JP2017128740A - Fluorescent body and method for producing the same, fluorescent body-containing composition and light-emitting device using the fluorescent body, and image display device and illumination device using the light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red fluorescent body which has a narrow half-value width of light-emission peak and is excellent in light-emission characteristics and a method for producing the same; a fluorescent body-containing composition and a light-emitting device using the fluorescent body; and an image display device and an illumination device using the light-emission device.SOLUTION: A fluorescent body contains a crystal phase having a chemical composition represented by formula [1]: MMF:R, where a ratio of Mn to the total molar number of Mand Mn is 1 mol% or more and 8 mol% or less, and a weight median diameter is 10 μm or more and 50 μm or less. In formula [1], Mcontains one or more elements selected from the group consisting of K and Na; Mis a metal element containing Si; and R represents an activating element containing at least Mn.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a phosphor emitting red 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 an illumination device using the light emitting device.

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

  Recently, an attempt has been made to use a semiconductor light emitting element as the light source of these three colors. However, it is not common to use semiconductor light emitting elements for all three colors because a circuit for compensating the color shift during use is required. Therefore, it is practical to obtain the desired three colors by converting the wavelength of light emitted from the semiconductor light emitting element using a phosphor. Specifically, blue, green, and red light are emitted using a near-ultraviolet light emitting semiconductor light emitting device as a light source, and light emitted from the blue light emitting semiconductor light emitting device is used as blue as it is. A method obtained by conversion is known.

  Among these, it is considered preferable to use a phosphor having a narrow half-value width of the emission peak as a phosphor used for display applications from the viewpoint of light utilization efficiency and the like. In addition, in the case of using for illumination purposes, it is preferable to use a phosphor having a narrow emission peak half-width in consideration of the balance with the luminous efficiency when used together with other phosphors in order to improve color rendering. it is conceivable that.

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

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

Specification of US Publication No. 2006/0169998 U.S. Pat. No. 3,576,756

The production method such as K ₂ TiF ₆ : Mn by evaporation to dryness in hydrofluoric acid described in Patent Document 1 is difficult to mass-produce from the viewpoint of safety and productivity.

  In addition, when the present inventors re-examined the method described in Patent Document 2, it was found that the obtained phosphor particles were fine, the luminance was low, and the practicality was insufficient.

  For these reasons, phosphors with a narrow emission peak half-value width and light-emitting devices using the same have been desired for display and lighting applications, but they have not been realized yet. Is the current situation.

  The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a red phosphor having a narrow emission peak half-value width and excellent emission characteristics, and a method for producing the same, and using this phosphor. The object is to provide 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 present inventors have studied in detail a method for producing a K ₂ SiF ₆ : Mn phosphor, and as a result, can obtain a phosphor having a smaller specific surface area and superior emission characteristics than the conventional one, The present invention has been completed by finding a technique that can be suitably used for applications such as light-emitting devices.

  That is, the gist of the present invention is the following (1) to (6).

(1) containing a crystal phase having a chemical composition represented by the following formula [1],
A phosphor characterized in that the ratio of Mn to the total number of moles of M ⁴ and Mn is 1 mol% or more and 8 mol% or less, and the weight median diameter is 10 μm or more and 50 μm or less.
M ¹ ₂ M ⁴ F ₆ : R (1)
(In 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, and R is an attachment containing at least Mn. Represents an active element.)

(2) A phosphor-containing composition comprising the phosphor according to (1) and a liquid medium.

(3) A light-emitting device including a first light-emitting body and a second light-emitting body that emits visible light when irradiated with light from the first light-emitting body. A light-emitting device comprising a first phosphor containing one or more of the phosphors described in 1).

(4) The second phosphor includes a second phosphor including one or more phosphors having emission peak wavelengths different from those of the first phosphor. (3) The light-emitting device of description.

(5) An illumination device comprising the light-emitting device according to (3) or (4).

(6) An image display device comprising the light-emitting device according to (3) or (4).

According to the present invention, it is possible to provide a red phosphor having a narrow half-value width of an emission peak and excellent emission characteristics.
Furthermore, the manufacturing method of this red fluorescent substance which improved safety | security and productivity compared with the past can also be provided.
In addition, by using the phosphor of the present invention, it is possible to provide a light emitting device, an illuminating device, and an image display device that have a wider color reproduction range and higher luminous efficiency than conventional ones.

It is a typical perspective view which shows one Example of the light-emitting device of this invention. FIG. 2A is a schematic cross-sectional view showing an embodiment of a bullet-type light emitting device of the present invention, and FIG. 2B is a schematic view showing an embodiment of the surface-mounted light-emitting device of the present invention. It is sectional drawing. It is typical sectional drawing which shows one Example of the illuminating device of this invention. It is a chart which shows the powder X-ray-diffraction pattern of the fluorescent substance obtained in Example 1-1, Example 1-2, and Comparative Example 1-1. It is a chart which shows the excitation and the 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 the comparative example 1-1. It is a SEM photograph of the phosphor obtained in Example 1-1, Example 1-2, and Example 1-9. It is a SEM photograph of the phosphor obtained in 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 the 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 the comparative example 2-2. It is a chart which shows the emission spectrum of the semiconductor light-emitting device produced by the 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 phosphor obtained in Example 1-16, Example 1-17, Example 1-18, and Example 1-19.

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

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

Further, in the phosphor composition formula in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition. For example, the composition formula “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” has “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. “Ca _1−x Sr _x Al ₂ O ₄ : Eu”, “Sr _1−x Ba _x Al ₂ O ₄ : Eu”, “Ca _1−x Ba _x Al ₂ O ₄ : Eu”, _{"Ca 1-x-y Sr x} Ba y Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <X + y <1).

[1. Phosphor]
[1-1. Composition 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.
M ¹ ₂ M ⁴ F ₆ : R (1)
(In the 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, and R contains at least Mn. Represents an activator element.)

In the above formula [1], M ¹ contains an element selected from the group consisting of potassium (K) and sodium (Na). Any one of these elements may be contained alone, or two of them may be contained in any ratio. In addition to the above, an alkali metal element such as Li, Rb, and Cs or a part of (NH ₄ ) may be contained 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 .

Of these, M ¹ preferably contains at least K. Usually, K is accounted for more than 90 mol% based on the total M ¹ amount, a case preferably 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 K.

In the above formula [1], M ⁴ contains at least Si. Usually, Si accounts for 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 M ⁴ amount. It is particularly preferable to use only Si. That is, it is particularly preferable that the phosphor containing a crystal phase having the chemical composition represented by the formula [1] contains a crystal phase having a chemical composition represented by the following formula [2].
M ¹ ₂ SiF ₆ : R ... [2]
(In the formula [2], M ¹ contains one or more elements selected from the group consisting of K and Na, and R represents an activator element containing at least Mn.)

In the above formula [1], elements that may be contained other than Si as M ⁴ include Ti, Zr, Ge, Sn, Al, Ga, B, In, Nb, Mo, Zn, Ta, and W. 1 type, or 2 types or more selected from the group consisting of, Re, and Mg.

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

  R preferably contains 90 mol% or more of Mn relative to the total amount of R, more preferably 95 mol% or more, particularly preferably 98 mol% or more, and particularly preferably contains 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 that. If the Mn concentration is too low, the absorption efficiency of the excitation light by the phosphor decreases, so the luminance tends to decrease. If it is too high, the absorption efficiency increases, but the internal quantum efficiency and luminance decrease due to concentration quenching. Tend to. The lower limit of the Mn concentration is more preferably 0.4 mol% or more, further preferably 1 mol% or more, and particularly preferably 2 mol% or more. Further, the upper limit of the Mn concentration is more preferably 20 mol% or less, further preferably 8 mol% or less, and particularly preferably 6 mol% or less.

  In addition, the chemical composition analysis of the Mn concentration contained in the phosphor in the present invention can be measured by, for example, SEM-EDX. In this method, in 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. Analyze. As the measuring apparatus, 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.

  The phosphor of the present invention is preferably manufactured by the method described in the phosphor manufacturing method described later. In the phosphor manufacturing method, for the following reasons, There is a slight deviation from the composition of the phosphor obtained. The phosphor of the present invention is characterized by having the above-mentioned specific composition as the composition of the obtained phosphor, not the raw material composition at the time of phosphor production.

Compared to Si ⁴⁺ ion radius (0.4 Å) ^{Mn 4+} ionic radius (0.53 Å) is large, ^{Mn 4+} _is not totally dissolved in K 2 SiF _6, since the partial solid solution, the charged composition 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 production method of the present invention described later, since the 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 characteristics when an emission spectrum is measured when excited with 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 605 nm or more, more preferably 610 nm or more, and usually 660 nm or less, especially 650 nm or less. If the emission peak wavelength λp is too short, it tends to be yellowish, whereas if it is too long, it tends to be dark reddish, which is not preferable because the characteristics as orange or red light may be deteriorated.

