JP2018178129A - Fluophor and manufacturing method therefor, fluophor-containing composition and light-emitting device using fluophor, and image display unit and luminaire using light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red fluophor narrow in half width of a luminescence peak and excellent in light-emitting property, a manufacturing method therefor, a fluophor-containing composition and a light-emitting device using the fluophor, and an image display unit and a luminaire using the light-emitting device.SOLUTION: There is provided a fluophor containing a crystal phase having a chemical composition represented by the following formula [1], and having percentage of Mn based on total molar number of Mand Mn of 0.1 mol% to 40 mol%, and having specific surface area of 1.3 m/g or less. MMF:R [1], wherein Mcontains one or more kind of element selected from a group consisting of K and Na, Mrepresents a metal element containing Si and R represents the activation element containing at least Mn.SELECTED DRAWING: Figure 1

Description

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

  White light, which is essential for lighting and display applications, is generally obtained by combining blue, green and red emissions according to the additive mixing principle of light. Therefore, for example, in a backlight for color liquid crystal display devices, which is a field of display applications, blue, green and red light emitters can be used to efficiently reproduce a wide range of colors on chromaticity coordinates. It is desirable that only the emission intensity be high and that the color purity be good. For example, the National Television Standard Committee (NTSC) is known as one of the standards of TV color gamut.

  Recently, attempts have been made to use semiconductor light emitting devices as light sources of these three colors. However, using semiconductor light emitting devices for all three colors is not common because it requires a circuit that compensates for the color shift during use. Therefore, it is practical to obtain the desired three colors by wavelength-converting the light emitted from the semiconductor light emitting element using a phosphor. Specifically, the method of emitting blue, green and red using a semiconductor light emitting element of near-ultraviolet emission as a light source and the emission from the semiconductor light emitting element of blue emission are used as blue as it is, and green and red are wavelengths by phosphors It is known how to obtain by transformation.

  Among them, as a phosphor used for display applications, it is considered preferable to use a phosphor having a narrow half width of a light emission peak from the viewpoint of light utilization efficiency and the like. In addition, even when used for lighting applications, in order to improve color rendering, it is preferable to use a phosphor having a narrow half width of the emission peak, in consideration of the balance with the light emission efficiency when used with other phosphors. it is conceivable that.

As a semiconductor light emitting device using a phosphor having a narrow half width of emission peak, a device using K ₂ TiF ₆ : Mn or the like as a red phosphor is known, and in the hydrofluoric acid as the phosphor, A method is known which is obtained by evaporation to dryness under the following conditions (see Patent Document 1).

  In addition, as a method for producing the phosphor, a method using a poor solvent precipitation method is also known (see Patent Document 2).

U.S. Patent Publication No. 2006/0169998 U.S. Pat. No. 3,576,756

The production method of K ₂ TiF ₆ : Mn or the like by evaporation to dryness in hydrofluoric acid described in Patent Document 1 is difficult for mass production from the aspect of safety and productivity.

  Moreover, when the present inventors further tried the method described in Patent Document 2, it was found that the obtained phosphor particles were fine, the luminance was low, and the practicability was insufficient.

  From such a thing, although the practical use of a phosphor having a narrow half width of a light emission peak and a light emitting device using the same has been desired for display and illumination applications, these have not been realized yet. Is the current situation.

  The present invention has been made in view of the above problems, and an object thereof is to provide a red phosphor having a narrow emission peak half width and excellent emission characteristics, and a method for producing the same, and using this phosphor A phosphor-containing composition and a light emitting device, and an image display device and a lighting device using the light emitting device.

In view of the above problems, the inventors of the present invention have studied in detail a method of producing a K ₂ SiF ₆ : Mn-based phosphor, and as a result, it is possible to obtain a phosphor having a smaller specific surface area and superior light emission characteristics than before. The present invention has been completed by finding a technology that can be suitably used for applications such as light emitting devices.

  That is, the present invention provides the following (1) to (10) as the gist.

(1) A crystal phase having a chemical composition represented by the following formula [1] is contained, and the ratio of Mn to the total number of moles of M ⁴ and Mn is 0.1 mol% or more and 40 mol% or less, And a specific surface area of 1.3 m ² / g or less.
M ¹ ₂ M ⁴ F ₆ : R ... [1]
(In the above-mentioned formula [1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ is a metal element containing Si, R contains at least Mn. Represents an activating element.)

(2) The phosphor according to (1), wherein the peak value of the particle size distribution is one.

(3) The phosphor according to (1) or (2), wherein the quarter deviation of the particle size distribution is 0.6 or less.

(4) A process comprising reacting a solution containing at least Si and F with a solution containing at least K, Mn, and F to obtain the compound represented by the formula [1]. The manufacturing method of the fluorescent substance in any one of (1) thru | or (3).

(5) A method for producing a phosphor containing a crystal phase having a chemical composition represented by the following formula [1], which is one or more selected from the group consisting of K, Na, Si, Mn, and F A method for producing a phosphor, comprising mixing two or more of a solution containing an element to precipitate the phosphor.
M ¹ ₂ M ⁴ F ₆ : R ... [1]
(In the above-mentioned formula [1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ is a metal element containing Si, R contains at least Mn. Represents an activating element.)

(6) A phosphor-containing composition comprising the phosphor according to any one of (1) to (3) and a liquid medium.

(7) A light emitting device comprising: a first light emitting body; and a second light emitting body that emits visible light by irradiation of light from the first light emitting body, wherein the second light emitting body A light emitting device comprising a first phosphor containing one or more of the phosphors according to any one of (1) to (3).

(8) The device according to (7), wherein the second phosphor includes a second phosphor including one or more phosphors having different emission peak wavelengths from the first phosphor as the second phosphor. The light emitting device as described.

(9) A lighting device comprising the light emitting device according to (7) or (8).

(10) An image display device comprising the light emitting device according to (7) or (8).

According to the present invention, it is possible to provide a red phosphor having a narrow emission peak half width and excellent emission characteristics.
Furthermore, it is possible to provide a method for producing the red phosphor with improved safety and productivity as compared to the prior art.
In addition, by using the phosphor of the present invention, it is possible to provide a light emitting device, a lighting device, and an image display device having a wider color reproduction range and higher emission efficiency than conventional.

It is a typical perspective view showing one example of a light emitting device of the present invention. Fig.2 (a) is typical sectional drawing which shows one Example of the cannonball type light-emitting device of this invention, FIG.2 (b) is typical which shows one Example of the surface mounted type light-emitting device of this invention. FIG. It is a typical sectional view showing one example of the lighting installation of the present invention. It is a chart which shows the powder X-ray-diffraction pattern of the fluorescent substance obtained by Example 1-1, Example 1-2, and Comparative Example 1-1. It is a chart which shows the excitation and emission spectrum of the fluorescent substance obtained in Example 1-1. It is a chart which shows the particle size distribution curve of the fluorescent substance obtained in Example 1-1, Example 1-2, and Example 1-9. It is a chart which shows the particle size distribution curve of the fluorescent substance obtained by Comparative Example 1-1. It is a SEM photograph of the fluorescent substance obtained in Example 1-1, Example 1-2, and Example 1-9. It is a SEM photograph of the fluorescent substance obtained by comparative example 1-1. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced in Example 2-1. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced by Comparative Example 2-1. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced in Example 2-2. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced in Example 2-3. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced by Comparative Example 2-2. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced by Comparative Example 2-3. It is a chart which shows the particle size distribution curve of the fluorescent substance obtained in Example 1-16, Example 1-17, Example 1-18, and Example 1-19. It is a SEM photograph of the fluorescent substance obtained in Example 1-16, Example 1-17, Example 1-18, and Example 1-19.

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

  In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

Further, in the composition formula of the phosphor in the present specification, the delimitation of each composition formula is indicated by being separated by a reading point (,). In addition, in the case where a plurality of elements are listed separated by a comma (,), it is indicated that one or two 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” is “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 " It is assumed that “Ca _1-x-y Sr _x Ba _y Al ₂ O ₄ : Eu” is comprehensively shown (however, in the above formula, 0 <x <1, 0 <y <1, 0). <X + y <1).

[1. Phosphor]
[1-1. Composition of phosphor]
The phosphor of the present invention contains a crystal phase having a chemical composition represented by the following formula [1], and the ratio of Mn to the total number of moles of M ⁴ and Mn is 0.1 mol% or more and 40 mol% or less The phosphor of
M ¹ ₂ M ⁴ F ₆ : R ... [1]
(In the above-mentioned formula [1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ is a metal element containing Si, R contains at least Mn. Represents an activating element.)

In the above formula [1], M ¹ contains an element selected from the group consisting of potassium (K) and sodium (Na). One of these elements may be contained alone, or two of these elements may be contained in any ratio. In addition to the above, it may partially contain an alkali metal element such as Li, Rb or Cs, or (NH ₄ ) as long as the performance is not affected. The content of Li, Rb, Cs and (NH ₄ ) is usually 10 mol% or less based on the total amount of M ¹ .

Among them, M ¹ preferably contains at least K. Usually, K occupies 90 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, and more preferably 99 mol% or more based on the total amount of M ^1. It is particularly preferable to use only K.

In the above formula [1], M ⁴ contains at least Si. Usually, Si accounts for 90 mol% or more based on the total M ⁴ amount is preferably when account for more than 97 mol%, more preferably if the account for at least 98 mol%, more preferably at least 99 mol% It is particularly preferable to use only Si. That is, it is particularly preferable that the phosphor containing the crystal phase having the chemical composition represented by the formula [1] contains the crystal phase having the chemical composition represented by the following formula [2].
M ¹ ₂ SiF ₆ : R ... [2]
(In the above formula [2], M ¹ contains one or more elements selected from the group consisting of K and Na, and R represents an activating element containing at least Mn.)

In the above Formula [1], as elements that may be contained as M ⁴ in addition to Si, Ti, Zr, Ge, Sn, Al, Ga, B, In, Nb, Mo, Zn, Ta, W 1 type, or 2 or more types selected from the group which consists of Re, and Mg are mentioned.

  In the above formulas [1] and [2], R is an activating element containing at least Mn, and as activating elements which may be contained as R in addition to Mn, Cr, Fe, Co, Ni, 1 type, or 2 or more types selected from the group which consists of Cu, Ru, and Ag are mentioned.

  R preferably contains at least 90 mol%, more preferably at least 95 mol%, particularly preferably at least 98 mol%, of Mn based on the total amount of R, and it is particularly preferable to contain only Mn.

In the phosphor of the present invention, the ratio of Mn to the total number of moles of M ⁴ and Mn (in the present invention, this ratio is hereinafter referred to as “Mn concentration”) is 0.1 mol% or more and 40 mol% or less It is characterized by If the Mn concentration is too low, the absorption efficiency of excitation light by the phosphor decreases, so the brightness tends to decrease. If the Mn concentration is too high, the absorption efficiency increases, but the internal quantum efficiency and brightness decrease due to concentration quenching. Tend to The lower limit of the more preferable Mn concentration is 0.4 mol% or more, more preferably 1 mol% or more, and particularly preferably 2 mol% or more. In addition, the upper limit of the Mn concentration is more preferably 20 mol% or less, still more preferably 8 mol% or less, and particularly preferably 6 mol% or less.

  The chemical composition analysis of the Mn concentration contained in the phosphor in the present invention can be measured, for example, by SEM-EDX. In this method, in a scanning electron microscope (SEM) measurement, the phosphor is irradiated with an electron beam (for example, an acceleration voltage of 20 kV), and characteristic X-rays emitted from each element contained in the phosphor are detected to detect the element. It is an analysis. For example, SEM (S-3400N) manufactured by Hitachi, Ltd. and energy dispersive X-ray analyzer (EDX) EX-250x-act manufactured by Horiba, Ltd. can be used as the measuring apparatus.

  The phosphor of the present invention is preferably manufactured by the method described in the method of manufacturing a phosphor described later, but in the method of manufacturing the phosphor, the preparation composition of the phosphor raw material and the following reasons. There is a slight deviation from the composition of the resulting phosphor. The phosphor of the present invention is characterized in that it has the above-mentioned specific composition as the composition of the obtained phosphor, not the feed composition of the raw material at the time of production of the phosphor.

The ion radius (0.53 Å) of Mn ⁴⁺ is larger than the ion radius (0.4 Å) of Si ⁴⁺ , and Mn ⁴⁺ does not totally dissolve in K ₂ SiF ₆ but partially dissolves, so In comparison, the substantially activated Mn ^{4 +} concentration is limited and reduced. However, even when the concentration of Mn ⁴⁺ contained in the phosphor is low, according to the manufacturing method of the present invention described later, since particle growth is promoted, sufficient absorption efficiency and luminance can be provided.

[1-2. Characteristics of phosphor]
<Emission spectrum>
The phosphor of the present invention preferably has the following features when the emission spectrum is measured when excited by light having a peak wavelength of 455 nm.

  The peak wavelength λp (nm) in the above-mentioned emission spectrum is usually larger than 600 nm, preferably in the range of 605 nm or more, more preferably 610 nm or more, and usually in the range of 660 nm or less, more preferably 650 nm or less. If the emission peak wavelength λp is too short, it tends to be yellowish, while if it is too long, it tends to take on a dark reddish color, which is not preferable because the characteristics as orange to red light may decrease.

  In the phosphor of the present invention, the full width at half maximum (hereinafter referred to as “FWHM” as appropriate) of the emission peak in the above emission spectrum is usually larger than 1 nm, preferably 2 nm or more, and further 3 nm. It is preferable that the thickness is in the range of less than 50 nm, usually 30 nm or less, further 10 nm or less, and further 8 nm or less. When the half width FWHM is too narrow, the emission intensity may decrease, and when it is too wide, the color purity may decrease.

