JP2010270196A - Phosphor, method for manufacturing phosphor, phosphor-containing composition, light-emitting device, lighting apparatus, image display, and fluorescent paint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red phosphor with improved afterglow characteristics, a method for manufacturing the same, a phosphor-containing composition and a light-emitting device using the phosphor, and an image display and a lighting apparatus using the light-emitting device. <P>SOLUTION: The phosphor contains Eu and Tm as activator elements, and the host crystal composition thereof is represented by the following formula [I]: M<SB>2</SB>Si<SB>5</SB>N<SB>8</SB>, wherein M is an alkaline earth metal element. The phosphor contains an element selected from the group consisting of Li and Zn. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a phosphor having excellent afterglow and a base crystal composition represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ , a method for producing the same, and the phosphor-containing composition, The present invention relates to a light emitting device, an image display device, and an illumination device using the above. Specifically, the matrix crystal composition containing Eu and Tm as the activating elements and an element selected from the group consisting of Li and Zn is represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N _8. The present invention relates to a phosphor and a manufacturing method thereof, and the phosphor-containing composition, a light emitting device, an image display device, and an illumination device using the composition.

Nitride phosphors that emit red light when irradiated with near-ultraviolet and blue light and have a host crystal structure represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ (hereinafter referred to as “258” as appropriate). (Referred to as Patent Document 1).
Patent Document 2 discloses that the persistence of the 258 phosphor can be improved by coexisting Tm as an activator of the 258 phosphor in addition to conventionally known Eu. Are listed.

Furthermore, Patent Document 3 describes that afterglow can be improved by adjusting the content of the activating element.
On the other hand, Patent Document 4 describes that by adding an alkali metal element or the like to a 258 phosphor, it acts as a sintering aid, and the 258 phosphor containing the alkali metal element or the like improves the luminance. ing.

Special table 2003-515665 gazette JP 2004-10786 A JP 2009-074077 A JP 2004-182780 A

Conventionally, phosphorescent phosphors have been widely used for fluorescent lamps, clock dials, and the like, but as commonly known red phosphorescent phosphors, La ₂ O ₂ S to which Mg or Ti is added is known. : Eu ³⁺ only. In addition, regarding a light emitting device using a phosphor, even if the light emitting diode suddenly stops emitting light, if the phosphor used has a long persistence (has a phosphorescent property), a display is displayed. Since light emission can be sustained as an element or a light source, the appearance of a phosphor having such characteristics is desired.

For this reason, although several methods for imparting afterglow to the 258-based phosphor are known as described above, since they have not yet been put into practical use, further measures for improving afterglow are provided. Appearance is desired.
The present invention was devised in view of the above problems, and includes afterglow that contains Eu and Tm as activator elements and whose parent crystal composition is represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N _8. The first object is to obtain a phosphor having higher persistence among phosphors having the property, and further, a method for producing the phosphor, a phosphor-containing composition using the phosphor, and a light emitting device Another object is to provide an illumination device and an image display device.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, Tm phosphor containing an element selected from the group consisting of Li and Zn. Found that afterglow was improved.
That is, the gist of the present invention is the following (1) to (12).
(1) A phosphor containing Eu and Tm as activators and having a matrix crystal composition represented by the following formula [I], comprising an element selected from the group consisting of Li and Zn Phosphor to be used.

M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)
(2) The phosphor according to (1), wherein Li is contained in a range of 50 mol% or less with respect to 1 mol of the phosphor.
(3) The phosphor according to (1), wherein Zn is contained in a range of 10 mol% or less with respect to 1 mol of the phosphor.
(4) A method for producing a phosphor in which a phosphor material is fired, Eu and Tm are included as activator elements, and a matrix crystal composition is represented by the following formula [I], and converted to 1 mol of the phosphor A method for producing a phosphor, comprising containing in the raw material mixture Li element in a range of 50 mol% or less relative to the raw material mixture.

M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)
(5) A method for producing a phosphor in which a phosphor material is fired, Eu and Tm are contained as activator elements, and a host crystal composition is represented by the following formula [I], and converted to 1 mol of the phosphor A method for producing a phosphor, characterized in that the raw material mixture contains Zn element in a range of less than 10 mol% with respect to the raw material mixture.

M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)
(6) The production method according to (4) or (5), wherein an alkaline earth metal hydride is used as the phosphor material.
(7) A phosphor-containing composition comprising the phosphor according to any one of (1) to (3) and a liquid medium.
(8) A light emitting device having a first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter,
A light emitting device comprising a first phosphor containing at least one phosphor according to any one of (1) to (3) as the second light emitter.
(9) An illumination device comprising the light-emitting device according to (8).
(10) An image display device comprising the light emitting device according to (8).
(11) A fluorescent paint containing the phosphor according to any one of (1) to (3).
(12) A laminate obtained by applying the fluorescent paint according to (11) to a substrate.

  According to the present invention, a 258-based phosphor having improved afterglow can be obtained, and a phosphor-containing composition, a light-emitting device, a lighting device, an image display device, a fluorescent paint, and the like using the phosphor-containing composition can be realized. be able to.

It is a typical perspective view which shows the positional relationship of an excitation light source (1st light emission body) and a fluorescent substance containing part (2nd light emission body) in an example of the light-emitting device of this invention. 2 (a) and 2 (b) are schematic cross sections showing an embodiment of a light emitting device having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). FIG. It is sectional drawing which shows typically one Embodiment of the illuminating device of this invention. It is a diagram showing the JCPDS pattern of the XRD spectra of the phosphors of Comparative Example 1 and Example 2 and _Ca 2 _Si 5 _{N 8} of the present invention. It is a figure which shows the emitted light intensity of each fluorescent substance of the comparative example 1 and Examples 1-6 of this invention. It is a figure which shows the emitted light intensity of 100 second after the excitation light stop of each fluorescent substance of the comparative example 1 and Examples 1-6 of this invention. It is a figure which shows the emitted light intensity of each fluorescent substance of the comparative example 2 of this invention, and Examples 7-12. It is a figure which shows the emitted light intensity of 100 second after the excitation light stop of each fluorescent substance of the comparative example 2 and Examples 7-12 of this invention. It is a figure which shows the XRD spectrum of the fluorescent substance of Example 14 of this invention. It is a figure which shows the emitted light intensity 10 second after the excitation light stop of each fluorescent substance of the comparative example 2 and Examples 13-15 of this invention. It is a figure which shows the emitted light intensity of 10 second after the excitation light stop of each fluorescent substance of Comparative Examples 2-4 of this invention. It is a figure which shows the emission spectrum of each fluorescent substance of the comparative example 1 and Examples 11 and 14 of this invention. It is a figure which shows the afterglow characteristic of each fluorescent substance of the comparative example 1 and Examples 11 and 14 of this invention.

Hereinafter, the present invention will be described in detail with reference to embodiments, examples, etc., but the present invention is not limited to the following embodiments, examples, etc., and may be arbitrarily changed without departing from the gist thereof. Can be implemented.
The relationship between the color name and the chromaticity coordinates in this specification is all based on the JIS standard (JIS Z8110 and Z8701).

In the composition formula of the phosphors 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 “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” has “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. If: the _{"Ca 1-x Sr x Al 2} O 4 Eu ": a _{"Sr 1-x Ba x Al 2} O 4 Eu ": the _{"Ca 1-x Ba x Al 2} O 4 Eu " _{"Ca 1-x-y Sr x} Ba 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).

1. Phosphor [1-1] Composition The phosphor of the present invention is a phosphor whose matrix crystal composition is represented by the following formula [I].
M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)
In the above formula [I], M is an alkaline earth metal element such as Mg, Ca, Sr and Ba,
Of these, Ba, Ca and Sr are preferred, and more preferably 50% or more of Ca is contained.

  Moreover, Eu and Tm are contained as an activating element. Here, the content of Eu with respect to the total number of moles of the M element and the activating element is usually 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less. In addition, preferably 0.05 mol% or more, more preferably 0.1 mol% or more, more preferably 0.2 mol% or more, still more preferably 0.25 mol% or more, and particularly preferably 0.3 mol% or more. More than mol%. On the other hand, if the amount of Eu is too large, concentration quenching tends to occur, and if the amount of Eu is too small, desired light emission intensity and afterglow intensity cannot be obtained.

The Tm content relative to the total number of moles of the M element and the activating element is preferably the same as the Eu content. Further, the ratio of the Tm addition amount to the Eu addition amount is preferably 0.5 or more, more preferably 0.8 or more, and preferably 2.0 or less, more preferably 1.5 or less.
The phosphor of the present invention is characterized in that the phosphor as described above contains an element selected from the group consisting of Li and Zn.

