide, etc. with a silicone-based material, the metal element can be present in the sealing member in the form of particles. .

The liquid medium may further contain known additives such as a diffusing agent, a filler, a viscosity modifier, and an ultraviolet absorber.
In addition, these additives may use only 1 type and may use 2 or more types together by arbitrary combinations and ratios.

{Configuration of light emitting device (others)}
The other configurations of the light emitting device of the present invention are not particularly limited as long as the first light emitting body and the second light emitting body described above are provided. Usually, the first light emitting body described above is formed on an appropriate frame. And a second light emitter. At this time, the second light emitter is excited by the light emission of the first light emitter (that is, the first and second phosphors are excited) to emit light, and the first light emitter emits light. And / or it arrange | positions so that light emission of a 2nd light-emitting body may be taken out outside. In this case, the first phosphor and the second phosphor are not necessarily mixed in the same layer. For example, the second phosphor is contained on the layer containing the first phosphor. For example, the phosphor may be contained in a separate layer for each color development of the phosphor, such as by stacking layers.

  In the light emitting device of the present invention, members other than the above-described excitation light source (first light emitter), phosphor (second light emitter), and frame may be used. Examples thereof include the aforementioned sealing materials. In addition to the purpose of dispersing the phosphor (second light emitter) in the light emitting device, the sealing material is provided between the excitation light source (first light emitter), the phosphor (second light emitter), and the frame. It can be used for the purpose of bonding.

{Embodiment of Light Emitting Device}
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

  FIG. 1 is a schematic perspective view showing a positional relationship between a first light emitter serving as an excitation light source and a second light emitter configured as a phosphor containing portion having a phosphor in an example of the light emitting device of the present invention. Shown in In FIG. 1, reference numeral 1 denotes a phosphor-containing portion (second light emitter), reference numeral 2 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter), and reference numeral 3 denotes a substrate. In order to create a state in which they are in contact with each other, LD (2) and phosphor-containing portion (second light emitter) (1) are produced separately, and their surfaces are brought into contact with each other by an adhesive or other means. Alternatively, the phosphor-containing portion (second light emitter) may be formed (molded) on the light emitting surface of the LD (2). As a result, the LD (2) and the phosphor-containing portion (second light emitter) (1) can be brought into contact with each other.

  When such an apparatus configuration is employed, the light loss is such that light from the excitation light source (first light emitter) is reflected by the film surface of the phosphor-containing portion (second light emitter) and oozes out. Therefore, the light emission efficiency of the entire device can be improved.

  FIG. 2A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the light emitting device (4), reference numeral 5 is a mount lead, reference numeral 6 is an inner lead, reference numeral 7 is an excitation light source (first light emitter), reference numeral 8 is a phosphor-containing resin portion, reference numeral 9 is a conductive wire, reference numeral Reference numeral 10 denotes a mold member.

  FIG. 2B is a representative example of a light-emitting device in a form called a surface-mount type, and light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the figure, reference numeral 22 is an excitation light source (first light emitter), reference numeral 23 is a phosphor-containing resin portion as a phosphor-containing portion (second light emitter), reference numeral 24 is a frame, reference numeral 25 is a conductive wire, Reference numerals 26 and 27 indicate electrodes.

{Use of light emitting device}
The application of the light-emitting device of the present invention is not particularly limited and can be used in various fields where ordinary light-emitting devices are used. However, since the color reproduction range is wide and the color rendering property is high, illumination is particularly important. It is particularly preferably used as a light source for a device or an image display device.

[Lighting device]
When the light-emitting device of the present invention is applied to a lighting device, the above-described light-emitting device may be appropriately incorporated into a known lighting device. For example, a surface-emitting illumination device (11) incorporating the above-described light-emitting device (4) as shown in FIG. 3 can be mentioned.

  FIG. 3 is a cross-sectional view schematically showing one embodiment of the illumination device of the present invention. As shown in FIG. 3, the surface-emitting illumination device has a number of light-emitting devices (13) (described above) on the bottom surface of a rectangular holding case (12) whose inner surface is light-opaque such as a white smooth surface. The light emitting device (4) corresponds to the lid portion of the holding case (12) by arranging a power source and a circuit (not shown) for driving the light emitting device (13) on the outside thereof. A diffuser plate (14) such as a milky white acrylic plate is fixed at a location for uniform light emission.