  In addition, in order to excite said fluorescent substance by the light of peak wavelength 455 nm, a xenon light source can be used, for example. The emission spectrum of the phosphor of the present invention can be measured, for example, by using a 150 W xenon lamp as an excitation light source, and a fluorescence measurement apparatus (manufactured by JASCO Corporation) equipped with a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics Co., Ltd.) as a spectrum measurement apparatus. And so on. The emission peak wavelength and the half width of the emission peak can be calculated from the obtained emission spectrum.

<Quantum efficiency / absorption efficiency>
The higher the internal quantum efficiency of the phosphor of the present invention, the better. The value is usually 50% or more, preferably 75% or more, more preferably 85% or more, and particularly preferably 90% or more. If the internal quantum efficiency is low, the luminous efficiency tends to decrease, which is not preferable.

  It is preferable that the phosphor of the present invention has a high external quantum efficiency. The value is usually 20% or more, preferably 25% or more, more preferably 30% or more, and particularly preferably 35% or more. If the external quantum efficiency is low, the luminous efficiency tends to decrease, which is not preferable.

  It is preferable that the phosphor of the present invention has a high absorption efficiency. The value is usually 25% or more, preferably 30% or more, more preferably 42% or more, and particularly preferably 50% or more. If the absorption efficiency is low, the emission efficiency tends to decrease, which is not preferable.

  The internal quantum efficiency, the external quantum efficiency, and the absorption efficiency can be measured by the methods described in the examples described later.

<Weight median diameter D ₅₀ >
The weight median diameter D ₅₀ of the phosphor of the present invention is preferably in the range of usually 3 μm or more, in particular 10 μm or more, and usually 50 μm or less, in particular 30 μm or less. When the weight median diameter D ₅₀ is too small, the luminance may decrease or the phosphor particles may 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 weight-average median diameter D ₅₀ of the phosphor in the present invention, for example, can be measured using a device such as a laser diffraction / scattering particle size distribution measuring apparatus.

<Specific surface area>
The specific surface area of the phosphor of the present invention is usually 1.3 m ² / g or less, preferably 1.1 m ² / g or less, particularly preferably at 1.0 m ² / g or less, typically 0.05 m ² / g or more, Among them, 0.1 m ² / g or more is preferable. If the specific surface area of the phosphor is too small, the phosphor particles will be large, so there is a tendency to cause uneven coating and clogging of the dispenser etc. If it is too large, the phosphor particles will be small and the contact area with the outside will be large It is inferior to sex. In addition, the smaller the specific surface area of the phosphor, the larger the phosphor particles, the higher the absorption efficiency, and the higher the luminance.
In addition, the specific surface area of the fluorescent substance in this invention is measured by BET 1 point method, for example using the Okura Riken Co., Ltd. product fully automatic specific surface area measuring apparatus (flow method) AMS1000A.

<Particle size distribution>
The phosphor of the present invention preferably has one peak value in its particle size distribution.
The fact that the peak value is 2 or more indicates that there is a peak value of single particle and a peak value of aggregate thereof. Therefore, having two or more peak values also means that single particles are very small. The phosphor of the present invention, in which the peak value of the particle size distribution is one, is large in single particles and very low in aggregates. As a result, the effect of improving the luminance and the effect of reducing the specific surface area and improving the durability due to the large growth of single particles can be obtained.
The particle size distribution of the phosphor in the present invention can be measured, for example, by a laser diffraction / scattering type particle size distribution measuring apparatus LA-300 manufactured by Horiba, Ltd.
Further, the width of the peak of the particle size distribution is preferably narrow. Specifically, the quarter deviation (QD) of the particle size distribution of the phosphor particles is usually 0.18 or more, preferably 0.20 or more, and usually 0.60 or less, preferably 0.40 or less, More preferably, it is 0.35 or less, and particularly preferably 0.30 or less.
The quarter deviation of the particle size distribution is smaller as the particle size of the phosphor particles is uniform. That is, the fact that the quarter deviation of the particle size distribution is small means that the width of the peak of the particle size distribution is narrow and the sizes of the phosphor particles are uniform.
Further, the quarter deviation of the particle size distribution can be calculated using a particle size distribution curve measured using a laser diffraction / scattering type particle size distribution measuring apparatus.

<Particle shape>
It is preferable that the particle shape of the phosphor of the present invention observed from the observation of the SEM photograph of the present invention is in the form of particles uniformly grown in three axial directions. When the particle shape grows uniformly in three axial directions, the specific surface area decreases, and the contact area with the outside is small, so the durability is excellent.
The SEM photograph can be taken, for example, by SEM (S-3400N) manufactured by Hitachi, Ltd.

[1-3. Method of manufacturing phosphor]
The method for producing the phosphor of the present invention is not particularly limited, but methods using poor solvents as in the method 1) below and methods 2) below (specifically the following 2-1) And the method which does not use a poor solvent like the method of 2-2).
1) Poor solvent precipitation method 2) After mixing two or more kinds of solutions containing one or more elements selected from the group consisting of K, Na, Si, Mn, and F, precipitates precipitated by mixing (phosphor In this method, it is preferable that all the elements of the elements constituting the target phosphor be contained in the solution to be mixed, and the combination of the solutions to be mixed is specifically the following 2 -1) and the following 2-2).
2-1) A method of mixing a solution containing at least Si and F with a solution containing at least K (and / or Na), Mn and F

2-2) A method of mixing a solution containing at least Si, Mn and F with a solution containing at least K (and / or Na) and F

Hereinafter, each manufacturing method will be described with a case where M ⁴ is Si as a representative example.

1) This method antisolvent precipitation method, for example, as described in Example 1-1 given later, as the starting compound for example an ^M ₁ 2 SiF ₆ and ^M ₁ 2 RF ₆ using (wherein, ^{M 1} , R has the same meaning as in the above-mentioned formula [1].) These are added to hydrofluoric acid in a predetermined ratio, dissolved under stirring and reacted, and then a poor solvent for the phosphor is added And a method of depositing a phosphor, which can be performed in the same manner as the method described in US Pat. No. 3,576,756.

  As described above, in the method described in US Pat. No. 3,576,756, there is a problem that the phosphor particles obtained are fine, the luminance is low, and they are not practical. In precipitating the phosphor, it was found that the target phosphor can be obtained by slowing the rate of addition of the poor solvent or dividingly adding the poor solvent instead of adding the poor solvent at one time.

As a combination of raw material compounds used in this poor solvent precipitation method, a combination of K ₂ SiF ₆ and K ₂ MnF ₆ , a combination of K ₂ SiF ₆ and KMnO ₄ , a combination of K ₂ SiF ₆ and K ₂ MnCl ₆ Etc. is preferred.
Specifically, the combination of K ₂ SiF ₆ and K ₂ MnF ₆ is
Combination of aqueous K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid, H ₂ SiF ₆ aqueous solution and K ₂ MnF ₆ ,
Water soluble K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid and silicates (SiO ₂ , Si alkoxide etc) and K ₂ MnF ₆ Combination of
A combination of potassium silicate (K ₂ SiO ₃ ), hydrofluoric acid and K ₂ MnF ₆ is mentioned.
Specifically, the combination of K ₂ SiF ₆ and KMnO ₄ is
Combination of a water-soluble K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid, H ₂ SiF ₆ aqueous solution and KMnO ₄ ,
Combination of water-soluble K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid and silicates (SiO ₂ , Si alkoxide etc.) and KMnO ₄ ,
A combination of potassium silicate (K ₂ SiO ₃ ), hydrofluoric acid and KMnO ₄ may be mentioned.
Specifically, the combination of K ₂ SiF ₆ and K ₂ MnCl ₆ is
A combination of a water-soluble K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid, H ₂ SiF ₆ aqueous solution and K ₂ MnCl ₆ ,
Water soluble K salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ etc.), hydrofluoric acid and silicates (SiO ₂ , Si alkoxide etc) and K ₂ MnCl ₆ Combination of
A combination of potassium silicate (K ₂ SiO ₃ ), hydrofluoric acid and K ₂ MnCl ₆ is mentioned.

  In addition, the water-soluble potassium salt in the method of the said water-soluble K salt and the below-mentioned 2-1) and 2-2) means the potassium salt whose solubility with respect to water in 15 degreeC is 10 weight% or more.

  Although these raw material compounds are used at such a ratio as to obtain a phosphor having a target composition, as described above, there is a slight difference between the charged composition of the phosphor raw material and the composition of the obtained phosphor, It is important to adjust the composition of the resulting phosphor to be the target composition.

The hydrogen fluoride concentration of hydrofluoric acid is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably It is used as an aqueous solution of 50% by weight or less. For example, in the case of using hydrofluoric acid having a hydrogen fluoride concentration of 40 to 50% by weight, the ratio of hydrofluoric acid (concentration 40 to 50% by weight) to 1 g of K ₂ SiF ₆ is about 30 to 60 ml It is preferred to use as such.

  The reaction can be carried out at atmospheric pressure and room temperature (20-30 ° C.).

  Usually, the starting compound is added to and mixed with hydrofluoric acid in a predetermined ratio, and when all the starting compound is dissolved, a poor solvent is added.

  As the poor solvent, usually, an organic solvent having a solubility parameter of 10 or more and less than 23.4, preferably 10 to 15 is used. Here, the solubility parameter is as defined below.

(Definition of dissolution parameter)
In the regular solution theory, since the force acting between the solvent and the solute is modeled as only the intermolecular force, it can be considered that the interaction which causes the liquid molecules to be aggregated is only the intermolecular force. From the molar heat of vaporization ΔH and the molar volume V, the solution parameter is defined as δ = δ (ΔH / V−RT), since the cohesive energy of the liquid is equivalent to the evaporation enthalpy. That is, it is calculated from the parallel roots (cal / cm ³ ) ^{1/2 of the} heat of vaporization required to evaporate one molar volume of liquid.
It is rare for the actual solution to be a regular solution, and forces other than intermolecular forces such as hydrogen bonding also work between solvent-solute molecules, and it is necessary to mix the two components or to separate them as they are mixed. It is determined thermodynamically by the difference between enthalpy and mixing entropy. However, substances with a close solubility parameter (Solubility Parameter; hereinafter sometimes referred to as “SP value”) tend to be mixed easily. Therefore, the SP value is also a standard for judging the ease of mixing the solute and the solvent.
In the regular solution theory, the force acting between the solvent and the solute is assumed to be only the intermolecular force, so the dissolution parameter is used as a measure to represent the intermolecular force. Although the actual solution is not limited to the regular solution, it is empirically known that the smaller the difference between the SP values of the two components, the higher the solubility.

  Such poor solvents include acetone (dissolution parameter: 10.0), isopropanol (dissolution parameter: 11.5), acetonitrile (dissolution parameter: 11.9), dimethylformamide (dissolution parameter: 12.0), acetic acid (Dissolution parameter: 12.6), ethanol (dissolution parameter: 12.7), cresol (dissolution parameter: 13.3), formic acid (dissolution parameter: 13.5), ethylene glycol (dissolution parameter: 14.2), Phenol (dissolution parameter: 14.5), methanol (dissolution parameter: 14.5 to 14.8), etc. may be mentioned, among which acetone is preferable because it does not contain a hydroxyl group (-OH) and dissolves well in water. These poor solvents may be used alone or in combination of two or more.

  The amount of the poor solvent used varies depending on the type, but usually 50% by volume or more, preferably 60% by volume or more, more preferably 70% by volume or more based on the phosphor material-containing hydrofluoric acid, and usually It is preferable to set it as 200 volume% or less, preferably 150 volume% or less, more preferably 120 volume% or less.

  The addition of the poor solvent may be divided addition or continuous addition, but as the addition rate of the poor solvent to the phosphor material-containing hydrofluoric acid, it is a relatively slow addition rate of 400 ml / hour or less, preferably 100 to 350 ml / hour. It is preferable from the viewpoint of obtaining a high-brightness phosphor having a small specific surface area as a target. However, if the addition rate is too slow, productivity is lost.

  The phosphor precipitated by the addition of the poor solvent is separated by filtration etc. and recovered by solid-liquid separation, and after washing with a solvent such as ethanol, water, acetone etc., usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 It is preferable to dry at a temperature of at least 300 ° C., preferably at most 250 ° C., more preferably at most 200 ° C. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated, but, for example, it is dried for about 1 to 2 hours.

2-1) Method of mixing a solution containing at least Si and F with a solution containing at least K, Mn and F to precipitate a product (phosphor) This method does not use a poor solvent Since the flammable organic solvent is not used as a poor solvent, industrial safety is improved; since no organic solvent is used, cost reduction can be achieved; and the same amount of phosphor is synthesized Since the amount of hydrofluoric acid required at the time of reduction is reduced to about 1/10 compared to the method of 1) above, further cost reduction can be achieved; compared to the method of 1) above, Particle growth is promoted, the specific surface area is small, the particle size is large, and it is possible to obtain a high-brightness phosphor excellent in durability;

The solution containing at least Si and F (hereinafter sometimes referred to as “solution I”) is hydrofluoric acid containing a SiF ₆ source.
The SiF ₆ source of this solution I is a compound containing Si and F, and it may be any compound having excellent solubility in the solution, such as H ₂ SiF ₆ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ , Rb ₂ SiF ₆ and Cs ₂ SiF ₆ can be used, and among these, H ₂ SiF ₆ is preferable because it has high solubility in water and does not contain an alkali metal element as an impurity. One of these SiF ₆ sources may be used alone, or two or more thereof may be used in combination.