  In addition, the phosphor of the present invention has a full width at half maximum (hereinafter, abbreviated as “FWHM” where appropriate) in the above-described emission spectrum, which is usually larger than 1 nm, especially 2 nm or more, and more preferably 3 nm. In addition, it is preferably in the range of usually less than 50 nm, especially 30 nm or less, more preferably 10 nm or less, and even more preferably 8 nm or less. If the full width at half maximum FWHM is too narrow, the emission intensity may decrease, and if it is too wide, the color purity may decrease.

  In order to excite the phosphor with light having a peak wavelength of 455 nm, for example, a xenon light source can be used. The emission spectrum of the phosphor of the present invention can be measured by, for example, a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a 150 W xenon lamp as an excitation light source and a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus. ) Or the like. The emission peak wavelength and the half width of the emission peak can be calculated from the obtained emission spectrum.

<Quantum efficiency and absorption efficiency>
The phosphor of the present invention is more preferable as its internal quantum efficiency is higher. 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 light emission efficiency tends to decrease, which is not preferable.

  The phosphor of the present invention is more preferable as its external quantum efficiency is higher. 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 light emission efficiency tends to decrease, which is not preferable.

  The phosphor of the present invention is preferably as its absorption efficiency is high. The value is usually 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 light emission efficiency tends to decrease, which is not preferable.

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

<Weight average median diameter _{D 50>}
The phosphor of the present invention preferably has a weight median diameter D ₅₀ in the range of usually 3 μm or more, especially 10 μm or more, and usually 50 μm or less, especially 30 μm or less. When the weight-average median diameter D ₅₀ is too small, and if the luminance is lowered, there is a case where phosphor particles tend to 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, In particular, it is preferably 0.1 m ² / g or more. If the specific surface area of the phosphor is too small, the phosphor particles are large, which tends to cause coating unevenness and clogging of the dispenser, etc. If too large, the phosphor particles are small, so the contact area with the outside increases and durability It becomes inferior. 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 brightness.
The specific surface area of the phosphor in the present invention is measured by the BET one-point method, for example, using a fully automatic specific surface area measuring device (flow method) AMS1000A manufactured by Okura Riken Co., Ltd.

<Particle size distribution>
The phosphor of the present invention preferably has one peak value in the particle size distribution.
A peak value of 2 or more indicates that there are a peak value due to single particles and a peak value due to aggregates thereof. Therefore, having a peak value of 2 or more also means that single particles are very small. The phosphor of the present invention having a single particle size distribution peak value has large single particles and very few aggregates. As a result, the luminance is improved, and the specific surface area is reduced due to the large growth of single particles, thereby improving the durability.
In addition, the particle size distribution of the phosphor in the present invention can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring apparatus LA-300 manufactured by Horiba, Ltd.
Further, the peak width of the particle size distribution is preferably narrow. Specifically, the quadrature 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, Most preferably, it is 0.30 or less.
In addition, the quarter deviation of the particle size distribution becomes smaller as the particle diameters of the phosphor particles are uniform. That is, the fact that the quarter deviation of the particle size distribution is small means that the peak width of the particle size distribution is narrow and the sizes of the phosphor particles are uniform.
The quadrature deviation of the particle size distribution can be calculated using a particle size distribution curve measured using a laser diffraction / scattering particle size distribution measuring device.

<Particle shape>
The particle shape of the phosphor of the present invention recognized from the observation of the SEM photograph of the present invention is preferably a granular shape that grows uniformly in the triaxial direction. When the particle shape grows evenly in the triaxial direction, the specific surface area becomes small, and the contact area with the outside is small, so that the durability is excellent.
In addition, this SEM photograph can be image | photographed, for example by Hitachi Ltd. SEM (S-3400N).

[1-3. Method for producing phosphor]
Although there is no restriction | limiting in particular in the method of manufacturing the fluorescent substance of this invention, The method of using a poor solvent like the method of the following 1), and the method of the following 2) (specifically the following 2-1) And a method that does not use a poor solvent, such as method 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, a precipitate (phosphor) precipitated by mixing In this method, it is preferable that the solution to be mixed contains all of the elements constituting the target phosphor. Specific combinations of the solutions to be mixed include the following 2 -1) and the following 2-2).
2-1) A method of mixing a solution containing at least Si and F and 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 and a solution containing at least K (and / or Na) and F

Hereinafter, M ⁴ is a typical example of the case of Si, is described for each of the manufacturing process.

1) Poor solvent precipitation method This method uses, for example, M ¹ ₂ SiF ₆ and M ¹ ₂ RF ₆ as raw material compounds as described in Example 1-1 described later (however, M ¹ , R has the same meaning as in the above formula [1].) These are added to hydrofluoric acid at a predetermined ratio, dissolved under stirring, reacted, and then a poor solvent for the phosphor is added. Thus, the phosphor is deposited and can be performed in the same manner as the method described in US Pat. No. 3,576,756.

  As described above, the method described in US Pat. No. 3,576,756 has the problem that the obtained phosphor particles are fine, have low brightness, and are not practical. However, the present inventors have added this poor solvent. It has been found that when the phosphor is deposited, the target phosphor can be obtained by slowing the addition rate of the poor solvent or by adding the poor solvent not at once, but by adding the poor solvent.

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 is used. Etc. are preferred.
As a combination of K ₂ SiF ₆ and K ₂ MnF ₆ , specifically,
A combination of 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 MnF ₆ ,
Soluble K salt _{(KF, KHF 2, KOH,} KCl, KBr, KI, potassium _acetate, etc. K 2 CO ₃₎ and hydrofluoric acid and silicates (such as _SiO 2, Si alkoxide) and _K 2 MnF ₆ A combination of
The combination of potassium silicate and _(K 2 SiO ₃₎ and hydrofluoric acid and _K 2 MnF ₆ and the like.
As a combination of K ₂ SiF ₆ and KMnO ₄ , specifically,
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 KMnO ₄ ;
The combination of water-soluble K salt _{(KF, KHF 2, KOH,} KCl, KBr, KI, potassium _acetate, etc. K 2 CO ₃₎ and hydrofluoric acid and silicates (such as _SiO 2, Si alkoxide) and KMnO ₄ ,
The combination of potassium silicate and _(K 2 SiO ₃₎ and hydrofluoric acid and KMnO ₄ and the like.
As a combination of K ₂ SiF ₆ and K ₂ MnCl ₆ , specifically,
The combination of water-soluble K salt and _{(KF, KHF 2, KOH,} KCl, KBr, KI, potassium _acetate, K 2 CO ₃ etc.) and hydrofluoric acid and _H 2 SiF ₆ solution and _K 2 MnCl _6,
Soluble K salt _{(KF, KHF 2, KOH,} KCl, KBr, KI, potassium _acetate, etc. K 2 CO ₃₎ and hydrofluoric acid and silicates (such as _SiO 2, Si alkoxide) and _K 2 MnCl ₆ A combination of
The combination of potassium silicate and _(K 2 SiO ₃₎ and hydrofluoric acid and _K 2 MnCl ₆ may be mentioned.

  The water-soluble K salt and the water-soluble potassium salt in the methods 2-1) and 2-2) described later refer to a potassium salt having a solubility in water at 15 ° C. of 10% by weight or more.

  These raw material compounds are used in such a ratio that a phosphor having the desired composition can be obtained, but as described above, there is a slight difference between the composition of the phosphor raw material and the composition of the obtained phosphor. It is important to adjust the composition of the obtained phosphor so that it becomes 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 Used as an aqueous solution of 50% by weight or less. For example, when hydrofluoric acid having a hydrogen fluoride concentration of 40 to 50% by weight is used, 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 preferable to use as described above.

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

  Usually, a raw material compound is added to and mixed with hydrofluoric acid at a predetermined ratio, and when all of the raw material compound is dissolved, a poor solvent is added.