  Then, the surface emitting illumination device (11) is driven to apply light to the excitation light source (first light emitter) of the light emitting device (13) to emit light, and part of the light emission is converted into the phosphor. The phosphor in the phosphor-containing resin part as the containing part (second light emitter) absorbs and emits visible light, while having high color rendering due to color mixing with blue light or the like that is not absorbed by the phosphor. Luminescence is obtained, and this light is transmitted through the diffusion plate (14) and emitted upward in the drawing, so that illumination light with uniform brightness can be obtained within the surface of the diffusion plate (14) of the holding case (12). Become.

[Image display device]
When the light emitting device of the present invention is used as a light source of an image display device, the specific configuration of the image display device is not limited, but it is preferably used together with a color filter. For example, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In each Example and each Comparative Example described later, various evaluations were performed by the following methods.

<Emission peak wavelength, relative emission peak intensity, and relative luminance>
The emission spectrum of the phosphor with excitation light having a wavelength of 465 nm was measured with a fluorescence spectrophotometer, and the emission peak wavelength was read.
The relative emission peak intensity was expressed as a relative value based on the emission peak intensity of the phosphor obtained in Reference Example 1 described later as a reference (100%).
Moreover, the relative brightness | luminance which made the value of the stimulus value Y of the fluorescent substance obtained in the below-mentioned Reference Example 1 100% from the stimulus value Y in the XYZ color system calculated based on JISZ8724 was calculated. The luminance was measured by cutting excitation blue light.

<Chemical composition>
The analysis was performed by ICP emission spectroscopy (Inductively Coupled Plasma-Atomic Emission Spectrometry; hereinafter sometimes referred to as “ICP method”) using an ICP chemical analyzer “JY 38S” manufactured by Jobibon.
N and O were analyzed by a total nitrogen oxygen analyzer (manufactured by LECO).

  In the following, the purity of the single metal used as the alloy raw material is 99.5% for Ca, 99.999% for Al, 99% for Eu, and 99.9999% for Si. It is a high purity product with a mol% or less.

[Example 1]
Each raw metal is weighed so that the metal element composition ratio is Ca: Al: Eu = 0.992: 1: 0.008, and the raw metal is dissolved and solidified in an argon atmosphere using an arc melter device. An alloy ingot having a metal element composition ratio of Ca: Al: Eu = 0.992: 1: 0.008 was obtained.
Next, this alloy lump was pulverized using an alumina mortar in a nitrogen atmosphere, and then sieved with a sieve having an opening of 100 μm, and the sieve was used as an alloy powder raw material. The alloy powder weight median diameter _{D 50} of the raw materials was 100μm or less.
Next, the alloy powder raw material and silicon nitride (Si ₃ N ₄ ) (manufactured by Ube Industries, Ltd., “Ca: Al: Eu: Si = 0.992: 1: 0.008: 1”) SN-E10 ") was weighed and mixed under a nitrogen atmosphere to obtain a raw material mixed powder. The weight median diameter D ₅₀ of the silicon nitride used was 0.5 μm.
30 g of this raw material mixed powder was filled in a boron nitride crucible (inner diameter 60 mm, height 28 mm). The packed bed height at that time was 25 mm.

The crucible filled with the mixed powder was set in an atmosphere firing furnace equipped with a graphite heating element.
After substituting the atmosphere firing furnace with nitrogen, it was heated to 1750 ° C. at a temperature rising rate of 300 ° C./hour while flowing nitrogen at atmospheric pressure. Furthermore, after maintaining at 1750 ° C. for 6 hours, the heating power was turned off and the mixture was naturally cooled to room temperature.

As a result of identifying the crystal phase generated in the obtained phosphor by powder X-ray diffraction, an orthorhombic crystal of CaAlSiN ₃ : Eu was generated. The results are shown in FIG.
Table 1 shows the composition analysis results and the measurement results of the light emission characteristics of this phosphor.

[Example 2]
Each raw metal is weighed so that the metal element composition ratio is Ca: Al: Eu = 0.984: 2: 0.016, and the raw metal is melted and solidified in an argon atmosphere using an arc melter device. An alloy having a metal element composition ratio of Ca: Al: Eu = 0.984: 2: 0.016 was obtained.
Also, each raw metal is weighed so that the metal element composition ratio is Ca: Si = 2: 1, and the raw metal is melted and solidified in an argon atmosphere using an arc melter device, and the metal element composition ratio is Ca. : An alloy with Si = 2: 1 was obtained.
Next, each of the two types of alloys was pulverized using an alumina mortar in a nitrogen atmosphere, and then sieved with a sieve having an opening of 100 μm, and the sieve was used as an alloy powder raw material. The alloy powder weight median diameter _{D 50} of the raw materials was 100μm or less both.
Two types of mixed alloy powder raw materials and silicon nitride (“SN-E10” manufactured by Ube Industries, Ltd.) are used so that the composition ratio is Ca: Al: Eu: Si = 0.922: 1: 0.008: 1. Weighed and mixed in a nitrogen atmosphere to obtain a raw material mixed powder.
30 g of this raw material mixed powder was filled in a boron nitride crucible (inner diameter 60 mm, height 28 mm). The packed bed height at that time was 25 mm.