The hydrogen fluoride concentration of this solution I is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight It is preferable that it is% or less. The SiF ₆ source concentration is usually 10% by weight or more, preferably 20% by weight or more, and usually 60% by weight or less, preferably 40% by weight or less. When the concentration of hydrogen fluoride in solution I is too low, when a solution (solution II) containing an Mn source described later (solution II) is added to solution I, the Mn ions are easily hydrolyzed, and the concentration of activated Mn changes. Since the amount of activity of Mn in the phosphor to be synthesized is difficult to control, the variation in the luminous efficiency of the phosphor tends to be large, and when it is too high, the danger in operation tends to be high. When the SiF ₆ source concentration is too low, the yield of the phosphor tends to decrease and the particle growth of the phosphor tends to be suppressed, and when it is too high, the phosphor particles tend to be too large.
Note that hydrofluoric acid can also be an F source (the same applies to solutions II to VI).

On the other hand, a solution containing at least K, Mn and F (hereinafter sometimes referred to as “solution II”) is hydrofluoric acid containing a K source and an Mn source.
As the K source of solution II, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO _{3 and the} like can be used. Among them, the concentration of hydrogen fluoride in the solution is KHF ₂ is preferred because it can be dissolved without lowering it and its safety is high due to its low heat of solution.

In addition, K ₂ MnF ₆ , KMnO ₄ , K ₂ MnCl ₆ or the like can be used as the Mn source of the solution II, and among them, it does not contain a Cl element which tends to distort the crystal lattice and destabilize it. K ₂ MnF ₆ is preferable because it can be stably present in hydrofluoric acid as MnF ₆ complex ion while maintaining the oxidation number (tetravalent) that can be activated, etc. Among the Mn sources, those including K also serve as the K source.

  Each of these K sources and Mn sources may be used alone or in combination of two or more.

The hydrogen fluoride concentration of this solution II is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight It is preferable that it is% or less. The total concentration of K source and Mn source is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and usually 45% by weight or less, preferably 40% by weight or less, more preferably Is preferably 35% by weight or less. If the concentration of hydrogen fluoride is too low, the raw material K ₂ MnF ₆ of the activating element contained in the solution II is unstable and easily hydrolyzed, and the concentration of Mn changes drastically, so the Mn activation in the synthesized phosphor is The variation in the luminous efficiency of the phosphor tends to be large because the amount is difficult to control, and when it is too high, the danger on operation tends to be high. In addition, when the concentrations of K and M sources are too low, the yield of the phosphor tends to decrease, and the particle growth of the phosphor tends to be suppressed, and when it is too high, the phosphor particles tend to be too large. .

  There is no particular limitation on the method of mixing the solution I and the solution II, and the solution II may be added and mixed while stirring the solution I, or even if the solution I is added and mixed while stirring the solution II good. Alternatively, the solution I and the solution II may be put into a container at one time and stirred and mixed.

By mixing the solution I and the solution II, the SiF ₆ source, the K source and the Mn source react with each other at a predetermined ratio to precipitate crystals of the target phosphor, so the crystals are separated by filtration etc. After washing with a solvent such as ethanol, water or acetone, usually 100.degree. C. or higher, preferably 120.degree. C. or higher, more preferably 150.degree. C. or higher, and usually 300.degree. C. or lower, preferably 250.degree. Preferably, drying is performed at 200 ° C. or less. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated, but, for example, it is dried for about 1 to 2 hours.

  In addition, also when mixing the solution I and the solution II, the composition of the phosphor as a product is a target composition in consideration of the difference between the preparation composition of the above-mentioned phosphor raw material and the composition of the phosphor to be obtained. It is necessary to adjust the mixing ratio of solution I and solution II.

2-2) Method of depositing a product (phosphor) by mixing a solution containing at least Si, Mn and F with a solution containing at least K (and / or Na) and F
This method is also characterized by using no poor solvent, and has the same advantages as the method 2-1).
Furthermore, according to the method 2-2), since K ₂ MnF ₆ is dissolved in the solution, it is possible to uniformly activate Mn as compared with the method 2-1). Therefore, since the Mn concentration to be actually activated is linearly controlled with respect to the preparation composition of the Mn concentration, there is an advantage that industrial quality control can be easily performed.

The solution containing at least Si, Mn and F (hereinafter sometimes referred to as “solution III”) is hydrofluoric acid containing a SiF ₆ source and an Mn source.
The SiF ₆ source of the solution III is a compound containing Si and F, and it may be a compound having excellent solubility in the solution, and H ₂ SiF ₆ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ , Rb ₂ SiF ₆ , Cs ₂ SiF ₆ or the like. Among these, H ₂ SiF ₆ is preferable because of high solubility in water and no alkali metal element as an impurity. One of these SiF ₆ sources may be used alone, or two or more thereof may be used in combination.

As the Mn source of the solution III, K ₂ MnF ₆ , KMnO ₄ , K ₂ MnCl ₆ or the like can be used. Among them, hydrofluoric acid as the MnF ₆ complex ion is maintained while maintaining the oxidation number (tetravalent) that can be activated, because it does not contain the Cl element which tends to distort and destabilize the crystal lattice. K ₂ MnF ₆ is preferred as it can be stably present therein. Among the Mn sources, those including K also serve as the K source. As the Mn source, one type may be used alone, or two or more types may be used in combination.

The hydrogen fluoride concentration of this solution III is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, particularly preferably 35% by weight or more, and usually 70% by weight or less, preferably 60% by weight % Or less, more preferably 50% by weight or less, particularly preferably 45% by weight or less. The SiF ₆ source concentration is usually 10% by weight or more, preferably 20% by weight or more, and usually 60% by weight or less, preferably 40% by weight or less. The Mn source concentration is usually 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 1% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less, more preferably It is preferable that it is 2 weight% or less. If the concentration of hydrogen fluoride in the solution III is too low, the Mn ion tends to be hydrolyzed, the activated Mn concentration changes, and the amount of Mn activity in the synthesized phosphor becomes difficult to control. There is a tendency for the variation in the luminous efficiency of the phosphor to be large. On the other hand, when the concentration of hydrogen fluoride is too high, there is a tendency for the danger on work to increase. When the SiF ₆ source concentration is too low, the yield of the phosphor tends to decrease and the particle growth of the phosphor tends to be suppressed, and when it is too high, the phosphor particles tend to be too large. In addition, when the concentration of the Mn source is too low, the yield of the phosphor tends to decrease, and the particle growth of the phosphor tends to be suppressed, and when it is too high, the phosphor particles tend to be too large.

On the other hand, a solution containing at least K and F (hereinafter sometimes referred to as “solution IV”) is hydrofluoric acid containing a K source.
As a K source of solution IV, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO _{3 and the} like can be used. Among them, KHF ₂ is preferable because it can be dissolved without lowering the concentration of hydrogen fluoride in the solution, and the heat of solution is small and the safety is high. As the K source, one type may be used alone, or two or more types may be used in combination.

The hydrogen fluoride concentration of this solution IV is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight It is preferable that it is% or less. The K source concentration is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and usually 45% by weight or less, preferably 40% by weight or less, more preferably 35% by weight or less Is preferred. If the hydrogen fluoride concentration is too low, for example, the raw material K ₂ MnF ₆ of the activating element contained in the solution III becomes unstable and easily hydrolyses when added to the solution III, and the Mn concentration drastically changes. Since the amount of activity of Mn in the phosphor to be synthesized is difficult to control, the variation in the luminous efficiency of the phosphor tends to be large, and when it is too high, the danger in operation tends to be high. When the concentration of the K source is too low, the yield of the phosphor tends to decrease, and the particle growth of the phosphor tends to be suppressed, and when it is too high, the phosphor particles tend to be too large.

  There is no particular limitation on the method of mixing the solution III and the solution IV, and the solution IV may be added and mixed while stirring the solution III, and even if the solution III is added and mixed while stirring the solution IV good. Alternatively, the solution III and the solution IV may be charged into a container at one time and stirred and mixed.

By mixing solution III and solution IV, SiF ₆ source, Mn source and K source react at a predetermined ratio to precipitate crystals of the target phosphor, so this crystal is separated by filtration etc. After washing with a solvent such as ethanol, water or acetone, usually 100.degree. C. or higher, preferably 120.degree. C. or higher, more preferably 150.degree. C. or higher, and usually 300.degree. C. or lower, preferably 250.degree. Preferably, drying is performed at 200 ° C. or less. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated, but, for example, it is dried for about 1 to 2 hours.

  In addition, also when mixing the solution III and the solution IV, the composition of the phosphor as a product is the target composition, taking into consideration the difference between the preparation composition of the above-mentioned phosphor material and the composition of the phosphor to be obtained. It is necessary to adjust the mixing ratio of the solution III and the solution IV so that

[1-4. Applications of Phosphors]
The phosphors of the present invention can be used in any application that uses phosphors. The phosphor of the present invention may be used alone as the phosphor of the present invention, but two or more of the phosphors of the present invention may be used in combination, or the phosphor of the present invention and other phosphors. It is also possible to use as an arbitrary combination phosphor mixture which used together or.

  Further, the phosphor of the present invention can be suitably used particularly for various light emitting devices ("light emitting device of the present invention" described later), taking advantage of the property of being able to be excited by blue light. Since the phosphor of the present invention is usually a red light emitting phosphor, for example, a violet to pink light emitting device can be manufactured by combining the phosphor of the present invention with an excitation light source emitting blue light. . Further, the phosphor of the present invention may be combined with an excitation light source emitting blue light and a phosphor emitting green light, or an excitation light source emitting near-ultraviolet light, a phosphor emitting blue light, and fluorescence emitting green light When the bodies are combined, the phosphor of the present invention is excited by blue light from an excitation light source that emits blue light or phosphor that emits blue light to emit red light, so a white light emitting device is manufactured. be able to.

  The light emission color of the light emitting device is not limited to white, and by selecting the combination and content of the phosphors appropriately, a light emitting device emitting light of any color such as a 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 (in particular, a backlight for liquid crystal) of an image display device or a lighting device.

[2. Phosphor-containing composition]
The phosphor of the present invention can also be used as a mixture with a liquid medium. In particular, when the phosphor of the present invention is used for applications such as light emitting devices, it is preferable to use the phosphor dispersed in a liquid medium. What disperse | distributed the fluorescent substance of this invention in the liquid medium is suitably called "the fluorescent substance containing composition of this invention."

[2-1. Phosphor]
There is no restriction on the type of the phosphor of the present invention to be contained in the phosphor-containing composition of the present invention, and it can be arbitrarily selected from those described above. Further, the phosphor of the present invention to be contained in the phosphor-containing composition of the present invention may be only one type, or two or more types may be used in combination in an optional combination and ratio. Furthermore, the phosphor-containing composition of the present invention may contain a phosphor other than the phosphor of the present invention as long as the effects of the present invention are not significantly impaired.

[2-2. Liquid medium]
The liquid medium used in the phosphor-containing composition of the present invention is not particularly limited as long as the performance of the phosphor is not impaired in the target range. For example, any inorganic material and / or organic material may be used as long as it exhibits liquid properties under desired conditions of use, suitably disperses the phosphor of the present invention and does not cause any undesirable reaction. it can.

  As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a metal alkoxide, a solution containing a ceramic precursor polymer or metal alkoxide by a sol-gel method, or an inorganic material (for example, siloxane) obtained by solidifying a combination thereof Inorganic materials having bonds or the like can be mentioned.

  As an organic type material, a thermoplastic resin, a thermosetting resin, a photocurable resin etc. are mentioned, for example. Specifically, for example, methacrylic resins such as methyl polymethacrylate; styrene resins such as polystyrene, styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; ethyl cellulose, cellulose acetate And cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.

  Among the above-mentioned inorganic materials and organic materials, particularly when using a phosphor for a light emitting device with a large output such as illumination, it is preferable to use a silicon-containing compound for the purpose of heat resistance, light resistance and the like.

  The silicon-containing compound refers to a compound having a silicon atom in the molecule, and examples thereof include organic materials such as polyorganosiloxane (silicone materials), inorganic materials such as silicon oxide, silicon nitride and silicon oxynitride, and borosilicate And glass materials such as phosphosilicates and alkali silicates. Among them, silicone materials are preferable in terms of transparency, adhesion, ease of handling, and excellent mechanical and thermal stress relaxation properties.

  The silicone-based material usually means an organic polymer having a siloxane bond as a main chain, and for example, silicone-based materials such as condensation type, addition type, improved sol-gel type, and photocurable type can be used.

  As the condensation type silicone material, for example, the members for semiconductor light emitting devices described in JP 2007-112973 to 112975, JP 2007-19459, JP 2008-34833, etc. can be used. The condensation type silicone material is excellent in adhesion to a package, an electrode, a member such as a light emitting element used in a semiconductor light emitting device, so that the addition of an adhesion improving component can be minimized and crosslinking is mainly due to siloxane bond. It has the advantage of being excellent in heat resistance and light resistance.

  As addition type silicone materials, for example, silicone materials for potting described in JP-A-2004-186168, JP-A-2004-221308, JP-A-2005-327777, etc., JP-A-2003-183881, Organic modified silicone materials for potting described in JP-A-2006-206919, etc., 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 high freedom of selection such as curing speed and hardness of a cured product, no component to be detached at the time of curing, difficulty in curing shrinkage, and excellent in deep area curability.

  Moreover, as an improved sol-gel type silicone material which is one of condensation type, for example, silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-11969, etc. can be used. It can be used suitably. The modified sol-gel type silicone material has the advantages of high crosslinking degree, high heat resistance and light resistance, excellent durability, low gas permeability, and excellent protection function of phosphor having low moisture resistance.

  As a photocurable silicone type material, the silicone material of Unexamined-Japanese-Patent No. 2007-131812, 2007-214543 grade | etc., Can be used suitably, for example. The photocurable silicone material has advantages such as excellent productivity because it cures in a short time, and that it is not necessary to apply a high temperature for curing, so that deterioration of the light emitting element is less likely to occur.

  These silicone materials may be used alone, or a plurality of silicone materials may be mixed and used if curing does not occur by mixing.