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

(Definition of dissolution parameters)
In the regular solution theory, the force acting between the solvent and the solute is modeled as only the intermolecular force, so it can be considered that the interaction causing the liquid molecules to aggregate is only the intermolecular force. Since the cohesive energy of the liquid is equivalent to the enthalpy of evaporation, the solubility parameter is defined as δ = √ (ΔH / V−RT) from the heat of molar evaporation ΔH and the molar volume V. That is, it is calculated from the parallel root (cal / cm ³ ) ^{1/2 of the} heat of evaporation required for evaporating 1 mol volume of liquid.
It is rare that the actual solution is a regular solution, and forces other than intermolecular forces such as hydrogen bonds also act between the solvent and solute molecules, and whether the two components mix or phase separate is a mixture of those components It is determined thermodynamically by the difference between enthalpy and mixed entropy. However, empirically, substances having similar solubility parameters (hereinafter sometimes referred to as “SP values”) tend to be mixed. Therefore, the SP value also serves as a standard for determining the ease of mixing of the solute and the solvent.
In regular solution theory, the force acting between the solvent and the solute is assumed to be only an intermolecular force, so the solubility parameter is used as a measure of the intermolecular force. Although an actual solution is not necessarily a regular solution, it is empirically known that the smaller the difference between the SP values of the two components, the greater the solubility.

  Such poor solvents include acetone (solubility parameter: 10.0), isopropanol (solubility parameter: 11.5), acetonitrile (solubility parameter: 11.9), dimethylformamide (solubility parameter: 12.0), acetic acid. (Solubility parameter: 12.6), ethanol (solubility parameter: 12.7), cresol (solubility parameter: 13.3), formic acid (solubility parameter: 13.5), ethylene glycol (solubility parameter: 14.2), Examples include phenol (solubility parameter: 14.5) and methanol (solubility parameter: 14.5 to 14.8). Among them, acetone is preferable because it does not contain a hydroxyl group (—OH) and dissolves well in water. These poor solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The amount of the poor solvent used varies depending on the type, but is usually 50% by volume or higher, preferably 60% by volume or higher, more preferably 70% by volume or higher, and usually 70% by volume with respect to the phosphor raw material-containing hydrofluoric acid. It is preferable to set it to 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 the addition rate of the poor solvent to the phosphor raw material-containing hydrofluoric acid is 400 ml / hour or less, preferably 100 to 350 ml / hour, which is a relatively slow addition rate. It is preferable to obtain a high-luminance phosphor having a small specific surface area. However, if this rate of addition is too slow, productivity is impaired.

  The phosphor deposited by the addition of the poor solvent is recovered by solid-liquid separation by filtration or the like, washed with a solvent such as ethanol, water, acetone, etc., and then usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 It is preferable to dry at a temperature of not less than 300 ° C., usually 300 ° C. or less, preferably 250 ° C. or less, more preferably 200 ° C. or less. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated. For example, the drying time is about 1 to 2 hours.

2-1) Method of precipitating product (phosphor) by mixing a solution containing at least Si and F and a solution containing at least K, Mn and F This method does not use a poor solvent Since it does not use a flammable organic solvent as a poor solvent, the safety is improved industrially; no organic solvent is used; therefore, the cost can be reduced; the same amount of phosphor is synthesized The amount of hydrofluoric acid required for the process is reduced to about 1/10 compared with the method 1), so that further cost reduction can be achieved; There is an advantage that particle growth is promoted, and a high-luminance phosphor having a small specific surface area, a large particle size, and excellent durability can be obtained.

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 the solution I may be a compound containing Si and F and has excellent solubility in the solution. 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. 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. These SiF ₆ sources may be used alone or in combination of two or more.

The hydrogen fluoride concentration of the 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. % Or less is preferable. 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. If the hydrogen fluoride concentration in the solution I is too low, Mn ions are easily hydrolyzed when a solution (solution II) containing a Mn source described later is added to the solution I, and the activated Mn concentration changes. Since the amount of Mn activation in the synthesized phosphor is difficult to control, there is a tendency that the luminous efficiency of the phosphor varies widely, and when it is too high, the risk of work tends to increase. Further, if the SiF ₆ source concentration is too low, the phosphor yield tends to decrease and the particle growth of the phosphor tends to be suppressed, and if too high, the phosphor particles tend to be too large.
Note that hydrofluoric acid can also serve as 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 a Mn source.
As the K source of the solution II, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ can be used. KHF ₂ is preferred because it can be dissolved without lowering, and because of its low heat of dissolution, it is highly safe.

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

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

The hydrogen fluoride concentration of the 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. % Or less is preferable. The concentration of the K source and Mn source is generally 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 hydrogen fluoride concentration is too low, the activation element raw material K ₂ MnF ₆ contained in the solution II is unstable and easily hydrolyzed, and the Mn concentration changes drastically. Therefore, the Mn activation in the synthesized phosphor Since it becomes difficult to control the amount, the variation in the luminous efficiency of the phosphor tends to increase, and when it is too high, the risk of work tends to increase. Further, if the K source and M source concentrations are too low, the phosphor yield tends to decrease, and the phosphor particle growth tends to be suppressed. If it is too high, the phosphor particles tend to be too large. .

  The mixing method of the solution I and the solution II is not particularly limited, and the solution II may be added and mixed while stirring the solution I, or the solution I may be added and mixed while stirring the solution II. good. Alternatively, the solution I and the solution II may be put into a container at a 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 the target phosphor crystal. 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 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more It is preferable to dry at 200 ° C. or lower. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated. For example, the drying time is about 1 to 2 hours.

  In mixing the solution I and the solution II, the composition of the phosphor as a product is changed to the target composition in consideration of the difference between the preparation composition of the phosphor raw material and the composition of the obtained phosphor. Therefore, it is necessary to adjust the mixing ratio of the solution I and the solution II.

2-2) A method of precipitating a product (phosphor) by mixing a solution containing at least Si, Mn, and F and a solution containing at least K (and / or Na) and F
This method is also characterized in that a poor solvent is not used, and has the same advantages as the above method 2-1).
Furthermore, according to the method 2-2), K ₂ MnF ₆ is dissolved in the solution, so that Mn can be activated more uniformly than the method 2-1). Therefore, since the Mn concentration actually activated with respect to the charged composition of the Mn concentration is controlled linearly, there is an advantage that quality control is easily performed industrially.

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 a Mn source.
The SiF ₆ source of the solution III may be a compound containing Si and F and has excellent solubility in the solution. H ₂ SiF ₆ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ Rb ₂ SiF ₆ , Cs ₂ SiF ₆ or the like can be used. Of these, H ₂ SiF ₆ is preferred because of its high solubility in water and the absence of alkali metal elements as impurities. These SiF ₆ sources may be used alone or in combination of two or more.

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 these, hydrofluoric acid is used as MnF ₆ complex ion while maintaining the oxidation number (tetravalent) that can be activated because it does not contain Cl element that tends to distort and destabilize the crystal lattice. K ₂ MnF ₆ is preferred because it can be stably present therein. Of the Mn sources, those containing K also serve as the K source. One type of Mn source may be used alone, or two or more types may be used in combination.

The hydrogen fluoride concentration of the 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 hydrogen fluoride concentration in the solution III is too low, Mn ions are easily hydrolyzed, the activated Mn concentration changes, and the amount of Mn activation in the synthesized phosphor becomes difficult to control. The variation in the luminous efficiency of the phosphor tends to increase. On the other hand, when the concentration of hydrogen fluoride is too high, the risk of work tends to increase. Further, if the SiF ₆ source concentration is too low, the phosphor yield tends to decrease and the particle growth of the phosphor tends to be suppressed, and if too high, the phosphor particles tend to be too large. Moreover, when the Mn source concentration is too low, the yield of the phosphor tends to decrease, and the particle growth of the phosphor tends to be suppressed. When the concentration 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 the solution IV, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO ₃ can be used. Among these, KHF ₂ is preferable because it can be dissolved without lowering the concentration of hydrogen fluoride in the solution, and has high safety because of its low heat of dissolution. K source may be used individually by 1 type, and may use 2 or more types together.

The hydrogen fluoride concentration of the 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. % Or less is preferable. 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. It is preferable that If the hydrogen fluoride concentration is too low, when added to the solution III, for example, the raw material K ₂ MnF ₆ of the activation element contained in the solution III becomes unstable and easily hydrolyzed, and the Mn concentration changes drastically. Since the amount of Mn activation in the synthesized phosphor is difficult to control, there is a tendency that the luminous efficiency of the phosphor varies widely, and when it is too high, the risk of work tends to increase. Moreover, when the K source concentration is too low, the yield of the phosphor tends to decrease and the particle growth of the phosphor tends to be suppressed. When the concentration is too high, the phosphor particles tend to be too large.

  The mixing method of the solution III and the solution IV is not particularly limited, and the solution IV may be added and mixed while stirring the solution III, or the solution III may be added and mixed while stirring the solution IV. good. Alternatively, the solution III and the solution IV may be put into a container at a time and stirred and mixed.

By mixing the solution III and the solution IV, the SiF ₆ source, the Mn source, and the K source react with each other at a predetermined ratio to precipitate the target phosphor crystal. 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 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more It is preferable to dry at 200 ° C. or lower. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated. For example, the drying time is about 1 to 2 hours.