As content of Li, it is larger than 0 mol% normally with respect to 1 mol of fluorescent substance, Preferably it is 1 mol% or more. Moreover, it is 50 mol% or less, Preferably it is 40 mol% or less.
The Zn content is usually greater than 0 mol%, preferably 1 mol% or more, with respect to 1 mol of the phosphor. Moreover, it is 10 mol% or less normally, Preferably it is 8 mol% or less.

Here, as the phosphor of the present invention, as long as the performance is not affected, the above formula [
A part of the nitrogen atom in I] may be replaced with an oxygen atom or a halogen atom. In this case, the oxygen atom content is 10 mol% or less, preferably 3 mol% or less, more preferably 1 mol% or less, based on the total number of moles of nitrogen atoms, oxygen atoms and halogen atoms. Further, the content of halogen atoms is usually 1 mol% or less with respect to the total number of moles of nitrogen atoms, oxygen atoms and halogen atoms.

[1-2] Afterglow Characteristics A phosphor having a matrix crystal composition represented by the following formula [I] and containing Eu and Tm as activating elements usually emits both fluorescence and phosphorescence. Compared with fluorescence, phosphorescence has the property of being emitted over a relatively long time after the point where irradiation of excitation light to the phosphor is stopped. The phenomenon in which light is emitted from the phosphor even after the point of time when the excitation light irradiation is stopped is called afterglow.

The phosphor of the present invention is characterized in that the afterglow is emitted for a long time (has a phosphorescent property). Specifically, under conditions of a temperature of 25 ° C. and a humidity of 10% to 70%, light (excitation light) having a wavelength of 455 nm is irradiated for 10 minutes, a time constant of 0.01 seconds, and a measurement interval of 0.2 seconds. In the case where afterglow characteristics are measured, the emission intensity of the phosphor 5 minutes after the excitation light irradiation is usually 6.1 × 10 ⁻³ % or more, preferably 6.5 with respect to the emission intensity during the excitation light irradiation. × 10 ⁻³ % or more, more preferably 7.0 × 10 ⁻³ % or more, and further preferably 8.0 × 10 ⁻³ % or more. In this case, the higher the emission intensity, the better. However, it is usually 1% or less.
In general, the afterglow time tends to increase as the irradiation intensity of the excitation light is increased and the irradiation time is increased. However, when the irradiation intensity and irradiation time of the excitation light exceed a certain threshold value, the afterglow time does not increase and the afterglow time becomes constant even if the irradiation intensity and irradiation time of the excitation light are further increased and increased. In the afterglow measurement according to the present invention, in consideration of the above-mentioned properties, a sufficient amount of excitation light is emitted so that the afterglow characteristics do not change even if the excitation light irradiation intensity is increased or the irradiation time is increased. And then measure.

[1-3] Other characteristics <Emission spectrum>
The phosphor of the present invention emits red light when excited by light in the near ultraviolet to blue region having a wavelength of 380 to 460 nm. Specifically, the emission peak wavelength in the emission spectrum when excited with light having a wavelength of 455 nm is usually 570 nm or more, preferably 590 nm or more, more preferably 600 nm or more, more preferably 610 nm or more, and usually 700 nm or less. Preferably it is 680 nm or less, More preferably, it is 650 nm or less, More preferably, it is 630 nm or less.

The half-value width of the emission peak is usually 60 nm or more, preferably 65 nm or more, more preferably 70 nm or more, and is usually 125 nm or less, preferably 120 nm or less, more preferably 115 nm or less.
In order to excite the phosphor with light having a wavelength of 455 nm, for example, a GaN-based LED can be used. In addition, the measurement of the emission spectrum of the phosphor of the present invention and the calculation of the emission peak wavelength, peak relative intensity and peak half width are, for example, F-4500 manufactured by Hitachi High-Technologies Corporation or FP manufactured by JASCO Corporation. It can be performed using a fluorescence measuring apparatus such as −6500.

<Particle size>
The phosphor of the present invention has a weight median diameter D ₅₀ of usually 0.01 μm or more, preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and usually 100 μm or less, preferably 30 μm or less. More preferably, it is in the range of 20 μm or less. When the weight-average median diameter D ₅₀ is too small, and the luminance decreases tends to phosphor particles aggregate. On the other hand, when the weight-average median diameter D ₅₀ is too large, there is a tendency for blockage, such as uneven coating or a dispenser.

The above-mentioned weight-average median diameter D _50, is a value obtained by the frequency particle size distribution curve. The frequency-based particle size distribution curve can be obtained by measuring the particle size distribution by a laser diffraction / scattering method. Specifically, the phosphor was dispersed in an aqueous solution containing a dispersant, and measured by a laser diffraction particle size distribution measuring device (Horiba LA-300) in a particle size range of 0.1 μm to 600 μm. Is. In this frequency particle size distribution curve, the accumulated value is the particle size value when the 50% and weight-average median diameter D _50.

[1-7] Use of phosphor The phosphor of the present invention can be used for any application using a phosphor. In addition, the phosphor of the present invention can be used alone, but two or more of the phosphors of the present invention can be used together, or the phosphor of the present invention and other phosphors It is also possible to use as a phosphor mixture of any combination.

  In addition, the phosphor of the present invention can be suitably used for various light-emitting devices (hereinafter referred to as “light-emitting device of the present invention”) taking advantage of the characteristic that it can be excited by blue light. Since the phosphor of the present invention is usually a red light-emitting phosphor, for example, when an excitation light source that emits blue light is combined with the phosphor of the present invention, a purple to pink light-emitting device can be manufactured. . In addition, the phosphor of the present invention is combined with an excitation light source that emits blue light and a phosphor that emits green light, or an excitation light source that emits near-ultraviolet light, a phosphor that emits blue light, and a fluorescence that emits green light. If the body is combined, the phosphor of the present invention emits red light when excited by blue light from an excitation light source that emits blue light or a phosphor that emits blue light, and thus a white light emitting device is manufactured. be able to.

The emission color of the light-emitting device is not limited to white, and by appropriately selecting the combination and content of phosphors, a light-emitting device that emits light in any color such as light bulb color (warm white) or pastel color is manufactured. can do. 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.
In addition to this, taking advantage of the long afterglow characteristic, it has been replaced with sulfide-based phosphorescent phosphors that have been used in the past, such as various instruments, dials of night clocks, safety sign boards, etc. It can also be used for various purposes. Specifically, display of vehicles such as airplanes, boats, cars, bicycles; road traffic signs, lane indications, indications on guardrails, indications of fishery buoys, etc., indications from gates to entrances, to helmets Display on various signs on displays, etc .; Outdoor displays such as signs and buildings, etc .; Indoor displays such as electrical appliance switches, etc .; Display of various keys and keyholes in homes, cars, bicycles, etc .; Writing instruments, night light Stationery such as inks, maps, and constellation charts; Toys such as jigsaw puzzles; Sports balls; Backlights for liquid crystals (used for watches and the like); Substitutes for isotopes used for discharge tubes, and the like.

2. Method for Producing Phosphor The phosphor of the present invention is a phosphor raw material powder and / or a fired product obtained by mixing and firing them (in the present specification, these are collectively referred to as a phosphor precursor). It can manufacture according to the well-known method of baking, The element chosen from the group which consists of Li and Zn is contained in the raw material mixture at this time, It is characterized by the above-mentioned.

Hereinafter, the phosphor raw material, the phosphor manufacturing method, and the like will be specifically described.
[2-1. Phosphor raw material]
Phosphor raw materials used in the production of the phosphor of the present invention (that is, M element raw material (hereinafter sometimes referred to as M source), Eu raw material, Tm raw material and Si raw material, and Li Examples of the raw material and the raw material of Zn include simple substances and compounds containing these elements. Among them, preferable examples include metals, alloys, imide compounds, amide compounds, oxynitrides, nitrides, oxides, Examples include hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates and halides. The phosphor material may be appropriately selected from these in consideration of the reactivity to the composite oxynitride and the low generation amount of NO _x , SO _x, etc. during firing.

Further, the impurities contained in the phosphor material are not particularly limited as long as the performance of the phosphor is not affected. However, with respect to Fe, Co, Cr, and Ni, those usually used are 1000 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less.
The weight median diameter of each phosphor material is usually 0.1 μm or more, preferably 0.5 μm or more, and usually 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 3 μm or less. Is used. For this reason, depending on the type of the phosphor material, pulverization may be performed in advance by a dry pulverizer such as a jet mill. As a result, each phosphor raw material can be uniformly dispersed in the raw material mixture, and the solid phase reactivity of the raw material mixture can be increased by increasing the surface area of the phosphor raw material, thereby suppressing the generation of impurity phases. It becomes. In particular, in the case of a nitride material, it is preferable to use a material having a smaller particle size than other phosphor materials from the viewpoint of reactivity.