[2-3. Liquid Media and Phosphor Content]
The content of the liquid medium is optional as long as the effects of the present invention are 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 It is usually at most 99 wt%, preferably at most 95 wt%, more preferably at most 80 wt%. There is no particular problem when the amount of liquid medium is large, but in order to obtain the desired chromaticity coordinates, color rendering index, luminous efficiency etc. in the case of semiconductor light emitting devices, the compounding ratio is usually as described above It is desirable to use a liquid medium. On the other hand, when the amount of the liquid medium is too small, the fluidity may be reduced and it may be difficult to handle.

  The liquid medium mainly serves as a binder in the phosphor-containing composition of the present invention. The liquid medium may be used singly or in combination of two or more in any combination and ratio. For example, when a silicon-containing compound is used for the purpose of improving heat resistance, light resistance, etc., other thermosetting resin such as epoxy resin is contained to the extent that the durability of the silicon-containing compound is not impaired. It is 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 optional 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 The content is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 75% by weight or less, preferably 60% by weight or less. In addition, the ratio of the phosphor of the present invention to the phosphor in the phosphor-containing composition is optional, but usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less. When the content of the phosphor in the phosphor-containing composition is too large, the flowability of the phosphor-containing composition may be poor and handling may be difficult, and when the content of the phosphor is too small, the light emission efficiency of the light emitting device may be reduced. There is a tendency.

[2-4. Other ingredients]
In the phosphor-containing composition of the present invention, in addition to the phosphor and the liquid medium, other components such as a metal oxide for adjusting the refractive index, a diffusing agent, and a filler as long as the effects of the present invention are not significantly impaired. You may contain additives, such as a viscosity modifier and a ultraviolet absorber. The other components may be used alone or in any combination of two or more in any proportion.

[3. Light emitting device]
A light emitting device (hereinafter referred to as “light emitting device” as appropriate) of the present invention comprises a first light emitting body (excitation light source) and a second light emitting body that emits visible light by irradiation of light from the first light emitting body. A light emitting device having the above-mentioned [1. [Phosphor] The first phosphor containing one or more of the phosphors of the present invention described in the section above.

  As the phosphor of the present invention, a phosphor which 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 a light emission peak in the wavelength range of 600 nm to 660 nm. The red phosphor of the present invention may be used alone or in any combination of two or more in any proportion.

  By using the red phosphor of the present invention, the light emitting device of the present invention exhibits high luminous efficiency with respect to the excitation light source (first light emitter) having light emission in the blue region, and further, a lighting device, liquid crystal It becomes an excellent light emitting device when used for a white light emitting device such as a display light source.

  Moreover, as a preferable specific example of the red fluorescent substance of this invention used for the light-emitting device of this invention, the above-mentioned [1. The phosphor of the present invention described in the column of “Phosphor” and the phosphor used in each example of the column of [Example] described later can be mentioned.

  The light emitting device of the present invention has a first light emitter (excitation light source) and uses at least the phosphor of the present invention as the second light emitter. It is possible to take any device configuration. Specific examples of the device configuration will be described later.

  The light emitting device of the present invention preferably has a luminous 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 measurement of the luminous spectrum 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 the voltage using a Fluke True RMS Multimeters Model 187 & 189 while conducting 20 mA, and calculating 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, using an excitation light source as described later as a first light emitter, in addition to a red phosphor as described above, a blue color as described later Phosphor that emits fluorescence (hereinafter referred to as “blue phosphor” as appropriate), phosphor that emits green fluorescence (hereinafter referred to as “green phosphor” as appropriate), phosphor that emits yellow fluorescence (hereinafter referred to as “yellow fluorescence appropriately Etc.) can be obtained by using any known combination of known phosphors such as “body” and the like and taking a known device configuration.

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

[3-1. Configuration of light emitting device (light emitter)]
<3-1-1. First light emitter>
The first light emitter in the light emitting device of the present invention emits light for exciting a second light emitter to be described later.

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

  As a specific numerical value of the light emission peak wavelength of a 1st light-emitting body, 200 nm or more is desirable normally. Among them, when blue light is used as excitation light, the emission peak wavelength is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less, more preferably 460 nm or less. It is desirable to use a light emitter that has. 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 is excited by near-ultraviolet light to emit blue light. It is preferable to select excitation light (near ultraviolet light) having a wavelength that matches the band. Specifically, it is desirable to use a light emitter 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 .

  Generally, a semiconductor light emitting element is used as the first light emitter, 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 the first light emitter is not limited to those exemplified in the present specification.

Among them, a GaN-based LED or LD using a GaN-based compound semiconductor is preferable as the first light emitter. This is because GaN-based LEDs and LDs have much higher luminous output and external quantum efficiency than SiC-based LEDs that emit light in this region, and by combining with the above-mentioned phosphors, extremely bright emission with low power is achieved. It is because it is obtained. For example, with respect to a current load of 20 mA, a GaN-based LED or LD usually has an emission intensity 100 times or more that of a SiC-based. As the GaN-based LED or LD, one 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 is preferable. Among them, a GaN-based LED having an In _x Ga _y N light emitting layer is particularly preferable because the light emission intensity is very high, and the multiple quantum well structure of the In _x Ga _Y N layer and the GaN layer is further preferable. preferable.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. Among GaN-based LEDs, 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.

The GaN-based LED basically includes the light emitting layer, the p layer, the n layer, the electrode, and the substrate, and the light emitting layer includes n-type and p-type Al _x Ga _Y N layers, a GaN layer, or In _x. Those having a heterostructure sandwiched by a Ga _Y N layer or the like are preferable because they have high light emission efficiency, and those whose quantum well structure has a heterostructure are more preferable because they have higher 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.

<3-1-2. Second light emitter>
The second light emitter in the light emitting device of the present invention is a light emitter which emits visible light by irradiation of the light from the first light emitter described above, and contains the first phosphor including the red phosphor of the present invention In addition, according to the use etc., it contains suitably 2nd fluorescent substance (blue fluorescent substance, green fluorescent substance, yellow fluorescent substance, orange fluorescent substance etc.) mentioned later. Also, for example, the second light emitter is configured by dispersing the first and second phosphors in the sealing material.

  There is no particular limitation on the composition of the phosphor other than the phosphor of the present invention used in the second light emitter. Specific examples of preferred crystal matrix are shown in the following table.

  However, there is no particular limitation on the elemental composition, and the above-mentioned host crystal and activating element or co-activating element can be partially substituted with the elements of the same family, and the obtained phosphor has light in the near ultraviolet to visible region Can be used as long as they absorb visible light and emit visible light.

  Specifically, although it is possible to use the following listed as phosphors, these are merely examples, and the phosphors that can be used in the present invention are not limited to these. In the following exemplification, as described above, phosphors that differ only in part of the structure are appropriately omitted and shown.

<3-1-2-1. First phosphor>
The second light emitter in the light emitting device of the present invention contains the first phosphor containing at least the above-mentioned phosphor of the present invention. The phosphors of the present invention may be used alone or in any combination of two or more in any proportion.
Moreover, as the first phosphor, in addition to the phosphor of the present invention, another kind of phosphor (same-color combined phosphor) that emits fluorescence of the same color as the phosphor of the present invention may be used.

  The weight median diameter of the first phosphor used in the light emitting device of the present invention is preferably in the range of usually 2 μm or more, in particular 5 μm or more, and usually 30 μm or less, in particular 25 μm or less. When the weight median diameter is too small, the luminance is lowered, and the phosphor particles tend to aggregate. On the other hand, when the weight median diameter is too large, coating unevenness and closure of a dispenser or the like tend to occur.

As the orange to red phosphors that can be used in combination with the phosphor of the present invention, any may 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 combined 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.

  Phosphors usable as such orange to red phosphors are shown in the following table.

Among the above, as a red phosphor, (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) ) Β-Diketone-based Eu complexes such as _{3, 1} and 10-phenanthroline complexes, carboxylic acid-based Eu complexes, and K ₂ SiF ₆ : Mn are preferred, and (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : More preferred are Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, and K ₂ SiF ₆ : Mn.
Further, as the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, ( Ca, Sr, Ba) AlSi (N, O) ₃ : Ce is preferred.

  The orange to red phosphors exemplified above may be used alone or in any combination of two or more in any proportion.

<3-1-2-2. 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 above-described first phosphor, depending on the application. The second phosphor is one or more types of phosphors having different emission peak wavelengths from the first phosphor. Since these second phosphors are usually used to adjust the color tone of light emission of the second light emitter, the second phosphor emits fluorescence of a color different from that of the first phosphor. Phosphors are often used. As described above, since a red phosphor is usually used as the first phosphor, a phosphor other than a red phosphor such as a blue phosphor, a green phosphor, a yellow phosphor, etc. is used as the second phosphor, for example. Use

The weight median diameter D ₅₀ of the second phosphor used in the light emitting device of the present invention is preferably in the range of usually 2 μm or more, in particular 5 μm or more, and usually 30 μm or less, in particular 25 μm or less. When the weight median diameter D ₅₀ is too small, the luminance is reduced, and the phosphor particles tend to aggregate. On the other hand, when the weight median diameter is too large, coating unevenness and closure of a dispenser or the like tend to occur.

(Blue phosphor)
When a blue phosphor is used as the second phosphor, any blue phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, still more preferably 460 nm or less It is preferred to be in the wavelength range. When the emission peak wavelength of the blue phosphor used is in this range, it overlaps with the excitation band of the phosphor of the present invention, and blue light from the blue phosphor can efficiently excite the phosphor of the present invention It is from.

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

Among the above, 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, (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu, preferably (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu and Ba ₃ MgSi ₂ O ₈ : Eu are more preferable, and Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu and BaMgAl ₁₀ O ₁₇ : Eu are particularly preferable.

  The blue phosphors exemplified above may be used alone or in any combination of two or more in any proportion.

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

  Phosphors that can be used as such yellow phosphors are shown in the following table.

Among the above, as a 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, (Ca, Ca) _{sr) Si 2 N 2 O 2} : Eu is preferred.

  The yellow phosphors exemplified above may be used alone or in any combination of two or more in any proportion.

(Green phosphor)
When a green phosphor is used as the second phosphor, any green phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the green phosphor is preferably in the range of usually 500 nm or more, particularly 510 nm or more, further 515 nm or more, usually 550 nm or less, in particular 542 nm or less, further 535 nm or less. When the emission peak wavelength is too short, it tends to be bluish, while when it is too long, it tends to be yellowish, and in any case, the characteristics as green light may be deteriorated.

  Phosphors that can be used as such a green phosphor are shown in the following table.

Among the above, as a 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 resulting light emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : CeCa 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.
In the case of using a light-emitting device obtained in the image display _{apparatus, (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.

  The green phosphors exemplified above may be used alone or in any combination of two or more in any proportion.

<3-1-2-3. Selection of second phosphor>
As said 2nd fluorescent substance, 1 type of fluorescent substance may be used independently, and 2 or more types of fluorescent substance may be used together by arbitrary combinations and a ratio. Further, the ratio of the first phosphor to the second phosphor is also arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, the amount of use of the second phosphor, the combination of the phosphors used as the second phosphor, the ratio thereof, and the like may be arbitrarily set according to the application of the light emitting device and the like.

For example, when the light emitting device of the present invention is configured as a light emitting device emitting red light, only the first phosphor (red phosphor) may be used, and the use of the second phosphor is generally unnecessary. .
On the other hand, when the light emitting device of the present invention is configured as a light emitting device for white light emission, the first light emitter, the first phosphor (red phosphor), and the first light emitter so as to obtain desired white light. It suffices to combine the two phosphors appropriately. Specifically, in the case where the light emitting device of the present invention is configured as a white light emitting light emitting device, examples of preferable combinations of the first light emitter, the first phosphor and the second phosphor are as follows: And combinations of (A) to (C).

(A) A blue light emitter (such as a blue LED) is used as the first light emitter, a red phosphor (such as the phosphor of the present invention) is used as the first phosphor, and a green phosphor is used as the second phosphor. Use the body or yellow phosphor. Examples of green phosphors include (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphors, CaSc ₂ O ₄ : Ce phosphors, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce phosphors, 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, M ₃ Si ₆ O ₁₂ N ₂ : Eu However, M is one or two or more types of green phosphors selected from the group consisting of alkaline earth metal elements. As the yellow phosphor, one or two selected from the group consisting of Y ₃ Al ₅ O ₁₂ : Ce phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, α-sialon phosphor Species or more yellow phosphors are preferred. Also, a green phosphor and a yellow phosphor may be used in combination.

(B) A near ultraviolet or ultraviolet light emitter (such as near ultraviolet or ultraviolet LED) is used as the first light emitter, and a red phosphor (such as the phosphor of the present invention) is used as the first phosphor; The blue phosphor and the green phosphor are used in combination as the phosphor of In this case, BaMgAl ₁₀ O ₁₇ : Eu and / or (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu is preferable as the blue phosphor. In addition, as a green phosphor, BaMgAl ₁₀ O ₁₇ : Eu, Mn, (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, M ₃ Si ₆ O ₁₂ N ₂ : Eu-based phosphor (where M represents an alkaline earth metal element), (Ba, Sr, Ca) ₄ Al ₁₄ O ₂₅ : One or two or more types of green phosphors selected from the group consisting of Eu and (Ba, Sr, Ca) Al ₂ O ₄ : Eu are preferable. Above all, since the color reproduction range of the display can be dramatically improved, it is preferable to use a phosphor having a narrow emission peak half width for all three types of red, blue and green. Specifically, a near ultraviolet LED and the present invention Phosphors, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu as a blue phosphor and (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, as a green phosphor It is preferable to use it in combination with Mn.