  In mixing the solution III and the solution IV, the composition of the phosphor as a product is changed to the target composition in consideration of the difference between the preparation composition of the phosphor raw material and the composition of the obtained phosphor. Therefore, it is necessary to adjust the mixing ratio of the solution III and the solution IV.

[1-4. Use of phosphor]
The phosphor of the present invention can be used for any application using the phosphor. In addition, the phosphor of the present invention can be used alone, but two or more of the phosphors of the present invention can be used together, or the phosphor of the present invention and other phosphors It is also possible to use as a phosphor mixture of any combination.

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

  The emission color of the light-emitting device is not limited to white, and by appropriately selecting the combination and content of phosphors, a light-emitting device that emits light in any color such as light bulb color (warm white) or pastel color is manufactured. can do. The light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.

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

[2-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention, It can select arbitrarily from what was mentioned above. Moreover, the fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, 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 within the intended range. For example, any inorganic material and / or organic material may be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause an undesirable reaction. it can.

  As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof, an inorganic material (for example, siloxane) And inorganic materials having a bond).

  Examples of organic materials include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

  Among the inorganic materials and organic materials described above, it is preferable to use a silicon-containing compound for the purpose of heat resistance, light resistance, etc., particularly when a phosphor is used for a high-power light emitting device such as illumination.

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

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

  As the condensed silicone material, for example, semiconductor light-emitting device members described in JP-A-2007-112973 to 112975, JP-A-2007-19459, JP-A-2008-34833, and the like can be used. Condensation-type silicone materials have excellent adhesion to components such as packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.

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

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

  As the photocurable silicone material, for example, silicone materials described in JP 2007-131812 A, JP 2007-214543 A, and the like can be suitably used. The photo-curing type silicone material has advantages such as excellent productivity because it is cured in a short time, and it is not necessary to apply a high temperature for curing, and the light-emitting element is hardly deteriorated.

  These silicone materials may be used alone, or a mixture of a plurality of silicone materials may be used if curing inhibition does not occur when mixed.

[2-3. Content ratio of liquid medium and phosphor]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 25% by weight or more, preferably 40% by weight or more, based on the entire phosphor-containing composition of the present invention. The amount is usually 99% by weight or less, preferably 95% by weight or less, more preferably 80% by weight or less. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, when there is too little liquid medium, fluidity | liquidity may fall and it may become difficult to handle.

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

  The content of the phosphor in the phosphor-containing composition of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 1% by weight or more with respect to the entire phosphor-containing composition of the present invention, It is preferably 3% by weight or more, more preferably 5% by weight or more, further 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. The proportion of the phosphor of the present invention in the phosphor in the phosphor-containing composition is also arbitrary, but is usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less. If the phosphor content in the phosphor-containing composition is too high, the flowability of the phosphor-containing composition may be inferior and difficult to handle, and if the phosphor content is too low, the light emission efficiency of the light-emitting device decreases. There is a tendency.

[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 are used unless the effects of the present invention are significantly impaired. Further, additives such as a viscosity modifier and an ultraviolet absorber may be contained. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

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

  As the phosphor of the present invention, a phosphor that emits fluorescence in the red region under irradiation of light from an excitation light source (hereinafter sometimes referred to as “the red phosphor of the present invention”) is usually used. The red phosphor of the present invention preferably has an emission peak in a wavelength range of 600 nm or more and 660 nm or less. Any one of the red phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.

  By using the red phosphor of the present invention, the light emitting device of the present invention exhibits high luminous efficiency with respect to an excitation light source (first light emitter) having light emission in the blue region. When used in a white light emitting device such as a display light source, the light emitting device is excellent.

  Moreover, as a preferable specific example of the red phosphor of the present invention used in the light emitting device of the present invention, [1. Examples thereof include the phosphor of the present invention described in the “Phosphor” column and the phosphors used in the respective Examples in the “Example” column described later.

  The light-emitting device of the present invention has a first light emitter (excitation light source), and at least the phosphor of the present invention is used as the second light emitter. It is possible to arbitrarily adopt the apparatus configuration. A specific example of the device configuration will be described later.

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

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

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

[3-1. Configuration of Light Emitting Device (Light Emitter)]
<3-1-1. First luminous body>
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

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

  As a specific numerical value of the emission peak wavelength of the first illuminant, 200 nm or more is usually desirable. Among these, when blue light is used as excitation light, 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 luminescent material having the same. On the other hand, when near-ultraviolet light is used as excitation light, the phosphor of the present invention is excited by blue light from a phosphor that emits blue light when excited by near-ultraviolet light. It is preferable to select excitation light (near ultraviolet light) having a wavelength suitable for the band. Specifically, it is desirable to use a luminescent material having an emission peak wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 410 nm or less, more preferably 400 nm or less. .

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

Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. As the GaN-based LED and LD, those having an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer are preferable. Among them, since the emission intensity is very high, the GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and more preferably a multiple quantum well structure having an In _X Ga _Y N layer and a GaN layer. preferable.

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

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

<3-1-2. Second luminous body>
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and contains the first phosphor including the red phosphor of the present invention. In addition, a second fluorescent material (a blue fluorescent material, a green fluorescent material, a yellow fluorescent material, an orange fluorescent material, etc.), which will be described later, is appropriately contained in accordance with the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

  There is no restriction | limiting in particular in the composition of fluorescent substance other than the fluorescent substance of this invention used in the said 2nd light-emitting body. Specific examples of preferred crystal matrixes are shown in the following table.

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

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

<3-1-2-1. First phosphor>
The 2nd light-emitting body in the light-emitting device of this invention contains the 1st fluorescent substance containing the fluorescent substance of the above-mentioned this invention at least. Any one of the phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.
In addition to the phosphor of the present invention, other types of phosphors that emit the same color fluorescence as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor.

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

Any orange or red phosphor that can be used in combination with the phosphor of the present invention can be used as long as the effects of the present invention are not significantly impaired.
At this time, the emission peak wavelength of the orange to red phosphor, which is the same color combination phosphor, is usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm. It is preferable to be in the following wavelength range.

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

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

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

<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 first phosphor described above, depending on the application. The second phosphor is one or more phosphors having different emission peak wavelengths from the first phosphor. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used. As described above, since a red phosphor is usually used as the first phosphor, examples of the second phosphor include phosphors other than the red phosphor such as a blue phosphor, a green phosphor, and a yellow phosphor. Is used.

Second phosphor weight-average median diameter D ₅₀ of which is used for the light emitting device of the present invention is usually 2μm or more and preferably 5μm or more, and usually 30μm or less is preferably in a range of inter alia 25μm or less. When the weight-average median diameter D ₅₀ is too small, and the luminance decreases tends to phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

(Blue phosphor)
When a blue phosphor is used 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, and further preferably 460 nm or less. It is preferable to be in the wavelength range. When the emission peak wavelength of the blue phosphor used is within this range, it overlaps with the excitation band of the phosphor of the present invention, and the phosphor of the present invention can be efficiently excited by the blue light from the blue phosphor. Because.

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

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

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

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

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

More in even, as the yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, Sr) Si ₂ N ₂ O ₂ : Eu is preferred.

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

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

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

Among these, as the green phosphor, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn is preferred.
When the obtained light-emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : 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 are preferable.
When the obtained light emitting device is used for an image display device, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, _{sr) 3 Si 6 O 12:} N 2: Eu, SrGa 2 S 4: Eu, BaMgAl 10 O 17: Eu, Mn are preferable.

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

<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 between the first phosphor and the second phosphor is also arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, the usage amount of the second phosphor, the combination and ratio of the phosphors used as the second phosphor, and the like may be arbitrarily set according to the use of the light emitting device.

For example, when the light emitting device of the present invention is configured as a red light emitting device, only the first phosphor (red phosphor) may be used, and the use of the second phosphor is usually unnecessary. .
On the other hand, when the light emitting device of the present invention is configured as a white light emitting device, the first light emitter, the first phosphor (red phosphor), and the first phosphor so as to obtain desired white light. The two phosphors may be combined appropriately. Specifically, examples of preferable combinations of the first light emitter, the first phosphor, and the second phosphor in the case where the light emitting device of the present invention is configured as a white light emitting device include the following: (A) to (C) are included.

(A) 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 green fluorescence is used as the second phosphor. Body or yellow phosphor. Examples of the green phosphor include (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, CaSc ₂ O ₄ : Ce phosphor, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce phosphor, and 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 represents an alkaline earth metal element), and one or more green phosphors selected from the group consisting of: 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, and α-sialon phosphor More than one kind of yellow phosphor is preferred. A green phosphor and a yellow phosphor may be used in combination.