  The crucible filled with the mixed powder was set in an atmosphere firing furnace equipped with a graphite heating element, and heat-treated in the same manner as in Example 1 to obtain a phosphor.

The obtained phosphor was subjected to confirmation of a generated phase, composition analysis, and measurement of emission characteristics in the same manner as in Example 1. The crystal phase of this phosphor was an orthorhombic crystal phase of CaAlSiN ₃ : Eu containing a small amount of AlN, as in Example 1. The powder X-ray diffraction measurement results are shown in FIG. 5, and the composition analysis results and the emission characteristic measurement results are shown in Table 1.

[Comparative Example 1]
Each metal is weighed so that the metal element composition ratio is Ca: Al: Si: Eu = 0.992: 1: 1: 0.008, and the raw metal is dissolved in an argon atmosphere using an arc melter device. And an alloy having a metal element composition ratio of Ca: Al: Si: Eu = 0.992: 1: 1: 0.008 was obtained. Next, this alloy was pulverized using an alumina mortar in a nitrogen atmosphere, and then sieved with a sieve having an opening of 50 μm, and the sieve was used as an alloy powder raw material.
This alloy powder raw material was filled in a boron nitride crucible (inner diameter: 60 mm, height: 28 mm) in an amount of 15 g (filled layer height: 8 mm) and set in an atmosphere firing furnace equipped with a graphite heating element. After replacing the atmosphere firing furnace with nitrogen, while flowing nitrogen at atmospheric pressure, the furnace was heated to 800 ° C. at a temperature rising rate of 200 ° C./hour, and the temperature was increased from 800 ° C. to 1050 ° C. at 10 ° C./hour. Subsequently, the temperature was raised to 1600 ° C. at 200 ° C./hour. Furthermore, after maintaining at 1600 ° C. for 5 hours, the heating power supply was turned off and the mixture was naturally cooled to room temperature. Next, the temperature was raised to 1750 ° C. at 900 ° C./hour, and further maintained at 1750 ° C. for 3 hours.

The obtained phosphor was subjected to confirmation of crystal phase, composition analysis, and measurement of emission characteristics in the same manner as in Example 1. As in Example 1, the crystal phase was an orthorhombic crystal phase of CaAlSiN ₃ : Eu containing a small amount of AlN. Table 1 shows the results of the composition analysis and the measurement results of the light emission characteristics.

[Comparative Example 2]
15 g of a boron nitride crucible (inner diameter: 60 mm, height: 28 mm) was filled in an alloy powder raw material produced in the same manner as in Comparative Example 1 (packed layer height: 8 mm) and set in an atmosphere firing furnace equipped with a graphite heating element. did. After the atmosphere firing furnace was replaced with nitrogen, the furnace was heated to 1600 ° C. at a rate of temperature increase of 300 ° C./hour while flowing nitrogen at atmospheric pressure. Furthermore, after maintaining at 1600 ° C. for 10 hours, the heating power was turned off and the mixture was naturally cooled to room temperature.
As a result, the whole body was a black lump and did not become a phosphor.

[Comparative Example 3]
30 g of a boron nitride crucible (inner diameter 60 mm, height 28 mm) was filled in the same manner as in Comparative Example 1 (inner diameter 60 mm, height 28 mm), and set in an atmosphere firing furnace equipped with a graphite heating element. did. After replacing the atmosphere firing furnace with nitrogen, while circulating nitrogen at atmospheric pressure, heat to 850 ° C. at a temperature increase rate of 200 ° C./hour, and increase the temperature from 850 ° C. to 1000 ° C. at 10 ° C./hour. Subsequently, the temperature was raised to 1600 ° C. at 200 ° C./hour. Furthermore, after maintaining at 1600 ° C. for 10 hours, the heating power was turned off and the mixture was naturally cooled to room temperature.
As a result, the whole body was a black lump and did not become a phosphor.