(C) A blue phosphor (such as a blue LED) is used as the first phosphor, a red phosphor (such as the phosphor of the present invention) is used as the first phosphor, and an orange fluorescence is used as the second phosphor Use the body. In this case, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

  In addition, the phosphor of the present invention is mixed with other phosphors (here, mixing does not necessarily mean that the phosphors are mixed, but means that different phosphors are combined. ) Can be used. In particular, mixing the phosphors in the combinations described above gives a preferred phosphor mixture. In addition, there is no restriction | limiting in particular in the kind of fluorescent substance mixed, and its ratio.

  The preferred combination of the first light emitter and the first and second phosphors will be more specifically described below according to the application of the light emitting device.

  Among these, the following combinations are more preferable.

  Among these, the following combinations are more preferable.

[3-2. Configuration of light emitting device (sealing material)]
In the light emitting device of the present invention, the first and / or second phosphors are usually dispersed in a liquid medium which is a sealing material (binder).
As the liquid medium, the aforementioned [4. The same ones as described in the section “Phosphor-Containing Composition” can be mentioned.

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

The present form of such a metal element is not particularly limited as long as the transparency of the sealing material is not impaired. For example, a uniform glass layer may be formed as a metalloxane bond, and may be present in the form of particles in the sealing member. When it is present in the form of particles, the internal structure of the particles may be amorphous or crystalline, but in order to give a high refractive index, it is preferably crystalline. The particle diameter is usually equal to or less than the light emission wavelength of the semiconductor light emitting device, preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less, in order not to impair the transparency of the sealing material. For example, by mixing particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, niobium oxide and the like in a silicone-based material, the above metal element can be made to exist in the form of particles in the sealing material .
In addition, the liquid medium may further contain known additives such as a diffusing agent, a filler, a viscosity adjusting agent, and an ultraviolet absorber.

[3-3. Light-emitting device configuration (Others)]
The light emitting device of the present invention is not particularly limited in its configuration, as long as the light emitting device of the present invention includes the first light emitter and the second light emitter described above, but usually, the first light emitter described above on a suitable frame And a second light emitter. At this time, the light emission of the first light emitter excites the second light emitter (that is, the first and second phosphors are excited) to generate light, and the light emission of the first light emitter And / or the light emission of the second light emitter is arranged to be extracted outside. In this case, the first phosphor and the second phosphor do not necessarily have to be mixed in the same layer, and for example, the second phosphor is contained on the layer containing the first phosphor. The phosphor may be contained in a separate layer for each color development of the phosphor, such as laminating the layers to be stacked.

  Further, in the light emitting device of the present invention, members other than the above-described excitation light source (first light emitter), phosphor (second light emitter) and frame may be used. As an example, the above-mentioned sealing material is mentioned. In the light emitting device, the sealing material is provided for the excitation light source (first light emitter), the phosphor (second light emitter) and the frame in addition to the purpose of dispersing the phosphor (second light emitter). It can be used for the purpose of bonding.

  The light emitting device of the present invention can be made a light emitting device suitable for a backlight source for an image display device to be described later by combining the phosphor of the present invention with another specific blue phosphor and a specific green phosphor. . That is, the phosphor of the present invention is excited to emit light having a wavelength from the ultraviolet region to the blue region, and the light emission is a narrow band in the red region and is excellent in temperature characteristics. To manufacture a semiconductor light emitting device as a back light source for an image display device which can set the light emission efficiency higher than before and set the color reproduction range wider than before by combining two or more kinds of phosphors. Can.

As the first light emitter, a semiconductor light emitting element having an emission wavelength from the above-mentioned ultraviolet region to the blue region, preferably a semiconductor light emitting element having an emission wavelength in the near ultraviolet region can be used.
Among the semiconductor light emitting devices, it is preferable to use a device with a small variation in luminous efficiency, particularly in a backlight light source application for an image display device using a plurality of semiconductor light emitting devices. Since many phosphors which are excited by the wavelength from the near ultraviolet region to the blue region largely change the excitation efficiency near a wavelength of 400 nm, it is particularly preferable to use a semiconductor light emitting device with less variation in light emission efficiency. Specifically, the degree of variation of the emission wavelength at which the emission efficiency in the semiconductor light emitting element is maximum is usually ± 5 nm or less, preferably ± 2.5 nm or less, and more preferably ± 1.25 nm or less.

  As two or more kinds of phosphors, the phosphor of the present invention, and specific blue phosphors and green phosphors which are excited by the light emission from the first light emitter, emit light in a narrow band, and have excellent temperature characteristics Combinations can be mentioned.

  As a combination of phosphors preferable as a semiconductor light emitting device as the above-mentioned backlight source for image display devices, the above-mentioned Table 6A, Table 6B, Table 7A, Table 7B, and Table 8 show “backlight application of image display device” Can be mentioned.

  Moreover, when using a sealing material for the said light-emitting device, it is preferable to use the above-mentioned silicone type material from the viewpoint of the resistance to degradation of the light emission wavelength of an ultraviolet region to a blue region and heat resistance. It is more preferable to use a base material.

  Furthermore, by combining a color filter that is optimum for the light emission wavelength of the light emitting device, it is possible to realize an image display with high color purity. That is, since the light emitting device is a light source combining light emission of blue, green and red having a narrow band and high emission intensity and excellent temperature characteristics, the light utilization efficiency is higher than before even at a high NTSC ratio and high temperature Also by using the semiconductor light emitting element of the power device, it is possible to obtain an excellent image display apparatus in which the light emission intensity is stable and the color shift is small.

[3-4. Embodiment of Light Emitting Device]
Hereinafter, the light emitting device of the present invention will be described in more detail by citing specific embodiments, but the present invention is not limited to the following embodiments, and within the scope not departing from the gist of the present invention It can be modified arbitrarily and implemented.

  FIG. 1 is a schematic perspective view showing the 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 one example of the light emitting device of the present invention. Shown in. The code | symbol 1 in FIG. 1 represents a fluorescent substance containing part (2nd light-emitting body), the code | symbol 2 represents surface emitting type GaN type LD as an excitation light source (1st light-emitting body), and the code | symbol 3 represents a board | substrate. The LD (2) and the phosphor-containing portion (second light emitter) (1) are separately prepared to make them in contact with each other, and the surfaces thereof are contacted by an adhesive or other means. The phosphor-containing portion (second light emitter) may be formed (formed) on the light emitting surface of the LD (2). As a result of these, it is possible to bring the LD (2) into contact with the phosphor-containing portion (second light emitter) (1).

  When such an apparatus configuration is adopted, the light quantity loss 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 leaks out As a result, the luminous efficiency of the entire device can be improved.

  FIG. 2 (a) is a representative example of a light emitting device generally referred to as a cannonball type, and emits light having an excitation light source (first light emitter) and a phosphor containing portion (second light emitter) It is a typical sectional view showing one example of an apparatus. In the light emitting device (4), reference numeral 5 is a mount lead, 6 is an inner lead, 7 is an excitation light source (first light emitter), 8 is a phosphor containing portion, 9 is a conductive wire, and 10 is Each refer to a mold member.

  Further, FIG. 2 (b) is a representative example of a light emitting device of a form called surface mounting type, and light emission having an excitation light source (first light emitter) and a phosphor containing portion (second light emitter) It is a typical sectional view showing one example of an apparatus. In the figure, reference numeral 22 denotes an excitation light source (first light emitter), reference numeral 23 denotes a phosphor-containing portion (second light emitter), reference numeral 24 denotes a frame, reference numeral 25 denotes a conductive wire, reference numerals 26 and 27 denote electrodes. Point to each.

[3-5. Applications of light emitting devices]
The application of the light emitting device of the present invention is not particularly limited, and it can be used in various fields where a normal light emitting device is used, but it has high color rendering properties and a wide color reproduction range. And as a light source of an image display apparatus.

<3-5-1. Lighting device>
In the case where the light emitting device of the present invention is applied to a lighting device, the light emitting device as described above may be appropriately incorporated into a known lighting device. For example, there can be mentioned a surface emitting lighting device (11) incorporating the above-mentioned light emitting device (4) as shown in FIG.

  FIG. 3 is a cross-sectional view schematically showing an embodiment of the lighting device of the present invention. As shown in FIG. 3, the surface emitting illumination device comprises a plurality of light emitting devices (13) (described above) on the bottom surface of a rectangular holding case (12) whose inner surface is light impermeable such as a white smooth surface. The light emitting device (4) is provided with a power supply and a circuit (not shown) for driving the light emitting device (13) provided outside the light emitting device (4), and corresponds to the lid of the holding case (12) A diffusion plate (14) such as a milky white acrylic plate is fixed at a location for uniforming light emission.

  Then, the surface light emitting illumination device (11) is driven to apply a voltage to the excitation light source (first light emitter) of the light emitting device (13) to emit light, and a part of the light emission is The phosphor in the phosphor-containing resin portion as the containing portion (second light emitter) absorbs light and emits visible light, while color mixing with a blue light etc. not absorbed by the phosphor is high. Light emission is obtained, and this light is transmitted through the diffusion plate (14) and emitted upward in the drawing to obtain illumination light of uniform brightness in the plane of the diffusion plate (14) of the holding case (12). Become.

<3-5-2. 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, in the case of a color image display device using a color liquid crystal display element as an image display device, the light emitting device is a backlight, and an optical shutter using liquid crystal and a color filter having pixels of red, green and blue Can be combined to form an image display device.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Method of measuring physical property values]
The physical property values of the phosphors obtained in the respective examples and comparative examples described later were measured and calculated by the following methods.

{Emission characteristic}
<Emission spectrum, emission peak wavelength, half width of emission peak>
The emission spectrum is measured at room temperature (25 ° C.) using a fluorescence measurement apparatus (manufactured by JASCO Corporation) equipped with a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics Co., Ltd.) as a spectrum measurement apparatus. did.
More specifically, the light from the excitation light source was passed through a diffraction grating spectrometer having a focal length of 10 cm, and only the excitation light having a wavelength of 455 nm or less was irradiated to the phosphor through an optical fiber. The light generated from the phosphor by irradiation with excitation light is dispersed by a diffraction grating spectrometer having a focal length of 25 cm, and the emission intensity of each wavelength is measured by a spectrum measuring device in a wavelength range of 300 nm to 800 nm, The emission spectrum was obtained through signal processing such as sensitivity correction. In addition, at the time of measurement, the slit width of the light receiving side spectroscope was set to 1 nm and measured.
The emission peak wavelength and the half width of the emission peak were calculated from the obtained emission spectrum.

<Brightness>
The relative luminance is the excitation value of 455 nm in the same manner from the stimulation value Y in the XYZ color system calculated in accordance with JIS Z8724 in the range excluding the excitation wavelength range from the emission spectrum in the visible range obtained by the above method. Stimulation similarly determined in the range excluding the excitation wavelength from the emission spectrum obtained by exciting the yellow phosphor Y ₃ Al ₅ O ₁₂ : Ce (product number: P46-Y3) manufactured by Kasei Optonix Co., Ltd. with light It was calculated as a relative value (hereinafter, may be simply referred to as “brightness”) with the value Y being 100%.

<Excitation spectrum>
The excitation spectrum was measured using a fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. at room temperature (25 ° C.). More specifically, the red emission peak at 631 nm was monitored to obtain an excitation spectrum in the wavelength range of 300 nm to 550 nm.

{Particle size}
<Weight median diameter D ₅₀ , and particle size distribution>
The particle size distribution of the phosphor was measured by a laser diffraction / scattering type particle size distribution analyzer LA-300 manufactured by Horiba, Ltd. Before the measurement, ethanol is used as the dispersion solvent to disperse the phosphor, and then the initial transmittance on the optical axis is adjusted to about 90%, and the influence of aggregation is observed while stirring the dispersion solvent with the magnet rotor. The measurement was performed with a minimum.
The weight median diameter D ₅₀ was calculated as the particle size value when the integrated value of the particle size distribution (corresponding to the weight-based particle size distribution curve) determined as described above was 50%.

<Quarterly Deviation of Particle Size Distribution (QD)>
The quarter deviation (QD) of the particle size distribution is calculated using the following equation, assuming that the median particle size D ₂₅ and D ₇₅ is the particle size value when the integrated value of the measured particle size distribution is 25% and 75%. Calculated.
QD = | D ₇₅ -D ₂₅ | / | D ₇₅ + D ₂₅ |

{Shape of phosphor particle}
<Scanning electron microscope (SEM) photograph>
In order to observe the shape and the like of the phosphor particles, in each of the examples and the comparative examples, using a SEM (S-3400N manufactured by Hitachi, Ltd.) 1000 times (Examples 1-2, 1-9), 5000 The SEM photograph was taken by double (Example 1-1, Comparative Example 1-1) or 2000 times (Example 1-16-Example 1-19).

<Specific surface area>
The measurement of the specific surface area was performed by a nitrogen adsorption BET one-point method, using a fully automatic specific surface area measuring device (flowing method) AMS 1000A manufactured by Okura Riken Co., Ltd.

{Analysis of chemical composition}
<SEM-EDX method>
The chemical composition analysis of the Mn concentration contained in the phosphor includes, as measuring devices, SEM (S-3400N) manufactured by Hitachi, Ltd. and energy dispersive X-ray analyzer (EDX) EX-250 x-act manufactured by Horiba, Ltd. It measured by SEM-EDX method using. Specifically, in a scanning electron microscope (SEM) measurement, the phosphor is irradiated with an electron beam at an accelerating voltage of 20 kV, and characteristic X-rays emitted from each element contained in the phosphor are detected to perform elemental analysis. went.

{Quantum efficiency}
<Absorption efficiency α _q , internal quantum efficiency η _i , and external quantum efficiency η _o >
In order to determine the quantum efficiency (absorption efficiency α _q , internal quantum efficiency η _i and external quantum efficiency _{o o} ), first, the measurement accuracy of the phosphor sample (for example, phosphor powder etc.) to be measured can be maintained. Then, the surface was sufficiently smoothed, packed in a cell, and attached to a light collecting device such as an integrating sphere.