(B) A near ultraviolet or ultraviolet light emitter (near ultraviolet or ultraviolet LED or the like) 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. As the phosphor, a blue phosphor and a green phosphor are used in combination. In this case, BaMgAl ₁₀ O ₁₇ : Eu and / or (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu are preferable as the blue phosphor. Further, as the 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 phosphor, SrGa ₂ S ₄ : Eu phosphor, Eu-activated β-sialon 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 : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : One or more green phosphors selected from the group consisting of Eu are preferred. Among these, since the color reproduction range of the display can be dramatically improved, it is preferable to use phosphors having a narrow emission peak half-value width for all three types of red, blue, and green. And (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 in combination with Mn.

(C) A blue phosphor (blue LED or the like) is used as the first phosphor, a red phosphor (such as the phosphor of the present invention) is used as the first phosphor, and 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 need to be mixed with each other, but means that different types of phosphors are combined). ) Can be used. In particular, when phosphors are mixed in the combination described above, a preferable phosphor mixture is obtained. In addition, there is no restriction | limiting in particular in the kind of fluorescent substance to mix, and its ratio.

  Hereinafter, a suitable combination of the first light emitter, the first phosphor, and the second phosphor will be described more specifically according to the use of the light emitting device.

  Of these, the following combinations are more preferable.

  Of 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 used by being dispersed in a liquid medium which is a sealing material (binder).
Examples of the liquid medium include [4. Examples thereof are the same as those described in the section “Fluorescent substance-containing composition”.

  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 metal elements that give a metal oxide having a high refractive index include Si, Al, Zr, Ti, Y, Nb, and B. These metal elements may be used alone or in combination of two or more in any combination and ratio.

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

[3-3. Configuration of light emitting device (others)]
The other configurations of the light emitting device of the present invention are not particularly limited as long as the first light emitting body and the second light emitting body described above are provided. Usually, the first light emitting body described above is formed on an appropriate frame. And a second light emitter. At this time, the second light emitter is excited by the light emission of the first light emitter (that is, the first and second phosphors are excited) to emit light, and the first light emitter emits light. And / or it arrange | positions so that light emission of a 2nd light-emitting body may be taken out outside. In this case, the first phosphor and the second phosphor are not necessarily mixed in the same layer. For example, the second phosphor is contained on the layer containing the first phosphor. For example, the phosphor may be contained in a separate layer for each color development of the phosphor, such as by stacking layers.

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

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

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

  As the two or more kinds of phosphors, specific blue phosphors and green phosphors that are excited by light emission from the phosphor of the present invention and 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 backlight light source for the image display device, Table 6A, Table 6B, Table 7A, Table 7B, and Table 8 show “use of backlight for image display device”. Can be mentioned.

  In the case of using a sealing material for the light emitting device, it is preferable to use the above-mentioned silicone-based material from the viewpoints of the deterioration resistance to the emission wavelength from the ultraviolet region to the blue region and the heat resistance. More preferably, a system material is used.

  Furthermore, an image display with high color purity can be realized by combining a color filter optimal for the emission wavelength of the light emitting device. That is, the light-emitting device is a light source that combines blue, green, and red light emission with a narrow band, high light emission intensity, and excellent temperature characteristics. By using the semiconductor light emitting element of the power device, an excellent image display device with stable light emission intensity and little color shift can be obtained.

[3-4. Embodiment of Light Emitting Device]
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

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

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

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

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

[3-5. Application of light emitting device]
The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, the illumination device is particularly preferable. And as a light source for image display devices.

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

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

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

<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, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Measurement method of physical properties]
The physical property values of the phosphors obtained in Examples and Comparative Examples described later were measured and calculated by the following methods.

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

<Luminance>
The relative luminance is a range obtained by removing the excitation wavelength range from the emission spectrum in the visible range obtained by the above-described method, and similarly, from the stimulus value Y calculated in accordance with JIS Z8724 in the XYZ color system, excitation at a wavelength of 455 nm. Stimulus obtained in the same manner as the emission spectrum obtained by exciting the yellow phosphor Y ₃ Al ₅ O ₁₂ : Ce (product number: P46-Y3) manufactured by Kasei Optonics Co., Ltd. with light. The value Y was calculated as a relative value (hereinafter, sometimes simply referred to as “luminance”) with 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 with a laser diffraction / scattering particle size distribution measuring apparatus LA-300 manufactured by Horiba. Before measurement, use ethanol as the dispersion solvent, disperse the phosphor, adjust the initial transmittance on the optical axis to about 90%, and influence the aggregation while stirring the dispersion solvent with a magnet rotor. Measurements were taken with a minimum.
The weight-average median diameter D ₅₀ was determined as described above, the integrated value of the particle size distribution (corresponding to a weight-based particle size distribution curve.) Was calculated as the particle size value when the 50%.

<Quarter deviation (QD) of particle size distribution>
The quadrature deviation (QD) of the particle size distribution is obtained by using the following equation when the measured particle size distribution is 25% and 75% and the particle size values are weight median diameters D ₂₅ and D _75. Calculated.
QD = | D ₇₅ -D ₂₅ | / | D ₇₅ + D ₂₅ |

{Phosphor particle shape}
<Scanning electron microscope (SEM) photograph>
In order to observe the shape of phosphor particles, etc., in each example and comparative example, SEM (manufactured by Hitachi, S-3400N) was used 1000 times (Example 1-2, Example 1-9), 5000. SEM photographs were taken at double magnification (Example 1-1, Comparative Example 1-1) or 2000 times (Example 1-16 to Example 1-19).

<Specific surface area>
The specific surface area was measured by a nitrogen adsorption BET one-point method using a fully automatic specific surface area measuring device (flow method) AMS1000A manufactured by Okura Riken Co., Ltd.

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

{Quantum efficiency}
<Absorption efficiency α _q , internal quantum efficiency η _i , and external quantum efficiency η _o >
When obtaining the quantum efficiency (absorption efficiency α _q , internal quantum efficiency η _i and external quantum efficiency η _o ), first, the measurement accuracy of the phosphor sample (for example, phosphor powder) to be measured is maintained. Then, the surface was sufficiently smoothed and packed in a cell, and attached to a condenser such as an integrating sphere.

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

  The phosphor sample to be measured was irradiated with light from the light emission source whose emission peak wavelength was adjusted, and a spectrum including light emission (fluorescence) and reflected light was measured with a spectrometer (MCPD7000 manufactured by Otsuka Electronics Co., Ltd.). .

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

First, the total photon number N of the latter excitation light was obtained as follows.
That is, a white reflector such as a “Spectralon” manufactured by Labsphere (having a reflectivity R of 98% for 455 nm excitation light) such as a material having a reflectivity R of almost 100% with respect to the excitation light is measured. The sample was 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 obtained. In addition, the integration interval of the following (Formula I) was 435 nm-465 nm. The numerical value represented by the following (formula I) is proportional to the total photon number N of the excitation light.

Moreover, the numerical value represented by the following (formula II) was calculated | required from the reflection spectrum I ((lambda)) when the fluorescent substance sample used as the measuring object of absorption efficiency (alpha) _q was attached to the condensing apparatus. Note that the integration interval in the above (formula II) is the same as the integration interval defined in the above (formula I). The numerical value obtained by the following (formula II) is proportional to the number of photons _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 η _i >
The internal quantum efficiency η _i was calculated as a value obtained by dividing the number of photons N _PL derived from the fluorescence phenomenon by the number of photons N _abs absorbed by the phosphor sample.

A numerical value represented by the following formula (III) was determined from the above I (λ). Note that the lower limit of the integration interval of (Formula III) was 466 nm to 780 nm. Figures are calculated by the following (Formula III) is proportional to the number N _PL of photons originating from the fluorescence phenomenon.

From the above, the internal quantum efficiency η _i was 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 obtained by the above procedure and the internal quantum efficiency η _i .

{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.
Using CuKα tube X-ray output = 45 kV, 40 mA
Divergence slit = automatic, irradiation width 10mm x 10mm
Detector = Semiconductor array detector X'Celerator used, Cu filter used Scanning range 2θ = 10 to 65 degrees Reading width = 0.0167 degrees Counting time = 10 seconds

[Raw materials]
The raw materials used in Examples and Comparative Examples described below 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 dissolved in this solution. While the solution was stirred, hydrogen peroxide solution was added dropwise to obtain a yellow precipitate when the molar ratio of KMnO ₄ and H ₂ O ₂ reached 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.