[Description of M source]
Among the M sources, specific examples of Mg raw materials (Mg sources) include MgO, Mg (OH) ₂ , basic magnesium carbonate (mMgCO ₃ .Mg (OH) ₂ .nH ₂ O), Mg (NO ₃ ). _{2 · 6H 2 O, MgSO 4} , Mg (C 2 O 4) · 2H 2 O, Mg (OCOCH 3) 2 · 4H 2 O, MgCl 2, MgF 2, Mg 3 N 2, MgNH, Mg (NH 2) ₂ etc. are mentioned. Among these, Mg ₃ N ₂ , MgNH, and Mg (NH ₂ ) ₂ are preferable.

Among the M sources, specific examples of the Ca raw material (Ca source) include CaO, Ca (OH) ₂ , CaCO ₃ , Ca (NO ₃ ) ₂ .4H ₂ O, CaSO ₄ .2H ₂ O, and Ca (C ₂ O ₄ ) · H ₂ O, Ca (OCOCH ₃ ) ₂ .H ₂ O, CaCl ₂ , CaF ₂ , Ca ₃ N ₂ , CaNH, Ca (NH ₂ ) _{2 and the} like. Among these, Ca ₃ N ₂ , CaNH, and Ca (NH ₂ ) ₂ are preferable.
Among the M sources, specific examples of Sr raw materials (Sr sources) include SrO, Sr (OH) ₂ .8H ₂ O, SrCO ₃ , Sr (NO ₃ ) ₂ , SrSO ₄ , Sr (C ₂ O ₄ ). _{· H 2 O, Sr (OCOCH} 3) 2 · 0.5H 2 O, SrCl 2, SrF 2, Sr 2 N, SrNH, Sr (NH 2) 2 and the like. Among these, Sr ₂ N, SrNH, and Sr (NH ₂ ) ₂ are preferable. This is because the stability in the air is good, it is easily decomposed by heating, it is difficult for undesired elements to remain, and it is easy to obtain high-purity raw materials.

Specific examples of the Ba source include BaO, Ba (OH) ₂ .8H ₂ O, BaCO ₃ , Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (C ₂ O ₄ ), Ba (OCOCH ₃ ) ₂ , BaCl _2. , BaF ₂ , Ba ₂ N, BaNH, Ba (NH ₂ ) _{2 and the} like. Of these, carbonates, oxides, and the like can be preferably used, but carbonates are more preferable from the viewpoint of handling because oxides easily react with moisture in the air. Of these, Ba ₂ N, BaNH, and Ba (NH ₂ ) ₂ are preferable. This is because the stability in the air is good, and it is easily decomposed by heating, so that undesired elements hardly remain and it is easy to obtain high-purity raw materials.

Here, when carbonate is used as the M source, it is preferable that the carbonate is preliminarily calcined and used as the raw material.
[Description of Eu source]
Specific examples of Eu raw materials (Eu sources) include Eu ₂ O ₃ , Eu ₂ (SO ₄ ) ₃ , Eu ₂ (C ₂ O ₄ ) ₃ · 10H ₂ O, EuCl ₂ , EuCl ₃ , EuF ₂ , EuF ₃ , Eu (NO ₃ ) ₃ .6H ₂ O, EuN, EuNH, Eu (NH ₂ ) _{2 and the} like. Among them, Eu ₂ O ₃ , EuCl ₂ , EuN, EuNH and the like are preferable, and Eu ₂ O ₃ , EuN, EuNH are particularly preferable.

[Description of Tm source]
Specific examples of the Tm source include compounds in which Eu is replaced with Tm in each compound listed as a specific example of the Eu source.
[Description of Si source]
As a Si raw material (Si source), it is preferable to use SiC, SiO ₂ or Si ₃ N ₄ , and more preferably Si ₃ N ₄ . It is also possible to use a compound as a SiO _2. Specific examples of such a compound include SiO ₂ , H ₄ SiO ₄ , Si (OCOCH ₃ ) _{4 and the} like. Si ₃ N ₄ preferably has a small particle diameter and high purity from the viewpoint of light emission efficiency from the viewpoint of reactivity. Furthermore, from the viewpoint of luminous efficiency, β-Si ₃ N ₄ is more preferable than α-Si ₃ N ₄ , and in particular, one having a small content ratio of carbon elements as impurities is preferable. The carbon content is preferably as small as possible, but is usually 0.01% by weight or more, usually 0.3% by weight or less, preferably 0.1% by weight or less, more preferably 0.05% by weight or less. is there.

On the other hand, from the viewpoint of increasing the particle diameter of the phosphor particles, it is preferable that the particle diameter of the raw material Si ₃ N ₄ is large.
[Description of Li source]
Specific examples of the Li source (Li source) include Li ₃ N, Li metal, Li ₂ CO ₃ , and LiOH. Among these oxygen it does not contain Li metal or Li ₃ N are preferred, particularly preferably Li ₃ N.

The Li source is usually greater than 0 mol%, preferably 1 mol% or more, and usually 50 mol% or less, preferably 40 mol% or less, relative to the raw material mixture converted to 1 mol of the phosphor. Use in a range.
[Description of Zn source]
Specific examples of the Zn raw material (Zn source) include Zn metal, ZnO, ZnS, ZnSO ₄ , and Zn (NO ₃ ). Of these, ZnS and Zn metal having a low oxygen content are preferable, and Zn metal is particularly preferable. However, ZnO can also be used because of the availability of high-purity raw materials and the ease of handling.

Further, the Zn source is usually in the range of more than 0 mol%, preferably 1 mol% or more, usually less than 10 mol%, preferably 8 mol% or less, relative to the raw material mixture converted to 1 mol of the phosphor. Use.
[Other explanation about phosphor material]
In the various phosphor materials, it is preferable to use a phosphor material having high purity and higher whiteness. This is to increase the luminous efficiency of the obtained phosphor. Specifically, it is preferable to use a phosphor material having a reflectance in the wavelength range of 380 nm to 780 nm of usually 60% or more, preferably 70% or more, more preferably 80% or more. In particular, at 525 nm, which is a wavelength close to the emission peak wavelength of the phosphor of the present invention, the reflectance of the phosphor material is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. Particularly preferably, it is 90% or more.

Of the plurality of phosphor materials, it is particularly preferable to use silicon nitride (Si ₃ N ₄ ) having a high reflectance. As the _Si 3 _{N 4} satisfying the reflectivity, as the amount of carbon is contained as an impurity is usually 0.2 weight% or less, preferably 0.1 wt% or less, more preferably 0.05 wt% Hereinafter, it is more preferably 0.03% by weight or less. The amount of impurity carbon is preferably as small as possible, but is usually 0.001% by weight or more. In addition, this reflectance should just measure a reflection spectrum in accordance with well-known methods, such as the method as described in WO2009 / 017206 pamphlet.

In addition, silicon nitride (Si ₃ N ₄ ) is preferably β-type rather than α-type. Examples of such silicon nitride include those described in WO2009 / 017206. However, the α type can be used in consideration of availability.
Further, the N element in the composition of the phosphor of the present invention is usually supplied at the time of phosphor production as an anion component of the phosphor material of each phosphor constituent element or as a component contained in the firing atmosphere. The

[2-2. Production method of phosphor: mixing step]
The phosphor of the present invention is obtained by weighing the phosphor materials so that the target composition is obtained, mixing them, and firing. In this case, it is preferable that the mixing is sufficiently performed using a ball mill or the like.
Although it does not specifically limit as said mixing method, Specifically, the well-known method which was mentioned as following (A) and (B) can be used arbitrarily. As for these various conditions, for example, known conditions such as mixing and using two kinds of balls having different particle diameters in a ball mill can be appropriately selected.

(A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle And a dry mixing method in which the above phosphor raw materials are pulverized and mixed.
(B) An alcoholic solvent such as ethanol or a solvent or dispersion medium such as water is added to the phosphor raw material described above, and mixed using, for example, a pulverizer, a mortar and pestle, or an evaporating dish and a stirring rod, and then a solution or slurry A wet mixing method in which the mixture is dried by spray drying, heat drying, natural drying, or the like.

Further, when mixing and pulverizing, the phosphor material may be sieved as necessary. In this case, various commercially available sieves can be used. However, it is preferable to use a resin such as a nylon mesh rather than a metal mesh such as a metal mesh in terms of preventing impurities from being mixed.
The mixing of the phosphor raw materials may be arbitrarily selected from the above-mentioned wet type and dry type according to the physical properties of the phosphor raw materials.