  An Xe lamp was attached to the condenser as a light source for exciting a phosphor sample. In addition, adjustment was performed using a filter, a monochromator (diffraction grating spectroscope), or the like so that the emission peak wavelength of the light emission source is monochromatic light of 455 nm.

  The light from the light emission source whose emission peak wavelength was adjusted was irradiated to the phosphor sample to be measured, and the spectrum including light emission (fluorescence) and reflected light was measured by a spectrometer (MCPD 7000 manufactured by Otsuka Electronics Co., Ltd.) .

<Absorption efficiency α _q >
The absorption efficiency α _q was calculated as a value obtained by dividing the photon number N _abs of the excitation light absorbed by the phosphor sample by the total photon number N of the excitation light.
The specific calculation procedure is as follows.

First, the total number of photons N of the latter excitation light was determined as follows.
That is, a white reflector such as “Spectralon” (having a reflectance R of 98% to excitation light of 455 nm) made of Labsphere, for example, is used as a measurement target, for example, a substance having a reflectance R of approximately 100% to excitation light. , Attached to the above-described light collecting device in the same arrangement as the phosphor sample, and the reflection spectrum was measured using the spectrometer (this reflection spectrum is hereinafter referred to as "I _ref (λ)").

From this reflection spectrum I _ref (λ), a numerical value represented by the following (formula I) was determined. The integration interval of the following (formula I) was 435 nm to 465 nm. The numerical value represented by the following (formula I) is proportional to the total number of photons N of excitation light.

Further, a numerical value represented by the following (formula II) was determined from the reflection spectrum I (λ) when the phosphor sample to be measured for the absorption efficiency α _q was attached to the light collecting device. The integration interval of the above (formula II) is the same as the integration interval determined by the above (formula I). The numerical value determined by the following (Formula II) is proportional to the photon number _Nabs of the excitation light absorbed by the phosphor sample.

From the above, the absorption efficiency α _q was calculated by the following equation.
Absorption efficiency α _q = N _abs / N = (formula II) / (formula I)

<Internal quantum efficiency _{i i} >
Internal quantum efficiency eta _i is a number N _PL of photons originating from the fluorescence phenomenon, the phosphor sample was calculated as a value obtained by dividing the number N _abs of the photons absorbed.

From the above I (λ), a numerical value represented by the following formula (III) was determined. The lower limit of the integration interval of (Formula III) is 466 nm to 780 nm. The numerical value determined by the following (formula III) is proportional to the number N _PL of photons derived from the fluorescence phenomenon.

From the above, and the internal quantum efficiency eta _i is calculated by the following equation.
η _i = (formula III) / (formula II)

<External quantum efficiency η _o >
The external quantum efficiency η _o was calculated by taking the product of the absorption efficiency α _q and the internal quantum efficiency η _i obtained by the above procedure.

{Powder X-ray diffraction measurement For general identification}
Powder X-ray diffraction was precisely measured with a powder X-ray diffractometer X'Pert manufactured by PANalytical. The measurement conditions are as follows.
Cu Kα tube used X-ray output = 45 kV, 40 mA
Divergence slit = automatic, irradiation width 10 mm × 10 mm
Detector = using semiconductor array detector X 'Celerator, using Cu filter Scanning range 2θ = 10 to 65 degree Reading width = 0.0167 degree Counting time = 10 seconds

[Used raw material]
The raw materials used by the below-mentioned Example and comparative example are shown in the following table.

[Synthesis of K ₂ MnF ₆ ]
Synthesis Example 1
K ₂ MnF ₆ can be obtained by the reaction formula shown below.

That is, KF powder or KHF ₂ powder was dissolved in hydrofluoric acid (47.3% by weight), and then KMnO ₄ powder was put into this solution and dissolved. While stirring the solution, a hydrogen peroxide solution was added dropwise to obtain a yellow precipitate when the molar ratio of KMnO ₄ to H ₂ O ₂ was 1.5. The precipitate was washed with acetone and dried at 130 ° C. for 1 hour to obtain K ₂ MnF ₆ .
In the following examples and comparative examples, K ₂ MnF ₆ synthesized as described above was used.

[Example and Comparative Example of Production of Phosphor (K ₂ SiF ₆ : Mn)]
Example 1-1
As raw material compounds, K ₂ SiF ₆ (1.7783 g) and K ₂ MnF ₆ (0.2217 g) were prepared so that the feed composition of each raw material of the phosphor would be K ₂ Si _0.9 Mn _0.1 F ₆ Under atmospheric pressure and room temperature, it was added with dissolution to 70 ml of hydrofluoric acid (47.3% by weight) with dissolution. After all the starting compounds were completely dissolved, 70 ml of acetone was added at a rate of 240 ml / hr while stirring the solution to precipitate the phosphor in a poor solvent. The resulting phosphors were each washed with ethanol and dried at 130 ° C. for 1 hour to obtain 1.7 g of a phosphor.

It was confirmed from the X-ray diffraction pattern of the obtained phosphor that K ₂ SiF ₆ : Mn was synthesized. The X-ray diffraction pattern of this K ₂ SiF ₆ : Mn is shown in FIG.

  The excitation spectrum and emission spectrum of the obtained phosphor are shown in FIG. From the excitation spectrum, it can be seen that the excitation peak is in the range of 450 to 460 nm, and the excitation light from the blue LED chip can be absorbed efficiently. In addition, as the emission peak of the phosphor obtained in this example, 631 nm is set as the main emission peak wavelength, and a narrow narrow band red color having a half width of 6 nm is exhibited, so that the fluorescence characteristics suitable for the purpose of the present invention It can be said that it shows.

Example 1-2
4.9367 g of KHF _{2 and} 0.8678 g of K ₂ MnF ₆ were weighed and dissolved in 20 ml of hydrofluoric acid (47.3% by weight). This solution was added to a mixed solution of 10 ml of a 33 wt% aqueous H ₂ SiF ₆ solution and 10 ml of hydrofluoric acid (47.3 wt%) while stirring at 26 ° C. to precipitate yellow crystals. The obtained crystals are referred to as No. After filtering through a 5 C filter paper, it was washed 4 times with 100 ml of ethanol and dried at 130 ° C. for 1 hour to obtain 6.2 g of a phosphor.

It was confirmed from the X-ray diffraction pattern of the obtained phosphor that K ₂ SiF ₆ : Mn was synthesized. The X-ray diffraction pattern of this K ₂ SiF ₆ : Mn is shown in FIG.

Example 1-9
4.9367 g of KHF ₂ was weighed and dissolved in 10 ml of hydrofluoric acid (47.3% by weight).
On the other hand, 0.8678 g of K ₂ MnF ₆ was weighed and added to a mixed solution of 10 ml of a 33 wt% H ₂ SiF ₆ aqueous solution and 40 ml of hydrofluoric acid (47.3 wt%) to prepare a dissolved solution . While stirring the solution at 26 ° C., hydrofluoric acid in which KHF ₂ was dissolved was added to the solution to precipitate yellow crystals. The obtained crystals are referred to as No. After filtering through a 5 C filter paper, it was washed 4 times with 100 ml of ethanol and dried at 150 ° C. for 2 hours to obtain 5.9 g of a phosphor.

Comparative Example 1-1
A phosphor was obtained in the same manner as in Example 1-1 except that acetone which is a poor solvent was added at once.
It was confirmed from the X-ray diffraction pattern of the obtained phosphor that K ₂ SiF ₆ : Mn was synthesized. The X-ray diffraction pattern of this K ₂ SiF ₆ : Mn is shown in FIG.

<Comparison of phosphors obtained in Examples 1-1, 1-2, 1-9 and Comparative Example 1-1>
Regarding the phosphors obtained in Examples 1-1, 1-2, 1-9, and Comparative Example 1-1, the Mn concentrations determined as a result of composition analysis by SEM-EDX (“analytical The same applies to the following.) Luminance (relative value when P46Y3 is 100), absorption efficiency, internal quantum efficiency and external quantum efficiency obtained from the emission spectrum obtained by excitation with light of wavelength 455 nm It is shown in Table 10.
In addition, the weight median diameter D ₅₀ and the quarter deviation (QD) of the particle size distribution obtained from the specific surface area measurement result and the particle size distribution measurement are shown in Table 11.
Furthermore, particle size distribution curves are shown in FIGS. 6A and 6B, and SEM photographs are shown in FIGS. 7A and 7B, respectively.

The following can be understood from the above results.
In Example 1-1, although the deposition rate by the addition of the poor solvent was made slower as compared with Comparative Example 1-1, the concentration of Mn as the activating element (analyzed Mn concentration in Table 10) was smaller. The brightness is high. This is considered to be attributable to the increase in internal quantum efficiency as a result of homogeneous activation of Mn ions by controlling the deposition rate.
In addition, it is considered from the particle size distribution curves of FIG. 6A and FIG. 6B that the phosphor of Comparative Example 1-1 has a double distribution and small particles are aggregated, while Example 1-1 In the phosphor of the present invention, a large number of particles can be synthesized compared to the phosphor of Comparative Example 1-1, and since there are few small particles, there is no aggregation, no double distribution, and one peak. . This is also apparent from the measurement results of the specific surface area and weight median diameter D _50.
The particles having a small specific surface area as obtained in Example 1-1 are considered to be improved in durability because the contact area with the outside decreases.
In addition, with regard to the quarter deviation of the particle size distribution, the value is smaller in the order of Example 1-1, Example 1-2, and Example 1-9. From this data and FIG. 6A, it can be seen that the smaller the quarter deviation, the narrower the peak of the particle size distribution, ie, the more uniform the particle size.

On the other hand, the phosphor obtained by the method of Example 1-2 and Example 1-9, the SEM photograph, as is clear from the particle size distribution curve, specific surface area and weight median diameter D _50, 2 double size Since there is no distribution and no small particles, large particles without aggregation are obtained. As a result, as a result of the absorption efficiency becoming significantly higher, the luminance is considered to become higher.
In addition, as for the phosphors obtained in Example 1-2 and Example 1-9, many particles of hexagonal hexahedron in shape are seen (FIG. 7A). The specific surface area is also significantly smaller than the phosphors of Example 1-1 and Comparative Example 1-1, and the contact area with the outside is reduced, so that the durability is also considered to be improved.

Examples 1-3 to 1-6
A phosphor was obtained in the same manner as in Example 1-1 except that the preparation concentration of Mn was changed as described in Table 12.
Analysis Mn concentration of the obtained phosphor, luminance (relative value when P46Y3 is 100) obtained from emission spectrum obtained by excitation with light of wavelength 455 nm, absorption efficiency, internal quantum efficiency and external quantum efficiency And the quarter deviation (QD) of the particle size distribution are shown in Table 12 together with the results of Example 1-1.

Examples 1-7, 1-8, 1-10 to 1-15>
A phosphor was obtained in the same manner as in Example 1-2 except that the preparation concentration of Mn was changed as described in Table 12.
Analysis Mn concentration of the obtained phosphor, luminance (relative value when P46Y3 is 100) obtained from emission spectrum obtained by excitation with light of wavelength 455 nm, absorption efficiency, internal quantum efficiency and external quantum efficiency And the quarter deviation (QD) of the particle size distribution are shown in Table 12 together with the results of Example 1-2 and Example 1-9.

  From Table 12, 1) In the synthesis by the poor solvent precipitation method represented by Examples 1-1, 1-3, 1-4, 1-5, and 1-6, the preparation Mn concentration is 10 mol% It is understood that the concentration is 15 mol% or less and the concentration present in the crystal, that is, the analysis Mn concentration is preferably 2 mol% to 4 mol%. In addition, a solution containing at least Si and F and a solution containing at least K, Mn, and F, as typified by Examples 1-2, 1-7, and 1-8, In the synthesis according to the mixing method, it is preferable that the preparation Mn concentration is 5 mol% to 15 mol%, and the concentration present in the crystal, that is, the analysis Mn concentration is 3 mol% to 5 mol%. I understand. Further, 2-2) a solution containing at least Si, Mn, and F as represented by Examples 1-9, 1-11, 1-12, 1-13, 1-14, and 1-15, In the synthesis by the method of mixing with a solution containing at least KF, the preparation Mn concentration is 3 mol% or more and 10 mol% or less, and the concentration present in the crystal, ie, the analysis Mn concentration is 2 mol% or more It turns out that it is preferable that it is mol% or less.

<Comparative Examples 1-2, 1-3>
A phosphor was obtained in the same manner as in Comparative Example 1-1 except that ethanol (Comparative Example 1-2) or acetic acid (Comparative Example 1-3) was used instead of acetone as the poor solvent.
The quarter deviation (QD) of the particle size distribution determined for the obtained phosphor is shown in Table 13 together with the result of Comparative Example 1-1.

  Moreover, as for the fluorescent substance obtained by the above-mentioned Example and comparative example, the light emission peak wavelength was 630 nm in all, and the half value width of the light emission peak was 6 nm.

<Examples 1-16 to 1-19>
4.9367 g of KHF ₂ was weighed, added to 45 ml of hydrofluoric acid (47.3% by weight) and 5 ml of pure water and dissolved (solution III: hydrofluoric acid concentration 43% by weight).
On the other hand, 4.3393 g of K ₂ MnF ₆ was weighed and added to a mixed solution of 50 ml of a 33 wt% H ₂ SiF ₆ aqueous solution and 200 ml of hydrofluoric acid (47.3 wt%) to prepare a dissolved solution (Solution IV). While stirring this solution IV at 26 ° C., the above-mentioned solution III of hydrofluoric acid in which KHF ₂ was dissolved was added to this solution IV to precipitate yellow crystals. The obtained crystals are referred to as No. After filtering through a 5 C filter paper, it was washed 4 times with 50 ml of ethanol and dried at 150 ° C. for 2 hours to obtain 29.6 g of a phosphor (Example 1-16).
In Examples 1-17 to 1-19, as described in Table 14 below, phosphors were synthesized under the same conditions as in Example 1-16 except that only the preparation amount was changed.