[Reference Example 1]
Powdered calcium nitride, powdered aluminum nitride, powdered silicon nitride and powdered europium nitride are nitrogen so that the metal element composition ratio is Ca: Al: Si: Eu = 0.992: 1: 1: 0.008. Weighed in an atmosphere and mixed using a mixer.
30 g of this mixed powder was packed into a boron nitride crucible (inner diameter 60 mm, height 28 mm) (packed layer height; 25 mm) and set in an atmosphere firing furnace equipped with a graphite heating element. After replacing the atmosphere firing furnace with nitrogen, the reactor was filled with nitrogen up to a pressure of 1 MPa, and then heated to 1800 ° C. at a temperature rising rate of 300 ° C./hour. Furthermore, it hold | maintained at 1800 degreeC for 2 hours. Thereafter, the heating power was turned off and the product was naturally cooled to room temperature. The nitrogen pressure in the furnace during heating and cooling was automatically exhausted or supplied so as to maintain 1 MPa.
The obtained phosphor was subjected to confirmation of the formation phase, composition analysis, and measurement of emission characteristics in the same manner as in Example 1. As in Example 1, the crystal phase was an orthorhombic crystal phase of CaAlSiN ₃ : Eu containing a small amount of AlN. Table 1 shows the results of the composition analysis and the measurement results of the light emission characteristics.

As is apparent from the results of Comparative Example 1 and Comparative Example 2, the conventional method using an alloy as a raw material cannot obtain a phosphor when the heating rate is increased.
In addition, as is apparent from the results of Comparative Examples 1 and 3, the conventional method using an alloy as a raw material obtains a phosphor when the amount of raw material to be subjected to nitriding is large even if the rate of temperature increase is slow. I can't.
On the other hand, according to the manufacturing method of the present invention, the phosphor can be manufactured in a large amount and in a shorter time than the method using a conventional alloy as a raw material.

[Example 3]
A light emitting device as shown in FIG. The light emitting device was manufactured according to the following procedure. In addition, about each component of Example 3, the component corresponding to FIG.2 (b) is drawn, and the code | symbol is suitably shown in parenthesis.
As the first light emitter (22), a 460 MB manufactured by Cree, which is a blue light emitting diode (hereinafter abbreviated as “LED” as appropriate), was used. This emits light at a dominant wavelength of 455 nm to 460 nm. This blue LED (22) was die-bonded to the electrode (27) at the bottom of the recess of the frame (24) using a silver paste as an adhesive. At this time, the silver paste as the adhesive was thinly and uniformly applied in consideration of the heat dissipation of the heat generated in the blue LED (22). Then, after heating at 150 degreeC for 2 hours and hardening a silver paste, the electrode of a blue LED (22) and the electrode (26) of a flame | frame (24) were wire-bonded. A gold wire having a diameter of 25 μm was used as the wire (25).

The red light-emitting phosphor (weight median diameter D ₅₀ = 18 μm) obtained in Example 1 and the green light-emitting phosphor Ba _1.39 Sr _0.46 Eu _0.15 SiO ₄ (weight median diameter) having an emission peak wavelength of 528 nm D ₅₀ = 13 μm) in a weight ratio of 23:77, an addition polymerization type silicone resin (SCR 1011 manufactured by Shin-Etsu Chemical Co., Ltd.), and a thickener (Leosil QS-30 manufactured by Tokuyama Co., Ltd.) Were mixed at a weight ratio of 1: 10: 0.1 to prepare a phosphor-containing composition. The obtained phosphor-containing composition was poured into the cup-shaped concave portion of the frame (24) and cured by heating to form the phosphor-containing portion (23), thereby manufacturing a light emitting device.

  When the obtained light-emitting device was driven by applying a current of 20 mA to the blue LED (22) at room temperature, it emitted white light. When the chromaticity value was measured according to JIS Z8701, it was (x, y) = (0.340, 0.335).

[Example 4]
In Example 3, Example 3 was used except that the red light-emitting phosphor obtained in Example 2 (weight median diameter D ₅₀ = 12 μm) was used instead of the red light-emitting phosphor obtained in Example 1. A light emitting device was manufactured by the same procedure as described above.
When the obtained light emitting device was made to emit light under the same conditions as in Example 3, it emitted white light. When the chromaticity point was measured, it was (x, y) = (0.327, 0.335).

It is a typical perspective view which shows one Example of the light-emitting device of this invention. FIG. 2A is a schematic cross-sectional view showing an embodiment of a bullet-type light emitting device of the present invention, and FIG. 2B is a schematic view showing an embodiment of the surface-mounted light-emitting device of the present invention. It is sectional drawing. It is typical sectional drawing which shows one Example of the illuminating device of this invention. 3 is a diagram showing a powder X-ray diffraction pattern of the phosphor obtained in Example 1. FIG. FIG. 4 is a diagram showing a powder X-ray diffraction pattern of the phosphor obtained in Example 2.