In addition, when nitride is used as a raw material, an inert gas such as argon gas or nitrogen gas is filled, for example, so that the nitride is not deteriorated by moisture, and mixer mixing is performed in a moisture-controlled glove box. preferable.
Furthermore, when mixing, the moisture in the atmosphere is preferably 10,000 ppm or less, more preferably 1000 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. Further, oxygen is preferably 1% or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and particularly preferably 10 ppm or less.

[2-3. Production method of phosphor: firing step]
A phosphor is obtained by firing the obtained mixture. This firing is preferably performed by filling the phosphor material in a container such as a crucible and firing at a predetermined temperature and atmosphere.
As the container, it is preferable to use a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each phosphor raw material. Examples of the material of the heat-resistant container used at the time of firing include, for example, metals such as alumina, quartz, boron nitride, silicon nitride, silicon carbide, platinum, molybdenum, tungsten, tantalum, niobium, or alloys containing them as a main component. And carbon (graphite). Here, the heat-resistant container made of quartz can be used for heat treatment at a relatively low temperature, that is, 1200 ° C. or less, and a preferable use temperature range is 1000 ° C. or less.

Examples of such heat-resistant containers are preferably boron nitride, graphite, silicon nitride, silicon carbide, platinum, molybdenum, tungsten, and tantalum heat resistant containers, more preferably boron nitride. , Graphite, and molybdenum.
In the temperature raising process at the time of firing, it is preferable that a part of the temperature is reduced. Specifically, at any time when the temperature is preferably room temperature or higher, and preferably 1500 ° C. or lower, more preferably 1200 ° C. or lower, and even more preferably 1000 ° C. or lower, the reduced pressure state (specific In general, it is preferably in the range of 10 ⁻² Pa or more and less than 0.1 MPa. Among them, it is preferable to introduce an inert gas or a reducing gas, which will be described later, into the system after reducing the pressure in the system and raise the temperature in that state.

At this time, if necessary, the target temperature may be maintained for 1 minute or longer, preferably 5 minutes or longer, more preferably 10 minutes or longer. The holding time is usually 5 hours or less, preferably 3 hours or less, more preferably 1 hour or less.
As the firing temperature for producing the phosphor of the present invention, a powder having good crystallinity is obtained at a firing temperature of around 1800 ° C. Therefore, the temperature is usually 1300 ° C or higher, more preferably 1400 ° C or higher, and usually 2000 ° C or lower, preferably 1900 ° C or lower.

Although it does not restrict | limit especially as a baking atmosphere, Usually, it carries out in inert gas atmosphere or reducing atmosphere. Here, as described above, the valence of the activating element is preferably a divalent atmosphere, so that a reducing atmosphere is preferable. In addition, only 1 type may be used for an inert gas and reducing gas, and 2 or more types may be used together by arbitrary combinations and a ratio.
Examples of the inert gas and the reducing gas include carbon monoxide, hydrogen, nitrogen, argon, methane, and ammonia. Of these, a nitrogen gas atmosphere is preferable, and a hydrogen gas-containing nitrogen gas atmosphere is more preferable. As the nitrogen (N ₂ ) gas, it is preferable to use a purity of 99.9% or more. When using hydrogen-containing nitrogen, it is preferable to reduce the oxygen concentration in the electric furnace to 20 ppm or less. Further, the hydrogen content in the atmosphere is preferably 1% by volume or more, more preferably 2% by volume or more, and 100% by volume or less of hydrogen gas may be used, but 10% by volume or less is preferable, and 5% by volume. The following is more preferable. This is because if the hydrogen content in the atmosphere is too high, the safety may decrease, and if it is too low, a sufficient reducing atmosphere may not be achieved.

Further, the inert gas and the reducing gas may be introduced before the start of temperature increase, may be introduced during the temperature increase, or may be introduced when the firing temperature is reached, but before the temperature increase is started. Or it is preferable to introduce in the middle of temperature rising.
Moreover, when calcination is performed under the flow of these inert gas and reducing gas, the calcination is usually performed at a flow rate of 0.1 to 10 liters / minute.

The firing time is usually 0.5 hours or longer, preferably 1 hour or longer, although it varies depending on the temperature and pressure during firing. The firing time is preferably longer, but is usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours or shorter, and further preferably 12 hours or shorter.
The pressure at the time of firing varies depending on the firing temperature and the like and is not particularly limited, but is usually 1 × 10 ⁻⁵ Pa or more, preferably 1 × 10 ⁻³ Pa or more, more preferably 0.01 MPa or more, and still more preferably 0.8. The upper limit is generally 5 GPa or less, preferably 1 GPa or less, more preferably 200 MPa or less, and even more preferably 100 MPa or less. Among these, the atmospheric pressure to about 1 MPa is industrially preferable in terms of cost and labor.

In the firing step, for example, a phosphor precursor other than the raw material mixture, such as a fired product obtained by mixing and firing a part or all of the phosphor raw materials, is combined with the raw material mixture, or they are replaced with the raw material mixture. Alternatively, it may be fired.
[2-4. flux]
In the phosphor of the present invention, a flux may coexist in the reaction system in the firing step. The type of flux is not particularly limited, _{examples, NH 4 Cl, NH 4 F} · HF , such as ammonium _halide; NaCO 3, alkali metal carbonates such as _{LiCO 3; LiCl, NaCl, KCl} , CsCl, LiF, Alkali metal halides such as NaF, KF, CsF; Alkaline earth metal halides such as CaCl ₂ , BaCl ₂ , SrCl ₂ , CaF ₂ , BaF ₂ , SrF ₂ ; EuCl ₂ , LaCl ₃ , CeCl ₃ , EuF ₂ Rare earth metal halides such as LaF ₃ , CeCl ₃ ; alkaline earth metal oxides such as CaO, SrO, BaO; B ₂ O ₃ , H ₃ BO ₃ , Na ₂ B ₄ O ₇ , K ₂ B ₄ O ₇ Boron oxide such as boric acid and borate compound of alkali metal or alkaline earth metal; Li ₃ PO ₄ , NH ₄ H ₂ PO ₄ , B phosphate compounds such as aHPO ₄ and Zn ₃ (PO ₄ ) ₂ ; aluminum halides such as AlF ₃ ; zinc halides such as ZnCl ₂ , ZnBr ₂ and ZnF ₂ , zinc oxide, zinc sulfide, zinc borate, phosphoric acid Zinc compounds such as zinc; periodic table group 15 element compounds such as Bi ₂ O ₃ ; Li ₃ N, Ca ₃ N ₂ , Sr ₃ N ₂ , Ba ₃ N ₂ , Sr ₂ N, Ba ₂ N, BN, etc. Alkali metals, alkaline earth metals, nitrides of Group 13 elements, and the like can be given.

The amount of flux used varies depending on the type of phosphor material, the type of flux, etc., but is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more for each flux. In addition, it is usually 20% by weight or less, more preferably 10% by weight or less.
In addition, only 1 type may be used for a flux and it may use 2 or more types together by arbitrary combinations and a ratio. When two or more types are used in combination, the amount of flux used is generally 40% by weight or less, preferably 30% by weight or less, and more preferably 25% by weight or less. The total amount is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more.

[2-5. Multistage firing]
In order to further advance the solid phase reaction in the firing step and improve the crystallinity, the firing step may be performed in multiple stages instead of one stage. For example, the raw material mixture obtained by the mixing step is first fired first (first firing step), then pulverized again with a ball mill or the like as necessary, and then fired again (second firing step). The method of performing once or more is mentioned. The re-baking (second baking step) may be performed as many times as secondary baking or tertiary baking. At this time, the fired product obtained by primary firing may be introduced into the subsequent firing only with the fired product, or a part of the above-described phosphor raw material mixed and fired is pulverized, and the remaining raw materials are mixed therein. And it can also take the aspect of baking.

The temperature of the primary firing is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 800 ° C. or higher, preferably 1000 ° C. or higher, and usually 1900 ° C. or lower, preferably 1800 ° C. or lower, more preferably 1700. It is the range below ℃.
Here, in order to obtain a phosphor having a uniform particle size, it is preferable to advance the solid phase reaction in a powder state by setting the primary firing temperature low. On the other hand, in order to obtain a high-luminance phosphor, it is preferable that the primary firing temperature is set high to produce a liquid phase and the raw materials are sufficiently mixed, and then the crystals are grown by secondary firing.

The time for the primary firing is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 hour or longer, preferably 2 hours or longer, and usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours. The time is less than or equal to 12 hours or less.
Conditions such as temperature and time in firing after the secondary firing are basically the same as those described in the above-mentioned firing step column.

The flux may be mixed before the primary firing or may be mixed before firing after the secondary firing. Also, the firing conditions such as the atmosphere may be changed between the primary firing and the secondary firing and thereafter.
The firing conditions at this time are appropriately selected within the same range as described above. However, among the firing temperatures in the two consecutive firing steps, the one having at least one step of setting the latter firing temperature to a higher temperature promotes the crystal growth of the phosphor and improves the crystallinity. This is preferable because it can be increased.