Analysis of the obtained phosphor (all prepared: Mn concentration is 10 mol%), the luminance determined from the emission spectrum obtained by excitation with light of wavelength 455 nm (relative value when P46Y3 is 100) The absorption efficiency, internal quantum efficiency and external quantum efficiency, as well as specific surface area, weight median diameter D ₅₀ , and quarter deviation of particle size distribution (QD) are shown in Table 15.
The particle size distribution curve is shown in FIG. 14 and the SEM photograph is shown in FIG.

In Examples 1-16 to 1-19, the preparation Mn concentration is 10 mol% as in Example 1-9, but the hydrofluoric acid concentration of the solution III is 47 wt% of Example 1-9. From 43% by weight (Examples 1-16), 41% by weight (Examples 1-17), 39% by weight (Examples 1-18), or 35% by weight (Examples 1-19) From these results, it can be seen that the hydrofluoric acid concentration of solution III is preferably 35% to 45% by weight.
Further, it is also understood from the results of Examples 1-16 to 1-19 that as the specific surface area is smaller, the absorption efficiency is higher and the luminance is also higher.
Each of the phosphors obtained in Examples 1-16 to 1-19 had a light emission peak wavelength of 630 nm and a half value width of the light emission peak of 6 nm.

[Example of semiconductor light emitting device and comparative example]
Example 2-1
As a blue light emitting diode (hereinafter, appropriately abbreviated as “LED”) emitting light with a half width of the emission peak of 22 nm to 28 nm at a dominant emission wavelength of 455 nm to 465 nm (emission peak wavelength of 451 nm to 455 nm) Using square chip GU35R460T, it was adhered to the terminal at the bottom of the recess of 3528 SMD type PPA resin package with a transparent die bond paste based on silicone resin. Thereafter, the transparent die-bonding paste was cured by heating at 150 ° C. for 2 hours, and then the blue LED and the electrode of the package were wire-bonded using a gold wire of 25 μm in diameter.

On the other hand, a green phosphor Ba _1.36 Sr _0.49 Eu _0.15 SiO ₄ having a light emission peak wavelength of 528 nm and a light emission peak half width of 68 nm manufactured in Synthesis Example 2 of phosphor described later (with “BSS” in Table 16) Red fluorescent substance (denoted as “KSF” in Table 16) having a light emission peak wavelength of 631 nm and a light emission peak half width of 6 nm synthesized in Example 1-1, and Toray Dow 0.880 g of Corning silicone resin (JCR 6101up) and 0.026 g of Aerosil (RX 200) manufactured by Nippon Aerosil Co., Ltd. are weighed and mixed using a stirring / defoaming device AR-100 manufactured by Shinky Co., Ltd. Obtained.

  Next, 4 μl of the phosphor-containing composition obtained as described above using a dispenser was poured into the recess of the SMD type resin package provided with the blue LED. Thereafter, the phosphor-containing composition was cured by heating at 70 ° C. for 1 hour and then at 150 ° C. for 5 hours to obtain a desired semiconductor light emitting device.

  A current of 20 mA was applied to the blue LED chip of the obtained white semiconductor light emitting device to emit light. The CIE chromaticity coordinate value of the light emission was measured, and it was x / y = 0.319 / 0.327. The obtained emission spectrum is shown in FIG. The white luminous flux from the semiconductor light emitting device for the light output from the blue LED was 236 lumens / W.

  When this semiconductor light emitting device is used as a liquid crystal back light, the chromaticity (x, y, Y) is obtained for a color image display obtained by combining this with the optimized color filter obtained in Production Example 1 described later. Was obtained as (0.321, 0.341, 27.3), and the color reproducibility (NTSC ratio) and color tone (color temperature) were obtained as NTSC ratio 95 and color temperature 5999 K, respectively. Here, the Y value in the chromaticity (x, y, Y) corresponds to the utilization efficiency of light emission from the backlight.

When using the semiconductor light emitting device of this example obtained by using the red phosphor of the present invention obtained in Example 1-1 while using the same light emission utilization efficiency, known CaAlSiN ₃ : Eu can be obtained. A higher NTSC ratio could be obtained than the semiconductor light emitting device of Comparative Example 2-1 described later obtained by using it.

  The emission spectrum of the semiconductor light emitting device is as follows: in a room maintained at a temperature of 25 ± 1 ° C., conduct current at 20 mA using color / illuminance measurement software made by Ocean Optics and a USB 2000 series spectrometer (integral sphere specification) The measurements were taken. From the data in the wavelength range of 380 nm to 780 nm of this emission spectrum, the chromaticity value (x, y, z) was calculated as the chromaticity coordinates in the XYZ color system specified by JIS Z 8701 (in this case, x + y + z = 1) In the present specification, the XYZ color system may be referred to as an XY color system, which is usually expressed as (x, y). The luminous efficiency (lm / W) was also calculated from the obtained emission spectrum. Moreover, the light emission peak wavelength of the fluorescent substance used by Example 2-1 to 2-3 and Comparative Example 2-1 to 2-3 and its half value width are also measured using said apparatus.

Comparative Example 2-1
In the preparation of the semiconductor light-emitting device of Example 2-1, 0.060 g of green phosphor Ba _1.36 Sr _0.49 Eu _0.15 SiO ₄ (denoted as “BSS” in Table 16), Mitsubishi Chemical Red phosphor “BR-101A” (CaAlSiN ₃ : Eu, described as “CASN” in Table 16) with a light emission peak wavelength of 650 nm and a light emission peak wavelength of 92 nm and a silicone manufactured by Shin-Etsu Chemical Co., Ltd. The semiconductor light emitting device of Comparative Example 2-1 was obtained by the same operation as Example 2-1 except that 0.618 g of resin (SCR1011) and 0.019 g of Aerosil (RX200) manufactured by Nippon Aerosil Co., Ltd. were weighed. .

  A current of 20 mA was applied to the blue LED chip of the obtained white semiconductor light emitting device to emit light. The CIE chromaticity coordinate value of the light emission was measured to be x / y = 0.312 / 0.319. The obtained emission spectrum is shown in FIG. The white luminous flux from the semiconductor light emitting device for the light output from the blue LED was 234 lumens / W.

  When this semiconductor light emitting device is used as a liquid crystal back light, the color image display device obtained by combining this with the optimized color filter obtained in Production Example 1 to be described later has chromaticity (x, y, Y) was determined to be (0.330, 0.331, 27.3), and color reproducibility (NTSC ratio) and color tone (color temperature) were determined to be NTSC ratio 87 and color temperature 5611 K, respectively.

Example 2-2
A 290 μm square chip C395MB290 manufactured by Cree was used as a near-ultraviolet LED emitting at a dominant emission wavelength of 390 nm to 400 nm, which was adhered to the terminal of the bottom of the recess of 3528 SMD type PPA resin package with a silicone resin based transparent die bond paste. . Thereafter, the transparent die-bonding paste was cured by heating at 150 ° C. for 2 hours, and then the near-ultraviolet LED and the electrode of the package were wire-bonded using a gold wire of 25 μm in diameter.

On the other hand, 0.038 g of Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu (described as “SCA” in Table 16) having a light emission peak wavelength of 450 nm and a light emission peak half width of 29 nm manufactured in Synthesis Example 3 of phosphor described later And 0.083 g of BaMgAl ₁₀ O ₁₇ : Eu, Mn (with “GBAM” in Table 16) having a light emission peak wavelength of 517 nm and a light emission peak half width of 27 nm manufactured in Synthesis Example 4 of phosphor described later Weighing 0.407 g of the red phosphor synthesized in Example 1-1 of the phosphor (described as “KSF” in Table 16) and 0.634 g of silicone resin (JCR 6101 up) manufactured by Toray Dow Corning, The mixture was mixed by a stirring and degassing apparatus AR-100 manufactured by Shinky Co., Ltd. to obtain a phosphor-containing composition.

  Next, 4 μl of the phosphor-containing composition obtained as described above was poured into the recess of the SMD type resin package provided with the near-ultraviolet LED using a dispenser. Thereafter, the phosphor-containing composition was cured by heating at 70 ° C. for 1 hour and then at 150 ° C. for 5 hours to obtain a desired semiconductor light emitting device.

  The near ultraviolet LED of the obtained white semiconductor light emitting device was driven by applying a current of 20 mA to emit light. The CIE chromaticity coordinate value of the light emission was measured to be x / y = 0.339 / 0.339. The obtained emission spectrum is shown in FIG. The white luminous flux from the semiconductor light emitting device for the light output from the near ultraviolet LED was 230 lumens / W.

The semiconductor light emitting device of the present example obtained by using the red phosphor of the present invention obtained in Example 1-1 while having semiconductor light emitting devices having substantially the same chromaticity coordinate values has an emission peak wavelength. It was possible to obtain a luminous flux per unit incident light energy significantly higher than the semiconductor light-emitting device of Comparative Example 2-2 described later obtained by using CaAlSiN ₃ : Eu having good color purity of 660 nm.

  Further, when this semiconductor light emitting device is used as a liquid crystal back light, the chromaticity (x, y) is obtained for a color image display device obtained by combining this with the optimized color filter obtained in Production Example 1 described later. , Y) is determined as (0.346, 0.374, 28.3), and the color reproducibility (NTSC ratio) and color tone (color temperature) are determined as NTSC ratio 116 and color temperature 5021 K, respectively. .

When using the semiconductor light emitting device of this example obtained by using the red phosphor obtained in Example 1-1 while having substantially the same light emission utilization efficiency, the light emission peak wavelength 660 nm and the light emission peak half width A significantly higher NTSC ratio could be obtained than the semiconductor light emitting device of Comparative Example 2-2 described later obtained by using CaAlSiN ₃ : Eu having good color purity of 95 nm.

Example 2-3 and Comparative Examples 2-2 and 2-3
In the preparation of the semiconductor light-emitting device of Example 2-2, operations are carried out in the same manner as in Example 2-2 except that the type and amount of phosphor used and the amount of silicone resin are changed as shown in Table 16. The semiconductor light-emitting devices of Example 2-3, Comparative example 2-2, and Comparative example 2-3 were obtained. In Example 2-3 and Comparative Example 2-3, Ba _0.7 Eu _0.3 having a light emission peak wavelength of 455 mm and a light emission peak half width of 51 nm, which were produced in Synthesis Example 5 of a phosphor described later as blue phosphors. MgAl ₁₀ O ₁₇ (denoted as “BAM” in Table 16) was used. Further, as the red phosphors of Comparative Example 2-2 and Comparative Example 2-3, a red phosphor “BR-101B” (CaAlSiN ₃ : Eu) having a light emission peak wavelength of 660 nm and manufactured by Mitsubishi Chemical Co., Ltd. "CASN 660" was used.

  A current of 20 mA was applied to the near-ultraviolet LED of the obtained semiconductor light emitting device to drive and emit light. The CIE chromaticity coordinate values of the light emission were measured, and the values were as shown in Table 17. Moreover, the emission spectrum of the semiconductor light-emitting device obtained by Example 2-3, Comparative Example 2-2, and Comparative Example 2-3 is shown in FIG. 11, FIG. 12, and FIG. 13, respectively.

Further, when this semiconductor light emitting device is used as a liquid crystal back light, the chromaticity (x, x) of a color image display device obtained by combining this with the optimized color filter obtained in Production Example 1 described later. y, Y), color reproducibility (NTSC ratio), and color tone (color temperature) were calculated and are shown in Table 17.

[Method of synthesizing phosphor]
The phosphors used in the above-described Examples 2-1 to 2-3 and Comparative examples 2-1 to 2-3 are synthesized as follows.

Synthesis Example 2
As phosphor raw materials, powders of barium carbonate (BaCO ₃ ), strontium carbonate (SrCO ₃ ), europium oxide (Eu ₂ O ₃ ), and silicon dioxide (SiO ₂ ) were used. Each of these phosphor materials has a purity of 99.9% or more and a weight median diameter D _{50 in} the range of 0.01 μm to 5 μm.
These phosphor materials were weighed so that the composition of the obtained phosphor was Ba _1.36 Sr _0.49 Eu _0.15 SiO ₄ .

The powders of these phosphor materials were mixed in an automatic mortar until they became sufficiently uniform, filled in an alumina crucible, and fired at 1000 ° C. for 12 hours in a nitrogen atmosphere under atmospheric pressure.
Next, the content of the crucible was taken out, and 0.1 mol of SrCl ₂ and 0.1 mol of CsCl were added as a flux to 1 mol of the phosphor, and mixed and ground in a dry ball mill.
The mixed and pulverized material obtained was again filled in an alumina crucible, solid carbon (in the form of a block) was placed thereon, and an alumina lid was placed thereon. After reducing the pressure to 2 Pa with a vacuum pump in a vacuum furnace, hydrogen-containing nitrogen gas (nitrogen: hydrogen = 96: 4 (volume ratio)) was introduced until atmospheric pressure. After repeating this operation again, firing was carried out by heating at 1200 ° C. for 4 hours under atmospheric pressure in a flow of hydrogen-containing nitrogen gas (nitrogen: hydrogen = 96: 4 (volume ratio)).
The obtained fired product is crushed by a ball mill, and after removing coarse particles through a sieve in a slurry state, it is washed with water and drained to remove fine particles, and after drying it is sieved to dissolve agglomerated particles. The phosphor (BSS) was produced by passing through.
The emission peak wavelength of the obtained green phosphor (BSS) was 528 nm, and the emission peak half width was 68 nm.