Explanation of symbols

1 Phosphor-containing part (second light emitter)
2 Excitation light source (first light emitter) (LD)
3 Substrate 4 Light-emitting device 5 Mount lead 6 Inner lead 7 Excitation light source (first light emitter)
8 Phosphor-containing resin part 9 Conductive wire 10 Mold member 11 Surface emitting illumination device 12 Holding case 13 Light emitting device 14 Diffusion plate 22 Excitation light source (first light emitter) (LED)
23 Phosphor-containing part (second light emitter)
24 frame 25 conductive wire 26 electrode 27 electrode

Claims (16)

Activating element M1, a valent metal element M2, a trivalent metal element M3, and a method for producing a nitride or oxynitride phosphor containing a tetravalent metal element M4, comprising at least an activating element as a raw material A method for producing a phosphor using an alloy containing M1 and a divalent metal element M2 and a nitride of a tetravalent metal element M4 and heating the raw material in an atmosphere containing a nitrogen element ,
The activation element M1 contains Eu and / or Ce,
50 mol% or more of the divalent metal element M2 is Ca and / or Sr, 50 mol% or more of the trivalent metal element M3 is Al, and 50 mol% or more of the tetravalent metal element M4 is Si. There is provided a method for producing a phosphor. The activation element M1 is selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, and Eu and / or Ce are essential elements. The tetravalent metal element M4 is one or more elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf and having Si as an essential element. The method for producing a phosphor according to claim 1, wherein The fluorescence according to claim 1 or 2 , wherein the trivalent metal element M3 is one or more elements selected from the group consisting of Al, Ga, In, and Sc and having Al as an essential element. Body manufacturing method. As a raw material, claims 1, characterized by using an alloy containing activator elements M1,2 divalent metal elements M2, and trivalent metal elements M3, and a nitride of tetravalent metal elements M4 3 The manufacturing method of the fluorescent substance of any one of these . As raw materials, an alloy containing an activating element M1, a divalent metal element M2, and a trivalent metal element M3, an alloy containing a divalent metal element M2 and a tetravalent metal element M4, and a tetravalent metal The method for producing a phosphor according to any one of claims 1 to 3, wherein a nitride of the metal element M4 is used. As raw materials, an alloy containing an activating element M1, a bivalent metal element M2, and a tetravalent metal element M4, an alloy containing a divalent metal element M2 and a trivalent metal element M3, and a tetravalent metal The method for producing a phosphor according to any one of claims 1 to 3, wherein a nitride of the metal element M4 is used. The method for producing a phosphor according to any one of claims 1 to 6 weight-average median diameter D ₅₀ of the alloy and wherein the at 200μm or less. As nitride tetravalent metal elements M4, method for manufacturing the phosphor according to any one of claims 1 to 7, characterized in that a powder is the weight-average median diameter D ₅₀ is 100μm or less. The method for producing a phosphor according to any one of claims 1 to 8 , wherein the nitride or oxynitride phosphor is a phosphor represented by the following general formula [1].
_{M1 a M2 b M3 c M4 d} N e O f [1]
(Wherein M1 is an activator element, M2 is a divalent metal element, M3 is a trivalent metal element, M4 is a tetravalent metal element, and a, b, c, e, Each f is a value within the following range.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5) A phosphor prepared by the method according to any one of claims 1 to 9, the phosphor-containing composition characterized by containing a liquid medium. A first light emitter and a second light emitter that emits visible light when irradiated with light from the first light emitter, wherein the second light emitter is any one of claims 1 to 9. A light-emitting device comprising one or more of the phosphors produced by the method described in 1. as a first phosphor. 12. The light emitting device according to claim 11 , wherein the second phosphor includes one or more phosphors having different emission peak wavelengths from the first phosphor as the second phosphor. . The first light emitter has a light emission peak in a wavelength range of 420 nm to 500 nm;
The light emitting device according to claim 12 , wherein the second light emitter contains, as the second phosphor, at least one kind of phosphor having a light emission peak in a wavelength range of 500 nm or more and 570 nm or less. . The first light emitter has a light emission peak in a wavelength range of 300 nm or more and 420 nm or less;
The second phosphor is, as the second phosphor, at least one phosphor having a light emission peak in a wavelength range of 420 nm or more and 500 nm or less, and at least one species having a light emission peak in a wavelength range of 500 nm or more and 570 nm. The light emitting device according to claim 12 , comprising: An image display device, characterized in that it comprises as a light source a light emitting device according to any one of claims 11 to 14. Lighting apparatus comprising: a light-emitting device according as the light source to any one of claims 11 to 14.

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