Moreover, in order to improve the durability of the phosphor, in addition to the above-described firing step, there may be a step of re-firing at a specific temperature.
The heat treatment temperature in the reheating step is usually 350 ° C. or higher, preferably 400 ° C. or higher, and usually 600 ° C. or lower, preferably 550 ° C. or lower, more preferably, although it depends on the atmosphere during the heat treatment. It is 500 degrees C or less.

As the atmosphere during the heat treatment in the reheating step, in addition to the same as described in the section of the firing step, an oxygen-containing inert gas such as air or oxygen-containing nitrogen can also be used. Is preferred.
In the case of using such an oxygen-containing gas, the oxygen concentration is usually preferably 1% or less.

Furthermore, from the viewpoint of suppressing a decrease in light emission intensity and light emission luminance, a temperature range of 350 ° C. or higher and 450 ° C. or lower is more preferable in the case of an oxygen-containing atmosphere, and more preferably in a nitrogen atmosphere. A temperature range of 350 ° C. or more and 550 ° C. or less can be given.
Examples of the pressure during the heat treatment in the reheating step are the same as those described in the section of the firing step.

The heat treatment time in the reheating step is usually 0.1 hour or longer, preferably 0.5 hour or longer. From the viewpoint of productivity, it is usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours. Hereinafter, it is more preferably 12 hours or less.
By having this reheating process, distortion and defects in the phosphor crystal are further reduced, the crystallinity of the phosphor is improved, and modification of the phosphor surface can be expected, improving the durability of the phosphor. It is thought that it contributes to.

  The re-baking step may be performed on the phosphor immediately after the firing step, but after the firing step, the phosphor after performing the below-described pulverization, washing, classification step, etc. preferable. At this time, it is preferable to have a process of washing with an acidic liquid medium such as an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid; or an aqueous solution of an organic acid such as acetic acid. In addition, when it has the process wash | cleaned with an acidic liquid medium, it is preferable to wash | clean further with water similarly to the below-mentioned method before a rebaking process so that an acid may not remain on fluorescent substance.

Further, the reheating treatment may be performed a plurality of times by changing the atmosphere. In that case, the treatment atmosphere may be changed by each reheating treatment, such as performing the reheating treatment in an H ₂ containing atmosphere after the reheating treatment in an oxygen containing atmosphere.
[2-7. Post-processing]
After the heat treatment in the above-described firing step, pulverization, washing, drying, classification treatment, and the like are performed as necessary.

[Crushing treatment]
The pulverization process is performed on the fired product when the obtained phosphor does not have a desired particle size, for example. The pulverization method is not particularly limited. For example, the dry pulverization method and the wet pulverization method described in the description of the phosphor raw material mixing step can be used, but the destruction of the generated phosphor crystal is suppressed, and the intended treatment such as secondary particle crushing is performed. In order to proceed, for example, balls such as alumina, silicon nitride, ZrO ₂ , glass, or the like, or balls such as iron cored urethane are placed and ball milling is performed for about 10 minutes to 24 hours. Is preferred. In this case, you may use 0.05-2 weight% of dispersing agents, such as alkali phosphates, such as organic acid and hexametaphosphoric acid.

[Cleaning treatment]
The cleaning treatment can be performed, for example, with water such as deionized water, an organic solvent such as ethanol, or an alkaline aqueous solution such as ammonia water. Also, for the purpose of removing the impurity phase adhering to the surface of the phosphor such as used flux and improving the light emission characteristics, for example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid; or organic such as acetic acid An aqueous acid solution can also be used. In this case, it is preferable to further wash with water after washing in an acidic aqueous solution.

As the degree of washing, it is preferable that the pH of the supernatant obtained by dispersing the washed phosphor in water 10 times by weight and allowing it to stand for 1 hour is neutral (about pH 7 to 9). This is because if it is biased to basic or acidic, the liquid medium or the like may be affected when mixed with the liquid medium or the like described later.
The degree of washing can also be expressed by the electrical conductivity of the supernatant obtained by dispersing the washed phosphor in 10 times the weight ratio of water and allowing it to stand for 1 hour. The electrical conductivity is preferably as low as possible from the viewpoint of light emission characteristics, but in consideration of productivity, the washing treatment is usually repeated until it is 10 mS / m or less, preferably 5 mS / m or less, more preferably 4 mS / m or less. It is preferable.

  As a method for measuring electrical conductivity, phosphor particles having a specific gravity heavier than water are obtained by stirring and dispersing in water 10 times the weight of the phosphor for a predetermined time, for example, 10 minutes, and then allowing to stand for 1 hour. The electrical conductivity of the supernatant liquid at this time may be measured using an electrical conductivity meter “EC METER CM-30G” manufactured by Toa Decay Co., Ltd. Although there is no restriction | limiting in particular as water used for a washing process and a measurement of electrical conductivity, Demineralized water or distilled water is preferable. Among them, those having particularly low electric conductivity are preferable, and those having a conductivity of usually 0.0064 mS / m or more, and usually 1 mS / m or less, preferably 0.5 mS / m or less are used. The electrical conductivity is usually measured at room temperature (about 25 ° C.).

[Classification processing]
The classification treatment can be performed, for example, by performing a water sieving or water tank treatment, or by using various classifiers such as various air classifiers or vibrating sieves. In particular, when dry classification using nylon mesh and water tank treatment are used in combination, a phosphor with good dispersibility having a weight median diameter of about 20 μm can be obtained.

  Here, in the water sieving or elutriation treatment, the aqueous medium is usually used to disperse the phosphor particles at a concentration of about 0.1 to 10% by weight in the aqueous medium and to suppress the deterioration of the phosphor. The pH is usually 4 or more, preferably 5 or more, and usually 9 or less, preferably 8 or less. Further, when obtaining phosphor particles having a weight median diameter as described above, in the water sieving and elutriation treatment, for example, particles of 50 μm or less are obtained, and then particles of 30 μm or less are obtained. Is preferable from the viewpoint of balance between work efficiency and yield. Moreover, as a minimum, it is preferable to perform the process of sieving a thing normally 1 micrometer or more, Preferably 5 micrometers or more.

〔surface treatment〕
Resin in the phosphor-containing portion of the light-emitting device described later in order to further improve the weather resistance such as moisture resistance when the light-emitting device is manufactured by the method described later using the obtained phosphor of the present invention In order to improve the dispersibility, a known surface treatment method such as coating the surface of the phosphor with a different substance may be performed as necessary.

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

[3-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention, It can select arbitrarily from what was mentioned above. Moreover, the fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, you may make the fluorescent substance containing composition of this invention contain fluorescent substances other than the fluorescent substance of this invention, unless the effect of this invention is impaired remarkably.

[3-2. Liquid medium]
The kind of the liquid medium used in the phosphor-containing composition of the present invention is not particularly limited, and a curable material that can be molded over the semiconductor light emitting element can be used.
The curable material is a fluid material that is cured by performing some kind of curing treatment. Here, the fluid state means, for example, a liquid state or a gel state. The curable material is not particularly limited as long as it secures the role of guiding the light emitted from the solid light emitting element to the phosphor. Moreover, only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.

As the inorganic material, for example, 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 a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having
On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include (meth) acrylic resins such as poly (meth) acrylic acid methyl; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.

  Among these curable materials, the phosphor-containing composition of the present invention preferably uses a silicon-containing compound that has little deterioration with respect to light emission from a semiconductor light-emitting device and is excellent in alkali resistance, acid resistance, and heat resistance. . The silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone compound), inorganic materials such as silicon oxide, silicon nitride, silicon oxynitride, borosilicate, phosphosilicate Examples thereof include glass materials such as salts and alkali silicates. Of these, silicone materials are preferred from the viewpoints of transparency, adhesion, ease of handling, mechanical and thermal adaptability relaxation characteristics, and the like.

The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and for example, condensation-type, addition-type, improved sol-gel type, photo-curing type silicone-based materials can be used.
As the condensed silicone material, for example, semiconductor light-emitting device members described in JP-A-2007-112973 to 112975, JP-A-2007-19459, JP-A-2008-34833, and the like can be used. Condensation-type silicone materials have excellent adhesion to components such as packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.

  Examples of the addition-type silicone material include potting silicone materials described in JP-A-2004-186168, JP-A-2004-221308, JP-A-2005-327777, JP-A-2003-183881, Organically modified silicone materials for potting described in JP-A-2006-206919, silicone materials for injection molding described in JP-A-2006-324596, silicone materials for transfer molding described in JP-A-2007-231173, etc. Can be suitably used. The addition-type silicone material has advantages such as a high degree of freedom in selection such as a curing speed and a hardness of a cured product, a component that does not desorb during curing, hardly shrinking due to curing, and excellent deep part curability.