[Examples and Comparative Examples for Production of Phosphor (K ₂ SiF ₆ : Mn)]
<Example 1-1>
K ₂ SiF ₆ (1.77783 g) and K ₂ MnF ₆ (0.2217 g) are used as the raw material compounds so that the raw material composition of each phosphor becomes K ₂ Si _0.9 Mn _0.1 F _6. Under atmospheric pressure and room temperature, it was dissolved in 70 ml of hydrofluoric acid (47.3% by weight) with stirring. After all the raw material compounds were 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. Each of the obtained phosphors was washed with ethanol and dried at 130 ° C. for 1 hour to obtain 1.7 g of the phosphor.

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

  Moreover, the excitation spectrum and emission spectrum of the obtained phosphor are shown in FIG. From the excitation spectrum, the excitation peak is in the range of 450 to 460 nm, and it can be seen that the excitation light from the blue LED chip can be efficiently absorbed. Further, as the emission peak of the phosphor obtained in this example, the main emission peak wavelength is 631 nm, and a narrow narrow band red with a half-value width of 6 nm is shown. Therefore, the fluorescent characteristic suitable for the purpose of the present invention is obtained. 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 wt%). While stirring this solution at 26 ° C., it was added to a mixed solution of 10 ml of 33 wt% H ₂ SiF ₆ aqueous solution and 10 ml of hydrofluoric acid (47.3% wt) to precipitate yellow crystals. The obtained crystals were designated as No. 1 After filtering with 5C 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.

From the X-ray diffraction pattern of the obtained phosphor, it was confirmed 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 a solution was prepared by adding it to a mixed solution of 10 ml of 33 wt% H ₂ SiF ₆ aqueous solution and 40 ml of hydrofluoric acid (47.3% wt). . While this solution was stirred at 26 ° C., hydrofluoric acid in which KHF ₂ was dissolved was added to this solution to precipitate yellow crystals. The obtained crystals were designated as No. 1 After filtering with 5C 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 phosphor.

<Comparative Example 1-1>
A phosphor was obtained in the same manner as in Example 1-1 except that acetone, which was a poor solvent, was added all at once.
From the X-ray diffraction pattern of the obtained phosphor, it was confirmed 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>
For the phosphors obtained in Examples 1-1, 1-2, 1-9 and Comparative Example 1-1, the Mn concentration obtained by the composition analysis by SEM-EDX (“analysis Mn concentration (mol) in Table 10” %) ". The same applies hereinafter.) The luminance (relative value when P46Y3 is 100), the absorption efficiency, the internal quantum efficiency, and the external quantum efficiency are determined from the emission spectrum obtained by excitation with light having a wavelength of 455 nm. Table 10 shows.
Further, Table 11 shows the weight median diameter D ₅₀ and the quadrature deviation (QD) of the particle size distribution obtained from the specific surface area measurement result and the particle size distribution measurement.
Further, the particle size distribution curves are shown in FIGS. 6A and 6B, and the SEM photographs are shown in FIGS. 7A and 7B, respectively.

From the above results, the following can be understood.
In Example 1-1, although the deposition rate due to the addition of the poor solvent was made slower than that in Comparative Example 1-1, the concentration of Mn, which is an activating element (analytical Mn concentration in Table 10), was reduced. The brightness is high. It is considered that this is because the internal quantum efficiency is increased as a result of the uniform activation of Mn ions by controlling the deposition rate.
In addition, from the particle size distribution curves of FIGS. 6A and 6B, the phosphor of Comparative Example 1-1 has a double distribution, and it is considered that small particles are aggregated, whereas Example 1-1. As compared with the phosphor of Comparative Example 1-1, a large number of large particles can be synthesized, and since there are few small particles, there is no aggregation, 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 have a small contact area with the outside, so that the durability is considered to be improved.
Moreover, about the quarter deviation of a particle size distribution, the value is small in 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 quadrant deviation, the narrower the peak width of the particle size distribution, that is, 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, it is considered that the luminance is increased as a result of the significant increase in absorption efficiency.
Further, in the phosphors obtained in Example 1-2 and Example 1-9, many tetrahedral hexahedral particles are observed in terms of morphology (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. Therefore, it is considered that the durability is also improved.

<Examples 1-3 to 1-6>
A phosphor was obtained in the same manner as in Example 1-1 except that the charged concentration of Mn was changed as described in Table 12.
Analytical Mn concentration of the obtained phosphor, luminance (relative value when P46Y3 is 100), absorption efficiency, internal quantum efficiency and external quantum efficiency obtained from an emission spectrum obtained by excitation with light having a wavelength of 455 nm And the quadrature 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 charged concentration of Mn was changed as described in Table 12.
Analytical Mn concentration of the obtained phosphor, luminance (relative value when P46Y3 is 100), absorption efficiency, internal quantum efficiency and external quantum efficiency obtained from an emission spectrum obtained by excitation with light having a wavelength of 455 nm And the quadrature deviation (QD) of the particle size distribution are shown in Table 12 together with the results of Examples 1-2 and 1-9.

  From Table 12, in the synthesis by 1) the poor solvent precipitation method represented by Examples 1-1, 1-3, 1-4, 1-5, and 1-6, the charged Mn concentration was 10 mol%. It is found that the concentration is 15 mol% or less and the concentration in the crystal, that is, the analytical Mn concentration is preferably 2 mol% or more and 4 mol% or less. Also, 2-1) a solution containing at least Si and F, and a solution containing at least K, Mn and F, as represented by Examples 1-2, 1-7 and 1-8 In the synthesis by the mixing method, the charged Mn concentration is 5 mol% or more and 15 mol% or less, and the concentration existing in the crystal, that is, the analytical Mn concentration is preferably 3 mol% or more and 5 mol% or less. 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 at least a solution containing KF, the charged Mn concentration is 3 mol% or more and 10 mol% or less, and the concentration existing in the crystal, that is, the analytical Mn concentration is 2 mol% or more and 6 mol% or less. It turns out that it is preferable that it is below mol%.

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

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

<Examples 1-16 to 1-19>
4.9367 g of KHF ₂ was weighed and added to 45 ml of hydrofluoric acid (47.3 wt%) and 5 ml of pure water to dissolve (solution III: hydrofluoric acid concentration 43 wt%).
On the other hand, 4.3392 g of K ₂ MnF ₆ was weighed and added to a mixed solution of 50 ml of 33 wt% H ₂ SiF ₆ aqueous solution and 200 ml of hydrofluoric acid (47.3 wt%) to prepare a solution. (Solution IV). While the solution IV was stirred at 26 ° C., the hydrofluoric acid solution III in which the KHF ₂ was dissolved was added to the solution IV to precipitate yellow crystals. The obtained crystals were designated as No. 1 After filtering with 5C 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 amount charged was changed.

Analysis of the obtained phosphors (both charged Mn concentration is 10 mol%) Mn concentration, luminance determined from emission spectrum obtained by excitation with light having a wavelength of 455 nm (relative value when P46Y3 is 100) Table 15 shows the absorption efficiency, internal quantum efficiency and external quantum efficiency, and the specific surface area, weight median diameter D ₅₀ , and quadrature deviation (QD) of the particle size distribution.
Further, 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 charged Mn concentration was 10 mol% as in Example 1-9, but the hydrofluoric acid concentration in Solution III was 47% by weight of Example 1-9. To 43 wt% (Example 1-16), 41 wt% (Example 1-17), 39 wt% (Example 1-18), or 35 wt% (Example 1-19) From these results, it can be seen that the hydrofluoric acid concentration of the solution III is particularly preferably 35% by weight to 45% by weight.
Also, from the results of Examples 1-16 to 1-19, it can be seen that the smaller the specific surface area, the higher the absorption efficiency and the higher the luminance.
The phosphors obtained in Examples 1-16 to 1-19 all had an emission peak wavelength of 630 nm and an emission peak half width of 6 nm.

[Examples and Comparative Examples of Semiconductor Light-Emitting Device]
<Example 2-1>
350 μm manufactured by Showa Denko KK as a blue light emitting diode (hereinafter, abbreviated as “LED” as appropriate) that emits light having a dominant emission wavelength of 455 nm to 465 nm (emission peak wavelength of 451 nm to 455 nm) and a half width of the emission peak of 22 nm to 28 nm. A square chip GU35R460T was used and adhered to the terminal at the bottom of the recess of the 3528 SMD type PPA resin package with a transparent die bond paste based on silicone resin. Then, after heating at 150 degreeC for 2 hours and hardening a transparent die-bonding paste, blue LED and the electrode of the package were wire-bonded using the gold wire with a diameter of 25 micrometers.