Synthesis Example 3
0.2 mol SrCO ₃ (Kanto Chemical Co.), 0.605 mol SrHPO ₄ (Kanto Chemical Co.), 0.050 mol Eu ₂ O ₃ (Shin-Etsu Chemical 99.99% purity), SrCl ₂ (Kanto 0.1 mol of Chemical Co., Ltd. product) was weighed and dry-mixed by a small V-type blender.
The obtained raw material mixture was filled in an alumina crucible and set in a box-type electric furnace. The temperature was raised to 1050 ° C. at a temperature rising rate of 5 ° C./min in the atmosphere under atmospheric pressure, and held for 5 hours to obtain a fired product (primary firing).
Then, after cooling to room temperature, the content of the crucible was taken out and crushed.
0.05 mol of SrCl ₂ was added to the obtained fired product, mixed with a small V-type blender, then filled in an alumina crucible, and the crucible was set in the same electric furnace as the primary firing. While flowing hydrogen-containing nitrogen gas (hydrogen: nitrogen = 4: 96 (volume ratio)) at a rate of 2.5 liters per minute, the temperature is raised to 950 ° C at a heating rate of 5 ° C / min under atmospheric pressure in a reducing atmosphere. And held for 3 hours (secondary firing). Then, after cooling to room temperature, the content of the crucible was taken out and crushed.

0.05 mol of SrCl ₂ was added to the obtained fired product, mixed with a small V-type blender, and then filled in an alumina crucible. The crucible was again set in the same electric furnace as the secondary firing. While flowing hydrogen-containing nitrogen gas (hydrogen: nitrogen = 4: 96 (volume ratio)) at 2.5 liters per minute, the temperature is raised to 1050 ° C at a heating rate of 5 ° C / min in a reducing atmosphere, at atmospheric pressure, And held for 3 hours.
The obtained fired mass was roughly crushed to a particle size of about 5 mm, and then treated with a ball mill for 6 hours to obtain a phosphor slurry.

In order to wash the phosphor, the phosphor slurry is stirred and mixed in a large amount of water, and allowed to stand until the phosphor particles settle, and then the supernatant liquid is discarded, the electric conductivity of the supernatant is 3 mS / m. It repeated until it became the following. After confirming that the electric conductivity of the supernatant liquid was 3 mS / m or less, classification was performed to remove fine particle and coarse particle phosphors.
The obtained phosphor slurry was dispersed in an aqueous Na ₃ PO ₄ solution of pH = 10, and after classification removal of small particles, a calcium phosphate treatment was performed. After dehydration, it was dried at 150 ° C. for 10 hours to obtain a phosphor (SCA): Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu.

  The emission peak wavelength of the obtained blue phosphor (SCA) was 450 nm, and the half width of the emission peak was 29 nm.

Synthesis Example 4
Barium carbonate (BaCO ₃ ), europium oxide (Eu ₂ O ₃ ), basic magnesium carbonate (mass 93.17 per mol of Mg), manganese carbonate (MnCO ₃ ), α-alumina (Al ₂ O ₃ ) as phosphor raw materials ) And aluminum fluoride (AlF 3) as a sintering aid. These phosphor materials _{are, Ba 0.455 Sr 0.245 Eu 0.3 Mg} 0.7 Mn 0.3 Al 10 was weighed amount such that the chemical compositions shown in _{O 17,} a phosphor baking aids It weighed so that it might be 0.8 weight% with respect to the total weight of a raw material, mixed in a mortar for 30 minutes, and filled in an alumina crucible. In order to create a reducing atmosphere at the time of firing, the alumina crucible was doubled, and bead-like graphite was placed in the space around the inner crucible, and firing was carried out in the air at 1550 ° C. for 2 hours. The obtained fired product was crushed to obtain a green phosphor (GBAM).

  The emission peak wavelength of the obtained green phosphor (GBAM) was 517 nm, and the half width of the emission peak was 27 nm.

Synthesis Example 5
0.7 mol of barium carbonate (BaCO ₃ ), 0.15 mol of europium oxide (Eu ₂ O ₃ ), 0.15 mol of basic magnesium carbonate (mass 93.17 per mol of Mg) as Mg, as phosphor raw materials, Weigh 5 moles of α-alumina (Al ₂ O ₃ ) and the chemical composition of the phosphor to be Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , mix in a mortar for 30 minutes, It was filled and fired for 5 hours at 1200 ° C. while flowing nitrogen in a box-type firing furnace, and after cooling, it was taken out from a crucible and crushed to obtain a precursor of a phosphor.
0.3% by weight of AlF ₃ is added to this precursor, ground and mixed in a mortar for 30 minutes, filled in an alumina crucible, and filled with nitrogen gas containing 4% by volume of hydrogen in a box atmosphere baking furnace The mixture was fired at 1450 ° C. for 3 hours, and the fired product obtained after cooling was crushed to obtain a pale blue powder.

To this powder, 0.42% by weight of AlF ₃ is added, ground and mixed for 30 minutes in a mortar, filled in an alumina crucible, beaded graphite is placed in the space around the crucible, Nitrogen is circulated at 4 liters per minute and fired at 1550 ° C. for 5 hours, and the obtained fired product is crushed by a ball mill for 6 hours, classified with a water tank and washed with water to obtain a blue phosphor (BAM) The
The emission peak wavelength of the obtained blue phosphor (BAM) was 455 nm, and the half width of the emission peak was 51 nm.

[Method of making optimized color filter]
The optimized color filters used in the above-described Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 are produced as follows.

<Production Example 1>
<Production of red pixel>
First, 55 parts by weight of benzyl methacrylate, 45 parts by weight of methacrylic acid and 150 parts by weight of propylene glycol monomethyl ether acetate are placed in a 500 ml separable flask, and the inside of the flask is sufficiently replaced with nitrogen. Thereafter, 6 parts by weight of 2,2′-azobisisobutyro nitrile is added, and the mixture is stirred at 80 ° C. for 5 hours to obtain a polymer solution. The weight average molecular weight of the synthesized polymer is 8000, and the acid value is 176 mg KOH / g. This is used as a binder resin.
Next, 75 parts by weight of propylene glycol monomethyl ether acetate, red pigment P.I. R. 16.7 parts by weight of 254, 4.2 parts by weight of acrylic dispersant "DB 2000" manufactured by Big Chemie Co., and 5.6 parts by weight of the binder resin produced as described above are mixed, and stirred for 3 hours with a stirrer to obtain solid content Prepare a millbase with a concentration of 25% by weight. The mill base was subjected to a dispersion treatment at a peripheral speed of 10 m / s and a residence time of 3 hours in a bead mill apparatus using 600 parts by weight of 0.5 mmφ zirconia beads and P.P. R. There are obtained 254 dispersed inks.
Moreover, the pigment is P.I. R. The above-mentioned P.I. R. A mill base is prepared with the same composition as the mill base of 254, and subjected to dispersion treatment for 3 hours at a residence time under the same dispersion conditions for P.P. R. There are obtained 177 dispersed inks.

Stir while 145 parts by weight of propylene glycol monomethyl ether acetate are purged with nitrogen, and raise the temperature to 120 ° C. Thereto, 20 parts by weight of styrene, 57 parts of glycidyl methacrylate and 82 parts by weight of monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped, and the resist solution is further stirred by 120 ° C. for 2 hours. create.
The dispersion ink obtained as described above and the resist solution obtained above are mixed and stirred in a weight ratio of R254: R177: clear resist = 24.1: 13.9: 62.0, and the final solid is obtained. A solvent (propylene glycol monomethyl ether acetate) is added so that the concentration becomes 25% by weight to obtain a red color filter composition.

The composition for a color filter thus obtained is applied on a 10 cm × 10 cm glass substrate (“AN 635” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet light with an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a red pixel sample for measurement. The film thickness of the red pixel after preparation is made to be 2.5 μm.

<Production of green pixels>
The above-mentioned pigment is changed to an azo nickel complex yellow pigment (hereinafter referred to as “pigment Y”) synthesized according to the production example (paragraph [0066]) of Example 2 of JP-A-2007-25687. P. R. A mill base is prepared with a composition similar to that of 254 mill base, and is subjected to dispersion treatment with a residence time of 2 hours under the same dispersion conditions to obtain a pigment Y dispersed ink.
Similarly, except that the pigment was changed to brominated zinc phthalocyanine, and the dispersant was changed to an acrylic dispersant "LPN6919" manufactured by Big Chemie, P.I. R. A mill base is prepared with the same composition as 254, and is subjected to dispersion treatment with a residence time of 3 hours under the same dispersion conditions to obtain a dispersion ink of brominated zinc phthalocyanine. The brominated zinc phthalocyanine pigment is synthesized by the method shown below.

  The dispersion ink obtained as described above and the resist solution produced above are mixed and stirred at a weight ratio of brominated zinc phthalocyanine pigment: pigment Y: clear resist = 22.4: 21.1: 56.5. Then, a solvent (propylene glycol monomethyl ether acetate) is added to a final solid concentration of 25% by weight to obtain a green color filter composition.

The composition for a color filter thus obtained is applied on a 10 cm × 10 cm glass substrate (“AN 635” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet light at an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a green pixel sample for measurement. The film thickness of the green pixel after preparation is made to be 2.5 μm.

(Synthesis of brominated zinc phthalocyanine)
Zinc phthalocyanine was manufactured using phthalodinitrile and zinc chloride as raw materials. This 1-chloro naphthalene solution had light absorption in the wavelength range of 600 to 700 nm. 3.1 parts by weight of sulfuryl chloride, 3.7 parts by weight of anhydrous aluminum chloride, 0.46 parts by weight of sodium chloride and 1 part by weight of zinc phthalocyanine are mixed at 40 ° C., and 4.4 parts by weight of bromine are dropped to obtain zinc The phthalocyanine was brominated. The mixture was allowed to react at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed at 80 ° C. with hot water and dried at 90 ° C. to obtain 3.0 parts by weight of a purified brominated zinc phthalocyanine crude pigment.

One part by weight of this brominated zinc phthalocyanine crude pigment, 12 parts by weight of ground sodium chloride, 1.8 parts by weight of diethylene glycol, and 0.09 parts by weight of xylene were charged in a double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out in 100 parts by weight of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried, and ground to obtain a brominated zinc phthalocyanine pigment.
The resulting brominated zinc phthalocyanine pigment had an average composition ZnPcBr ₁₄ Cl ₂ (Pc: phthalocyanine) according to halogen content analysis by mass spectrometry, and contained 14 bromine in average in one molecule.

<Production of Blue Pixels>
The pigment is P.I. G. The above-mentioned P.I. R. A mill base is prepared with the same composition as the mill base of 254, and is subjected to dispersion treatment with a residence time of 1 hour under the same dispersion conditions. G. A dispersion ink of 15: 6 is obtained.
Moreover, the pigment is P.I. V. The above-mentioned P.I. R. A mill base is prepared with a composition similar to that of 254 mill base, and subjected to dispersion treatment with a residence time of 2 hours under the same dispersion conditions. V. Obtain 23 dispersed inks.
The dispersion ink obtained as described above and the resist solution prepared above are mixed and stirred at a weight ratio of B15: 6: V23: clear resist = 14.4: 4.9: 80.7, and the final A solvent (propylene glycol monomethyl ether acetate) is added so that the solid concentration becomes 25% by weight, to obtain a blue color filter composition.

The composition for a color filter thus obtained is applied on a 10 cm × 10 cm glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet light with an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a blue pixel sample for measurement. The film thickness of the blue pixel after preparation is made to be 2.5 μm.

1 Phosphor-containing part (second luminous body)
2 Excitation light source (first light emitter) (LD)
Reference Signs List 3 substrate 4 light emitting device 5 mount lead 6 inner lead 7 excitation light source (first light emitter)
DESCRIPTION OF SYMBOLS 8 fluorescent substance containing part 9 electroconductive wire 10 mold member 11 surface emitting lighting apparatus 12 holding case 13 light emitting apparatus 14 diffusion plate 22 excitation light source (1st light-emitting body)
23 Phosphor-containing part (second luminous body)
24 frame 25 conductive wire 26, 27 electrode

Claims (10)

Contains a crystal phase having a chemical composition represented by the following formula [1],
The ratio of Mn to the total number of moles of M ⁴ and Mn is 0.1 mol% or more and 40 mol% or less, and
A phosphor having a specific surface area of 1.3 m ² / g or less.
M ¹ ₂ M ⁴ F ₆ : R ... [1]
(In the above-mentioned formula [1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ is a metal element containing Si, R contains at least Mn. Represents an activating element.)   The phosphor according to claim 1, wherein the peak value of the particle size distribution is one.   The phosphor according to claim 1 or 2, wherein a quarter deviation of the particle size distribution is 0.6 or less.   A method comprising the steps of: reacting a solution containing at least Si and F with a solution containing at least K, Mn, and F to obtain the compound represented by the formula [1]. The manufacturing method of the fluorescent substance of any one of 1 thru | or 3. A method for producing a phosphor containing a crystal phase having a chemical composition represented by the following formula [1],
A method for producing a phosphor, comprising mixing two or more of a solution containing one or more elements selected from the group consisting of K, Na, Si, Mn, and F to precipitate a phosphor.
M ¹ ₂ M ⁴ F ₆ : R ... [1]
(In the above-mentioned formula [1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ is a metal element containing Si, R contains at least Mn. Represents an activating element.)   A phosphor-containing composition comprising the phosphor according to any one of claims 1 to 3 and a liquid medium. What is claimed is: 1. A light emitting device comprising: a first light emitting body; and a second light emitting body that emits visible light by irradiation of light from the first light emitting body,
A light emitting device comprising a first phosphor containing one or more of the phosphors according to any one of claims 1 to 3 as the second light emitter.   8. The light emission according to claim 7, wherein the second light emitter includes a second phosphor including one or more phosphors having different emission peak wavelengths from the first phosphor. apparatus.   A lighting device comprising the light emitting device according to claim 7.   An image display apparatus comprising the light emitting device according to claim 7.

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