  Moreover, as an improved sol-gel type silicone material that is one of the condensation types, for example, the silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-119569 and the like can be used. It can be used suitably. The improved sol-gel type silicone material has an advantage that it has a high degree of crosslinking, heat resistance, light resistance and durability, and is excellent in the protective function of a phosphor having low gas permeability and low moisture resistance.

As the photocurable silicone material, for example, silicone materials described in JP 2007-131812 A, JP 2007-214543 A, and the like can be suitably used. The ultraviolet curable silicone material has advantages such as excellent productivity because it cures in a short time, and it is not necessary to apply a high temperature for curing, so that the light emitting element is hardly deteriorated.
These silicone materials may be used alone, or a mixture of a plurality of silicone materials may be used if curing inhibition does not occur when mixed.

[3-3. Content ratio of liquid medium and phosphor]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 25% by weight or more, preferably 40% by weight or more, based on the entire phosphor-containing composition of the present invention. The amount is usually 99% by weight or less, preferably 95% by weight or less, more preferably 80% by weight or less. 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, the mixing ratio as described above is usually used. It is desirable to use a liquid medium. On the other hand, when there is too little liquid medium, fluidity | liquidity may fall and it may become 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 using a silicon-containing compound for the purpose of improving heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin are contained so as not to impair the durability of the silicon-containing compound. Also good. 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.

  The content of the phosphor 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 usually 1% by weight or more with respect to the entire phosphor-containing composition of the present invention, Preferably it is 5 weight% or more, More preferably, it is 20 weight% or more, and is 75 weight% or less normally, Preferably it is 60 weight% or less. The proportion of the phosphor of the present invention in the phosphor in the phosphor-containing composition is also arbitrary, but is usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less. If the phosphor content in the phosphor-containing composition is too high, the flowability of the phosphor-containing composition may be inferior and difficult to handle, and if the phosphor content is too low, the light emission efficiency of the light-emitting device decreases. There is a tendency.

[3-4. Other ingredients]
In the phosphor-containing composition of the present invention, other than the phosphor and the liquid medium, for example, a metal oxide for adjusting the refractive index described later, or a diffusing agent, unless the effect of the present invention is significantly impaired. Additives such as fillers, viscosity modifiers, and UV absorbers may be included. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

4. Light-Emitting Device A light-emitting device of the present invention (hereinafter appropriately referred to as “light-emitting device”) includes a first light emitter (excitation light source) and a second light source that emits visible light when irradiated with light from the first light emitter. And a first phosphor containing at least one phosphor of the present invention described in the above-mentioned section “1, Phosphor” as the second light emitter. Is.

As the phosphor of the present invention, a phosphor that emits fluorescence in the red region under irradiation of light from an excitation light source (hereinafter sometimes referred to as “the red phosphor of the present invention”) is usually used. The red phosphor of the present invention preferably has an emission peak in a wavelength range of 550 nm to 700 nm. Any one of the red phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.

By using the red phosphor of the present invention, the light emitting device of the present invention exhibits high luminous efficiency with respect to an excitation light source (first light emitter) having light emission in the blue region. When used in a white light emitting device such as a display light source, the light emitting device is excellent.
In addition, preferred specific examples of the red phosphor of the present invention used in the light emitting device of the present invention include the phosphor of the present invention described in the above-mentioned “1, Phosphor” column, and the [Example] described later. The phosphor used in each example in the column is listed.

The light-emitting device of the present invention has a first light emitter (excitation light source), and at least the phosphor of the present invention is used as the second light emitter. It is possible to arbitrarily adopt the apparatus configuration. A specific example of the device configuration will be described later.
As the emission peak in the red region in the emission spectrum of the light emitting device of the present invention, one having an emission peak in the wavelength range of 580 nm or more and 650 nm or less is preferable.

  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).

  The light emitting device of the present invention preferably has a light emission efficiency of usually 10 lm / W or more, particularly 30 lm / W or more, particularly 50 lm / W or more. The luminous efficiency is obtained by obtaining the total luminous flux from the result of the emission spectrum measurement using the light emitting device as described above and dividing the lumen (lm) value by the power consumption (W). The power consumption is obtained by measuring a voltage using a True RMS Multimeters Model 187 & 189 manufactured by Fluke in a state in which 20 mA is energized, and obtaining the product of the current value and the voltage value.

  Among the light emitting devices of the present invention, in particular, as a white light emitting device, specifically, an excitation light source as described later is used as the first light emitter, and in addition to the red phosphor as described above, a blue light source as described later is used. A phosphor that emits fluorescence (hereinafter referred to as “blue phosphor” as appropriate), a phosphor that emits green fluorescence (hereinafter referred to as “green phosphor” as appropriate), and a phosphor that emits yellow fluorescence (hereinafter referred to as “yellow fluorescence” as appropriate). It is obtained by using known phosphors such as “body”) in any combination and adopting a known device configuration.

Here, the white color of the white light emitting device is any of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.
[4-1. Configuration of light emitting device]
<4-1-1. 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 emission peak wavelength of the first illuminant is not particularly limited as long as it overlaps with the absorption wavelength of the second illuminant described later, and an illuminant having a wide 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 in 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 blue light is used as excitation light, it 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, and even more preferably 460 nm. It is desirable to use a light emitter having the following emission peak wavelength. On the other hand, when near-ultraviolet light is used as excitation light, the phosphor of the present invention is excited by blue light from a phosphor that emits blue light when excited by near-ultraviolet light. It is preferable to select excitation light (near ultraviolet light) having a wavelength suitable for the band. Specifically, it is desirable to use a luminescent material having an emission peak wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 410 nm or less, more preferably 400 nm or less. .

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a laser diode (LD), 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 significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. 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. As the GaN-based LED and LD, those having an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer are preferable. Among them, since the emission intensity is very high, the GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and more preferably a multiple quantum well structure having an In _X Ga _Y N layer and a GaN layer. preferable.

In the above, the value of X + Y is usually a value 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 heterostructure sandwiched between Ga _Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure 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.
<4-1-2. 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 contains the first phosphor including the red phosphor of the present invention. In addition, a second fluorescent material (a blue fluorescent material, a green fluorescent material, a yellow fluorescent material, an orange fluorescent material, etc.), which will be described later, is appropriately contained in accordance with the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

Used for the in the second luminescent material is not particularly limited to the phosphor composition other than the phosphor of the present invention, the host _{crystal, Y 2 O 3, YVO 4} , Zn 2 SiO 4, Y 3 Metal oxides typified by Al ₅ O ₁₂ , Sr ₂ SiO ₄ , metal nitrides typified by (Ca, Sr) AlSiN ₃ , phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, etc. And CeS, Pr, Nd, Pm, Sm, Eu, Tb, Dy, sulfides typified by ZnS, SrS, CaS, etc., oxysulfides typified by Y ₂ O ₂ S, La ₂ O ₂ S, etc. , Ho, Er, Tm, Yb, and other rare earth metal ions, and Ag, Cu, Au, Al, Mn, Sb, and other metal ions are combined as activators or coactivators.

  Specific examples of preferred crystal matrixes are shown in the following table.

However, the matrix crystal and the activator element or 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.

<4-1-2-1. First phosphor>
The 2nd light-emitting body in the light-emitting device of this invention contains the 1st fluorescent substance containing the fluorescent substance of the above-mentioned this invention at least. 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 the same color fluorescence as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor. Usually, the phosphor of the present invention is a red phosphor. Therefore, as the first phosphor, other types of red phosphors or phosphors emitting orange fluorescence (hereinafter referred to as “orange phosphors” as appropriate). Can be used in combination.

  The weight median diameter of the first phosphor used in the light emitting device of the present invention is usually in the range of 2 μm or more, especially 5 μm or more, and usually 30 μm or less, especially 20 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.

Any orange or red phosphor that can be used in combination with the phosphor of the present invention 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, which is the same color combination phosphor, 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. It is preferable to be in the following wavelength range.

  The phosphors that can be used as such orange or red phosphors are shown in the following table.

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, Eu (dibenzoylmethane) ) ₃ · 1,10-phenanthroline complexes of β- diketone Eu complex, a carboxylic acid Eu _complex, K 2 _SiF 6: Mn is _{preferred, (Ca, Sr, Ba)} 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, and K ₂ SiF ₆ : Mn are more preferable.