On the other hand, a green phosphor Ba _1.36 Sr _0.49 Eu _0.15 SiO ₄ having an emission peak wavelength of 528 nm and an emission peak half-value width of 68 nm manufactured in Synthesis Example 2 of the phosphor described later (in Table 16, “BSS” 0.051 g), 0.189 g of red phosphor synthesized in Example 1-1 having an emission peak wavelength of 631 nm and an emission peak half width of 6 nm (indicated as “KSF” in Table 16), Toray Dow Corning's silicone resin (JCR6101up) 0.880g and Nippon Aerosil's Aerosil (RX200) 0.026g are weighed and mixed in a stirring deaerator AR-100 manufactured by Sinky Corporation. Obtained.

  Next, 4 μl of the phosphor-containing composition obtained as described above using a dispenser was injected into the concave portion of the SMD type resin package in which the blue LED was installed. 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 emitted light was measured and found to be x / y = 0.319 / 0.327. The obtained emission spectrum is shown in FIG. The white luminous flux from the semiconductor light emitting device with respect to the light output from the blue LED was 236 lumen / W.

  When this semiconductor light emitting device is used as a liquid crystal backlight, a chromaticity (x, y, Y) is used for a color image display device obtained by combining this with an optimized color filter obtained in Production Example 1 described later. ) (0.321, 0.341, 27.3), and color reproducibility (NTSC ratio) and color tone (color temperature) were determined to be NTSC ratio 95 and color temperature 5999K, respectively. Here, the Y value in chromaticity (x, y, Y) corresponds to the utilization efficiency of light emitted 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, a known CaAlSiN ₃ : Eu is used. It was possible to obtain a higher NTSC ratio than the semiconductor light emitting device of Comparative Example 2-1 described later obtained by use.

  Note that the emission spectrum of the semiconductor light emitting device was energized at 20 mA using a color / illuminance measurement software manufactured by Ocean Optics and a USB2000 series spectroscope (integral sphere specification) in a room maintained at a temperature of 25 ± 1 ° C. Measurements were made. Chromaticity values (x, y, z) were calculated as chromaticity coordinates in the XYZ color system defined by JIS Z8701 from the data in the wavelength region of 380 nm to 780 nm of this emission spectrum (in this case, x + y + z = 1). In the present specification, the XYZ color system may be referred to as an XY color system, and is usually expressed as (x, y). Luminous efficiency (lm / W) was also calculated from the obtained emission spectrum. Moreover, the emission peak wavelength and the half value width of the phosphors used in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 were also measured using the above-described apparatus.

<Comparative Example 2-1>
In the production 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 (indicated as “BSS” in Table 16) and Mitsubishi Chemical Corporation ) Manufactured by Shin-Etsu Chemical Co., Ltd., 0.010 g of red phosphor “BR-101A” (CaAlSiN ₃ : Eu, indicated as “CASN” in Table 16) having an emission peak wavelength of 650 nm and an emission peak half width of 92 nm A semiconductor light emitting device of Comparative Example 2-1 was obtained in the same manner as in 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 emitted light was measured and found to be x / y = 0.512 / 0.319. The obtained emission spectrum is shown in FIG. The white luminous flux from the semiconductor light emitting device with respect to the light output from the blue LED was 234 lumen / W.

  When this semiconductor light emitting device is used as a liquid crystal backlight, a color image display device obtained by combining this with an optimized color filter obtained in Production Example 1 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 5611K, respectively.

<Example 2-2>
As a near-ultraviolet LED that emits light with a dominant emission wavelength of 390 to 400 nm, a 290 μm square chip C395MB290 manufactured by Cree was used, and this was bonded to a terminal at the bottom of a recess of a 3528 SMD type PPA resin package with a silicone resin-based transparent die bond paste. . Then, after heating at 150 degreeC for 2 hours and hardening a transparent die-bonding paste, near ultraviolet LED and the electrode of the package were wire-bonded using the gold wire with a diameter of 25 micrometers.

On the other hand, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu (expressed as “SCA” in Table 16) 0.038 g having an emission peak wavelength of 450 nm and an emission peak half-value width of 29 nm produced in Synthesis Example 3 of phosphor described later 0.083 g of BaMgAl ₁₀ O ₁₇ : Eu, Mn (expressed as “GBAM” in Table 16) having an emission peak wavelength of 517 nm and an emission peak half-value width of 27 nm manufactured in Synthesis Example 4 of phosphor described later, 0.407 g of the red phosphor synthesized in Example 1-1 of the phosphor (referred to as “KSF” in Table 16) and 0.634 g of Toray Dow Corning silicone resin (JCR6101up) were weighed, The mixture was mixed with a stirring deaerator AR-100 manufactured by Shinky Corporation to obtain a phosphor-containing composition.

  Next, 4 μl of the phosphor-containing composition obtained as described above using a dispenser was injected into the concave portion of the SMD type resin package in which the near ultraviolet LED was installed. 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 emitted light was measured and found 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 with respect to the light output from the near ultraviolet LED was 230 lumen / W.

Although the semiconductor light emitting device has substantially the same chromaticity coordinate value, the semiconductor light emitting device of this example obtained by using the red phosphor of the present invention obtained in Example 1-1 has the emission peak wavelength. A luminous flux per unit incident light energy significantly higher than that of the semiconductor light emitting device of Comparative Example 2-2 described later obtained by using CaAlSiN ₃ : Eu having a good color purity of 660 nm could be obtained.

  Further, when this semiconductor light emitting device is a liquid crystal backlight, a color image display device obtained by combining this with an optimized color filter obtained in Production Example 1 described later has chromaticity (x, y Y) was determined to be (0.346, 0.374, 28.3), and color reproducibility (NTSC ratio) and color tone (color temperature) were determined to be NTSC ratio 116 and color temperature 5021K, respectively. .

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

<Example 2-3 and Comparative Examples 2-2 and 2-3>
In the production of the semiconductor light emitting device of Example 2-2, the same operation as in Example 2-2 was performed except that the type and amount of the phosphor used and the amount of the silicone resin were changed as shown in Table 16. 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 luminescence peak wavelength of 455 mm and a luminescence peak half-value width of 51 nm manufactured in Synthesis Example 5 of phosphor described later is used as a blue phosphor. MgAl ₁₀ O ₁₇ (shown as “BAM” in Table 16) was used. In addition, as the red phosphors of Comparative Examples 2-2 and 2-3, the red phosphor “BR-101B” (CaAlSiN ₃ : Eu, manufactured by Mitsubishi Chemical Corporation) having an emission peak wavelength of 660 nm is shown in Table 16. "CASN660") was used.

  The near-ultraviolet LED of the obtained semiconductor light-emitting device was driven by applying a current of 20 mA to emit light. When the CIE chromaticity coordinate value of the luminescence was measured, the values shown in Table 17 were obtained. In addition, emission spectra of the semiconductor light emitting devices obtained in Example 2-3, Comparative Example 2-2, and Comparative Example 2-3 are shown in FIGS. 11, 12, and 13, respectively.

Further, when this semiconductor light emitting device is a liquid crystal backlight, the chromaticity (x, 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 shown in Table 17.

[Synthesis method of phosphor]
The phosphors used in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 described above were 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 may also, at a purity of 99.9% or more, _{the weight-average} median diameter _{D 50} is 0.01μm or more, in the range below 5 [mu] m.
These phosphor raw materials were weighed so that the composition of the obtained phosphor was Ba _1.36 Sr _0.49 Eu _0.15 SiO ₄ .

These phosphor raw material powders were mixed in an automatic mortar until sufficiently uniform, filled in an alumina crucible, and fired at 1000 ° C. for 12 hours in a nitrogen atmosphere under atmospheric pressure.
Next, the contents of the crucible were taken out, 0.1 mol of SrCl ₂ and 0.1 mol of CsCl were added as flux with respect to 1 mol of the phosphor, and mixed and ground by a dry ball mill.
The obtained mixed pulverized product was again filled into an alumina crucible, and solid carbon (block shape) 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 was reached. After repeating this operation again, firing was performed by heating at 1200 ° C. for 4 hours under atmospheric pressure under flowing hydrogen-containing nitrogen gas (nitrogen: hydrogen = 96: 4 (volume ratio)).
After the obtained fired product is crushed by a ball mill, coarse particles are removed through a sieve while in a slurry state, then washed with water, rinsed with water, washed away with fine particles, dried, and sieved to break up the agglomerated particles. The phosphor (BSS) was manufactured by passing through.
The obtained green phosphor (BSS) had an emission peak wavelength of 528 nm and an emission peak half width of 68 nm.