Further, as the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ Si
O ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce are preferable.
<4-1-2-2. Second phosphor>
The second light emitter in the light emitting device of the present invention may contain a phosphor (that is, a second phosphor) in addition to the first phosphor described above, depending on the application. The second phosphor is one or more phosphors having different emission peak wavelengths from 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. As described above, since a red phosphor is usually used as the first phosphor, examples of the second phosphor include phosphors other than the red phosphor such as a blue phosphor, a green phosphor, and a yellow phosphor. Is used.

Second phosphor weight-average median diameter D ₅₀ of which is used for the light emitting device of the present invention is usually 2μm or more and preferably 5μm or more, and usually 30μm or less is preferably in a range of inter alia 20μm or less. When the weight-average median diameter D ₅₀ is too small, and the luminance decreases tends to 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.

<Blue phosphor>
When a blue phosphor is used in addition to the phosphor of the present invention, 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 less than 500 nm, preferably 490 nm or less, more preferably 480 nm or less, more preferably 470 nm or less, It is particularly preferable that the wavelength range is 460 nm or less. When the emission peak wavelength of the blue phosphor used is within this range, it overlaps with the excitation band of the phosphor of the present invention, and the phosphor of the present invention can be efficiently excited by the blue light from the blue phosphor. Because.

  The following table shows phosphors that can be used as such blue phosphors.

Among these, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba , Ca, Mg, Sr) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is preferred, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, Ba ₃ MgSi ₂ O ₈ : Eu is more preferred, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, BaMgAl ₁₀ O ₁₇ : Eu are particularly preferable.

<Green phosphor>
When a green phosphor is used in addition to the phosphor of the present invention, 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 preferably in the range of usually 500 nm or more, particularly 510 nm or more, more preferably 515 nm or more, and usually less than 550 nm, especially 542 nm or less, more preferably 535 nm or less. 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 the characteristics as green light may deteriorate.

  The phosphors that can be used as such green phosphors are shown in the table below.

Among these, as the green phosphor, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn is preferred.

When the obtained light-emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce
Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr ) ₃ Si ₆ O ₁₂ : N ₂ : Eu is preferred.

When the obtained light emitting device is used for an image display device, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, _{sr) 3 Si 6 O 12:} N 2: Eu, SrGa 2 S 4: Eu, BaMgAl 10 O 17: Eu, Mn are preferable.
<Yellow phosphor>
When a yellow phosphor is used in addition to the phosphor of the present invention, 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.

  The phosphors that can be used as such yellow phosphors are shown in the table below.

More in even, as the yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, Sr) Si ₂ N ₂ O ₂ : Eu is preferred.
Specifically, when the semiconductor light emitting device of the present invention is configured as a white light emitting device, examples of preferable combinations of the semiconductor light emitting element, the phosphor of the present invention, and other phosphors include the following ( A combination of A) to (C) can be mentioned.

(A) A blue light emitter (blue LED or the like) is used as a semiconductor light emitting element, the phosphor of the present invention is used as a red phosphor, and a green phosphor or a yellow phosphor is used as another phosphor. As the green phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, (Ca, Sr) Sc ₂ O ₄ : Ce phosphor, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce-based phosphor, SrGa ₂ S ₄ : Eu-based phosphor, Eu-activated β-sialon-based phosphor, (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu-based phosphor, and M _One or two or more green phosphors selected from the group consisting of ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element) are preferred. The yellow phosphor is a kind selected from the group consisting of Y ₃ Al ₅ O ₁₂ : Ce phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, and α-sialon phosphor Two or more yellow phosphors are preferred. A green phosphor and a yellow phosphor may be used in combination.

(B) A near-ultraviolet light emitter (near-ultraviolet LED or the like) is used as the semiconductor light-emitting element, the phosphor of the present invention is used as the red phosphor, and the blue phosphor and the green phosphor are used as the other phosphors. In this case, blue phosphors include (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu, and (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ). ) ₆ (Cl, F) ₂ : One or more blue phosphors selected from the group consisting of Eu are preferable. Further, as the green phosphor, in addition to the green phosphor exemplified in the above section (A), (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, Mn, (Ba, Sr, Ca) ₄ Al ₁₄ O ₂₅ : Eu, and _{(Ba, Sr, Ca) Al} 2 O 4: one or two or more of the green phosphor selected from the group consisting of Eu is preferred.

(C) A blue light emitter (blue LED or the like) is used as the semiconductor light emitting element, the phosphor of the present invention is used as the red phosphor, and an orange phosphor is further used. In this case, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.
Further, the combination of the phosphors described above will be described more specifically below.
When a blue light emitting element such as a blue LED is used as a semiconductor light emitting element and used for a backlight of an image display device, the combinations shown in the following table are preferable.

  Table 7 shows more preferable combinations among the combinations shown in Table 6.

  Further, particularly preferred combinations are shown in Table 8.

Each color phosphor shown in Tables 6 to 8 has an excellent temperature characteristic that is excited by light in the blue region, emits light in the red region and the green region, respectively, and has little change in emission peak intensity due to temperature change. Yes.
Therefore, by combining two or more kinds of phosphors including these color phosphors with a semiconductor light emitting element that emits light in the blue region, the light emission efficiency for the color image display device of the present invention can be set higher than before. It can be set as the semiconductor light-emitting device suitable for the light source used for a light.

When a solid light emitting element that emits light in the near ultraviolet to ultraviolet region and a phosphor are used in combination, the phosphor combinations shown in Tables 6 to 8 above are further combined with (Sr, Ca, Ba, Mg) ₁₀ ( PO ₄ ) ₆ (Cl, F): Eu, and (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu selected from the group consisting of Eu It is preferable to combine phosphors, and it is more preferable to combine (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F): Eu or (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu. preferable. At this time, it is preferable to combine BaMgAl ₁₀ O ₁₇ : Eu, Mn as the green phosphor.
Furthermore, when a phosphor having afterglow is used as a phosphor other than the phosphor of the present invention, the color of afterglow can be changed. For example, the afterglow of various colors, such as white, pink, and yellow, can be obtained by using the red phosphor of the present invention and a blue and / or green afterglow phosphor. Blue, blue-green, and green long afterglow phosphors that can be used in such applications include (Ca, Sr) Al ₂ O ₄ : Eu, Nd, (Ca, Sr, Ba) (Al, B) ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, (Ca, Sr, Ba) ₂ MgSi ₂ O ₇ : Eu, Dy, (Ca, Sr, Ba) ₃ MgSi ₂ O ₇ : Eu, Dy ZnS: Cu, Co and the like.

[4-2. 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 denotes a mount lead, reference numeral 6 denotes an inner lead, reference numeral 7 denotes an excitation light source (first light emitter), reference numeral 8 denotes a phosphor-containing portion, reference numeral 9 denotes a conductive wire, reference numeral 10 Indicates 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 portion (second light emitter), reference numeral 24 is a frame, reference numeral 25 is a conductive wire, reference numerals 26 and 27 are electrodes. Respectively.

[4-3. Application of light emitting device]
The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, the illumination device is particularly preferable. And as a light source for image display devices.
<4-3-1. 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.

<4-3-2. 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. 5. Fluorescent paint and laminate using the same The phosphor of the present invention is dispersed in various organic solvents and / or binder resins such as acrylic resin, epoxy resin, polyimide resin, and glass, and further added as necessary. By adding an agent, a fluorescent paint (hereinafter referred to as “the fluorescent paint of the present invention” as appropriate) can be obtained.

  The fluorescent paint of the present invention may contain only one kind of the phosphor of the present invention, or may contain two or more kinds in any combination and ratio. Further, the fluorescent paint of the present invention may contain a phosphor other than the phosphor of the present invention, and even in that case, may contain only one type of phosphor other than the phosphor of the present invention, Two or more kinds may be included in any combination and ratio.

What is necessary is just to set arbitrarily content of the fluorescent substance in the fluorescent paint of this invention according to a well-known technique.
The fluorescent paint can be applied to various labels / display boards, toys, etc., as described in the above-mentioned use of the phosphor. The fluorescent paint is applied on a substrate for each use and dried on the substrate. It can be set as the laminated body which laminated | stacked the fluorescent substance layer. In addition to the substrate and the phosphor layer, the laminated body may have other layers according to each application at an arbitrary place.

  The thickness of the phosphor layer at this time is usually 10 μm or more, preferably 100 μm or more, and is usually 5 mm or less, preferably 1 mm or less.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
(Measurement methods for various physical properties)
<Luminescence peak intensity>
At spectrofluorimeter F-4500 manufactured by Hitachi High-Technologies Corporation at room temperature
The emission spectrum of 455 nm excitation was measured, and the peak height was defined as the emission peak intensity.