<Synthesis Example 3>
SrCO ₃ (Kanto Chemical Co., Ltd.) 0.2 mol, SrHPO ₄ (Kanto Chemical Co., Ltd.) 0.605 mol, Eu ₂ O ₃ (Shin-Etsu Chemical 99.99% purity) 0.050 mol, SrCl ₂ (Kanto Chemical Co., Ltd.) 0.1 mol was weighed and dry mixed with a small V-type blender.
The obtained raw material mixture was filled in an alumina crucible and set in a box-type electric furnace. In the atmosphere, under atmospheric pressure, the temperature was raised to 1050 ° C. at a rate of temperature increase of 5 ° C./min and held for 5 hours to obtain a fired product (primary firing).
Subsequently, after cooling to room temperature, the contents of the crucible were taken out and crushed.
0.05 mol of SrCl ₂ was added to the obtained fired product, mixed with a small V-type blender, 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 was raised to 950 ° C. at a heating rate of 5 ° C./min in a reducing atmosphere at atmospheric pressure. And held for 3 hours (secondary firing). Subsequently, after cooling to room temperature, the contents of the crucible were 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 into an alumina crucible. Again, the crucible was set in the same electric furnace as the secondary firing. While flowing hydrogen-containing nitrogen gas (hydrogen: nitrogen = 4: 96 (volume ratio)) at a rate of 2.5 liters per minute, the temperature was 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 calcined mass was coarsely pulverized 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, allowed to stand until the phosphor particles settle, and then the supernatant liquid is discarded. The electrical conductivity of the supernatant liquid is 3 mS / m. Repeat until: After confirming that the electrical conductivity of the supernatant was 3 mS / m or less, the fine particles and coarse particles of the phosphor were removed by classification.
The obtained phosphor slurry was dispersed in an aqueous Na ₃ PO ₄ solution having pH = 10, and small particles were classified and removed, followed by a calcium phosphate treatment. After dehydration, the phosphor (SCA): Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu was obtained by drying at 150 ° C. for 10 hours.

  The resulting blue phosphor (SCA) had an emission peak wavelength of 450 nm and an emission peak half width of 29 nm.

<Synthesis Example 4>
As phosphor materials, barium carbonate (BaCO ₃ ), europium oxide (Eu ₂ O ₃ ), basic magnesium carbonate (mass per mol of 93.17), manganese carbonate (MnCO ₃ ), α-alumina (Al ₂ O ₃₎ In addition, aluminum fluoride (AlF3) was used as a baking aid. These phosphor raw materials are weighed in such an amount as to have a chemical composition represented by Ba _0.455 Sr _0.245 Eu _0.3 Mg _0.7 Mn _0.3 Al ₁₀ O ₁₇ , and the firing aid is used as the phosphor. It weighed so that it might become 0.8 weight% with respect to the total weight of a raw material, it mixed for 30 minutes in the mortar, and filled the crucible made from an alumina. In order to create a reducing atmosphere at the time of firing, alumina crucibles were doubled, beaded graphite was placed in the space around the inner crucible, and fired in air at 1550 ° C. for 2 hours. The obtained fired product was crushed to obtain a green phosphor (GBAM).

  The obtained green phosphor (GBAM) had an emission peak wavelength of 517 nm and an emission peak half width of 27 nm.

<Synthesis Example 5>
As a phosphor raw material, 0.7 mol of barium carbonate (BaCO ₃ ), 0.15 mol of europium oxide (Eu ₂ O ₃ ), 1 mol of basic magnesium carbonate (mass of 93.17 per 1 mol of Mg) as Mg, α-alumina (Al ₂ O ₃ ) was weighed so that 5 mol of the phosphor had a chemical composition of Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , mixed in a mortar for 30 minutes, and placed in an alumina crucible. It was filled and fired at 1200 ° C. for 5 hours while flowing nitrogen in a box-type firing furnace. After cooling, it was taken out from the crucible and crushed to obtain a phosphor precursor.
To this precursor, 0.3% by weight of AlF ₃ is added, ground and mixed in a mortar for 30 minutes, filled in an alumina crucible, and in a nitrogen gas containing 4% by volume of hydrogen in a box-type atmosphere firing furnace. Was baked at 1450 ° C. for 3 hours, and the fired product obtained after cooling was crushed to obtain a light blue powder.

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

[Production method of optimized color filter]
The optimized color filters used in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 described above were manufactured 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 substituted with nitrogen. Thereafter, 6 parts by weight of 2,2′-azobisisobutyronitrile is added and 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 mgKOH / 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 an acrylic dispersant “DB2000” manufactured by Big Chemie, and 5.6 parts by weight of the binder resin produced as described above were mixed and stirred for 3 hours with a stirrer to obtain a solid content. A millbase with a concentration of 25% by weight is prepared. This mill base was dispersed in a bead mill using 600 parts by weight of 0.5 mmφ zirconia beads at a peripheral speed of 10 m / s and a residence time of 3 hours. R. 254 dispersion ink is obtained.
In addition, the pigment is P.I. R. 177 except for the change to P.177. R. A mill base was prepared with the same composition as the mill base of H.254, and dispersed for 3 hours with a residence time under the same dispersion conditions. R. 177 dispersion ink is obtained.

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

The color filter composition thus obtained is applied onto a 10 cm × 10 cm glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) using a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet rays having 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 thickness of the red pixel after fabrication is set to 2.5 μm.

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

  The dispersion ink obtained as described above and the resist solution produced above were mixed and stirred at a weight blending 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 so that the final solid content concentration is 25% by weight to obtain a green color filter composition.

The color filter composition thus obtained is applied onto a 10 cm × 10 cm glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet rays having an exposure amount of 100 mJ / cm ² , developed with an alkaline 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 fabrication is set to 2.5 μm.

(Synthesis of brominated zinc phthalocyanine)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride. This 1-chloronaphthalene solution had light absorption in the wavelength range of 600 to 700 nm. A mixture of 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 was added at 40 ° C., and 4.4 parts by weight of bromine was added dropwise. Phthalocyanine was brominated. The mixture was reacted 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 with hot water at 80 ° C., and dried at 90 ° C. to obtain 3.0 parts by weight of a purified crude brominated zinc phthalocyanine pigment.

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

<Production of blue pixels>
Pigment is changed to P.I. G. 15: 6 except for the above change. R. A mill base was prepared with the same composition as the mill base of No. 254 and subjected to dispersion treatment under the same dispersion conditions with a residence time of 1 hour. G. A 15: 6 dispersion ink is obtained.
In addition, the pigment is P.I. V. 23 except for the change to P.23. R. A mill base was prepared with the same composition as the mill base of No. 254 and subjected to a dispersion treatment under the same dispersion conditions with a residence time of 2 hours. V. 23 dispersion inks are obtained.
The dispersion ink obtained as described above and the resist solution produced above were mixed and stirred at a weight blending ratio of B15: 6: V23: clear resist = 14.4: 4.9: 80.7, and finally A solvent (propylene glycol monomethyl ether acetate) is added so that the solid content concentration is 25% by weight to obtain a blue color filter composition.

The color filter composition thus obtained is applied onto 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 rays having 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 fabrication is set to 2.5 μm.

1 Phosphor-containing part (second light emitter)
2 Excitation light source (first light emitter) (LD)
3 Substrate 4 Light-emitting device 5 Mount lead 6 Inner lead 7 Excitation light source (first light emitter)
DESCRIPTION OF SYMBOLS 8 Fluorescent substance containing part 9 Conductive wire 10 Mold member 11 Surface light-emitting illuminating device 12 Holding case 13 Light-emitting device 14 Diffusion plate 22 Excitation light source (1st light-emitting body)
23 Phosphor-containing part (second light emitter)
24 Frame 25 Conductive wire 26, 27 Electrode

Claims (6)

Containing a crystal phase having a chemical composition represented by the following formula [1],
A phosphor characterized in that the ratio of Mn to the total number of moles of M ⁴ and Mn is 1 mol% or more and 8 mol% or less, and the weight median diameter is 10 μm or more and 50 μm or less.
M ¹ ₂ M ⁴ F ₆ : R (1)
(In 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, and R is an attachment containing at least Mn. Represents an active element.)   A phosphor-containing composition comprising the phosphor according to claim 1 and a liquid medium. A light emitting device comprising: a first light emitter; and a second light emitter that emits visible light by irradiation of light from the first light emitter,
A light emitting device comprising a first phosphor containing one or more of the phosphors according to claim 1 as the second phosphor.   4. The light emitting device according to claim 3, wherein the second phosphor includes a second phosphor including one or more phosphors having emission peak wavelengths different from those of the first phosphor. 5. apparatus.   An illumination device comprising the light-emitting device according to claim 3.   An image display device comprising the light-emitting device according to claim 3.

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