<Afterglow characteristics>
The afterglow measurement was carried out at room temperature using a spectrofluorimeter F-4500 manufactured by Hitachi High-Technologies Corporation in the following experimental procedure.
After setting the measurement sample at a predetermined position on the spectrofluorometer, in the measurement program FL Solution, the measurement mode is “time change”, the excitation wavelength is 310 nm, the fluorescence wavelength (detection wavelength) is 600 nm, the measurement time is 600 s, The waiting time was 0 s, the excitation side slit was 10.0 nm, the light receiving side slit was 10.0 nm, the photomultiplier voltage was 700 V, and the response was 0.08 s.

  The excitation light shutter was opened and the measurement program was run. Immediately after excitation, the excitation light shutter was manually closed, and the time change measurement for a predetermined time was performed. The afterglow characteristics were evaluated by comparing the emission intensity after 10 seconds and after 100 seconds after the excitation light was cut off.

<XRD measurement>
Powder X-ray diffraction measurement (XRD) was performed by a PANaltical powder X-ray diffraction measurement apparatus X′Pert MPD equipped with a Cu—Kα tube.
(Comparative Example 1)
Ca ₃ N ₂ (manufactured by Aldrich), Eu ₂ O ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.), Tm ₂ O ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.), Si ₃ N ₄ (Ube Industries, Ltd.) Manufactured by SN-E10) was mixed well so that the molar ratio of Ca: Eu: Tm: Si = 1.99: 0.005: 0.005: 5. This was put in a boron nitride crucible and heated at 1650 ° C. for 4 hours in a nitrogen atmosphere and a pressure of 0.05 MPa using a high-frequency heating electric furnace.

The obtained powder was put into 1.6 mol / L nitric acid and stirred for 3 hours to remove unreacted raw materials and oxidation products. This was dehydrated and dried to obtain a Ca ₂ Si ₅ N ₈ : Eu, Tm phosphor. Powder XRD was measured for the obtained phosphor. The results are shown in FIG. It agrees well with the powder XRD pattern (JCPDS-ICDD-PDF, 82-2489) of Ca ₂ Si ₅ N ₈ in FIG. 4C, indicating that this crystal phase is obtained.

(Examples 1-6)
The same procedures as in Comparative Example 1 were performed except that Li ₃ N (manufactured by Aldrich) was added to the raw material mixture of Comparative Example 1, and each phosphor of Examples 1 to 6 was obtained. The amount of Li element added to 1 mol of the phosphor raw material is as shown in Table 9.

The powder XRD measurement result of the phosphor of Example 2 is shown in FIG. It is found that this crystal phase is obtained in good agreement with the powder XRD pattern (JCPDS-ICDD-PDF, 82-2489) of Ca ₂ Si ₅ N ₈ described in FIG.
Moreover, the result of having measured the luminescence peak intensity | strength and the afterglow characteristic (luminescence intensity 100 seconds after excitation light stop) of each fluorescent substance of the comparative example 1 and Examples 1-6 is shown in FIG.5 and FIG.6.
From this result, it can be seen that the afterglow characteristics of the phosphor are improved by including Li.

(Comparative Example 2)
A phosphor of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that CaH ₂ (manufactured by Kanto Chemical Co., Inc.) was used instead of Ca ₃ N ₂ as a raw material.
(Examples 7 to 12)
The same procedures as in Comparative Example 2 were performed except that Li ₃ N (manufactured by Aldrich) was added to the raw material mixture of Comparative Example 2, and phosphors of Examples 7 to 12 were obtained. The amount of Li element added to 1 mol of the phosphor raw material is as shown in Table 10.

7 and 8 show the results of measuring the emission peak intensity and the afterglow characteristics (emission intensity after 100 seconds after stopping the excitation light) of the phosphors of Comparative Example 2 and Examples 7-12.
From this result, it can be seen that the afterglow characteristics of the phosphor can be improved by including Li, although the optimum range differs depending on the type of raw material.
(Examples 13 to 15)
The same procedure as in Comparative Example 2 was performed except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the raw material mixture of Comparative Example 2, and phosphors of Examples 3 to 15 were obtained. The addition amount of Zn element with respect to 1 mol of the phosphor raw material is as shown in Table 11.

The result of powder XRD measurement of the phosphor obtained in Example 14 is shown in FIG. The powder XRD measurement result is in good agreement with the powder XRD pattern (JCPDS-ICDD-PDF, 82-2489) of Ca ₂ Si ₅ N ₈ shown in FIG. It can be seen that a crystalline phase is obtained.
Furthermore, the result of having measured the afterglow characteristic (emission intensity | strength 10 seconds after excitation light stop) of each fluorescent substance of the comparative example 2 and Examples 13-15 is shown in FIG.

From this result, it is understood that the afterglow characteristics of the phosphor can be improved by containing Zn.
(Comparative Examples 3 and 4)
Comparative Example 2 was the same as Comparative Example 2 except that MgO (Wako Pure Chemical Industries, Ltd.) was added to the raw material mixture of Comparative Example 2 so that the Mg element was 5 mol% or 10 mol% with respect to 1 mol of the phosphor raw material. The phosphors of Comparative Examples 3 and 4 were obtained.

FIG. 11 shows the results of measuring the afterglow characteristics (the emission intensity after 10 seconds after stopping the excitation light) of the phosphors of Comparative Examples 2-4.
From these results, it is understood that when Mg is contained, the afterglow of the phosphor is shortened in proportion to the amount.
Further, the emission characteristics at the excitation wavelength of 455 nm were measured for the phosphors of Comparative Example 1, Example 11 and Example 14. FIG. 12 shows the emission spectrum, and Table 11 shows the characteristic values. Further, afterglow characteristics of these phosphors were measured by the following method. After setting the measurement sample at a predetermined position of the spectrofluorometer F-4500, in the measurement program FL Solution, the measurement mode is “time change”, the excitation wavelength is 455 nm, the fluorescence wavelength (detection wavelength) is 600 nm, and the measurement time is The initial waiting time was 600 s, the excitation side slit was 10.0 nm, the light receiving side slit was 10.0 nm, the photomultiplier voltage was 400 V, and the response was 0.01 s.
The excitation light shutter was opened and the measurement program was run. After the elapse of 600 s of the initial waiting time, the excitation light shutter was manually closed and the time change measurement for a predetermined time was performed. FIG. 13 shows the evaluation results of the afterglow intensity after the elapse of a predetermined time normalized with the emission intensity just before the excitation light blockage (during excitation light irradiation) as 1, and Table 12 shows the results after 5 minutes after 5 minutes. The afterglow intensity evaluation results after minutes and 8.5 minutes and the afterglow intensity after 8.5 minutes normalized by the emission intensity after 3 minutes are shown.

  From the above results, it can be seen that the phosphor containing Zn is more excellent in afterglow characteristics.

  The present invention can be used in any field where light is used. For example, in addition to indoor and outdoor lighting, image display devices and fluorescent devices for various electronic devices such as mobile phones, household appliances, and outdoor displays are used. It can be suitably used for paints and the like.

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 part (second light emitter)
DESCRIPTION OF SYMBOLS 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 (1st light emission body)
23 Phosphor-containing part (second light emitter)
24 frames
25 Conductive wire
26, 27 electrodes

Claims (12)

A phosphor containing Eu and Tm as activators and having a host crystal composition represented by the following formula [I], the phosphor containing an element selected from the group consisting of Li and Zn .
M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)   The phosphor according to claim 1, wherein Li is contained in a range of 50 mol% or less with respect to 1 mol of the phosphor.   The phosphor according to claim 1, wherein Zn is contained in a range of 10 mol% or less with respect to 1 mol of the phosphor. A method of producing a phosphor having a matrix crystal composition represented by the following formula [I], containing Eu and Tm as activating elements by firing a phosphor material, and a raw material mixture converted to 1 mol of the phosphor A method for producing a phosphor characterized by containing Li element in a range of 50 mol% or less in the raw material mixture.
M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.) A method of producing a phosphor having a matrix crystal composition represented by the following formula [I], containing Eu and Tm as activating elements by firing a phosphor material, and a raw material mixture converted to 1 mol of the phosphor A method for producing a phosphor, characterized in that the raw material mixture contains Zn in a range of less than 10 mol%.
M ₂ Si ₅ N ₈ [I]
(In the formula [I], M represents an alkaline earth metal element.)   6. The production method according to claim 4, wherein an alkaline earth metal hydride is used as the phosphor material. A phosphor-containing composition comprising: the phosphor according to any one of claims 1 to 3; and a liquid medium. A light emitting device having a first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter,
A light emitting device comprising a first phosphor containing at least one phosphor according to any one of claims 1 to 3 as the second light emitter.   An illumination device comprising the light-emitting device according to claim 8.   An image display device comprising the light emitting device according to claim 8.   The fluorescent paint containing the fluorescent substance of any one of Claims 1-3.   A laminate obtained by applying the fluorescent paint according to claim 11 to a substrate.

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