JP2008050593A - Fluorophor-containing composition, light emitter, illuminator, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorophor-containing composition which can prevent the precipitation of the fluorophor for a time until cured, in a process for charging the composition in a light emitter. <P>SOLUTION: This fluorophor-containing composition comprising fine silica particles, a fluorophor, and a liquid medium is characterized in that the hydroxyl group concentration of the fine silica particles measured by the following method (I) for measuring a hydroxyl group concentration is 0.3 to 2 particles/nm<SP>2</SP>. The method (I) for measuring the hydroxyl group concentration comprises (1) measuring a specific surface area (m<SP>2</SP>/g) per g of the silica particles by BET method; (2) drying 1 g of the fine silica particles at 100°C for one hour in a vacuum of 10<SP>-2</SP>hPa, reacting the dried fine silica particles with 10 g of LiAlH<SB>4</SB>in 1 L of diethylene glycol dimethyl ether, and determining the volume b (ml) of the generated H<SB>2</SB>; (3) calculating the concentration of the hydroxyl groups according to an expression: hydroxyl group concentration (groups/nm<SP>2</SP>)=(6×10<SP>23</SP>×b)/(22400×a×10<SP>18</SP>). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a phosphor-containing composition, a light emitting device, a lighting device, and an image display device. Specifically, the phosphor-containing composition in which the phosphor is less precipitated during the period from filling to the light-emitting device and curing, the light-emitting device formed using the phosphor-containing composition, and the light-emitting device are used. The present invention relates to an illumination device and an image display device formed in this manner.

Phosphors as wavelength conversion materials are gallium nitride (GaN) light emitting diodes with high luminous efficiency (light emitting diodes) that are attracting attention as semiconductor light emitting devices that emit light in the near ultraviolet to blue region, as materials for white light emitting devices. Hereinafter, it is used in combination with “LED” as appropriate, and a semiconductor laser diode (hereinafter referred to as “LD” where appropriate), and the light emitting device is an image display device or illumination device. It is used as a luminescence source.
The phosphor is required to have high wavelength conversion efficiency with respect to excitation light in the near-ultraviolet region to blue region where the light emitting efficiency of the semiconductor light emitting device is high (Patent Documents 1 and 2).

  On the other hand, when manufacturing the light-emitting device, in order to place the phosphor at a desired position of the light-emitting device, the phosphor-containing composition in which the phosphor is dispersed in a liquid medium is usually filled (injected) into the device, Thereafter, a step of curing the composition is included. However, during this process, the phosphor may settle before the injected phosphor-containing composition is cured, and the phosphor distribution inside the phosphor-containing composition may be biased, so that light emission occurs. There was a problem in terms of effective use of the phosphor. In order to solve this problem, for example, by using a liquid medium having a high viscosity or by adding an inorganic filler such as silicon oxide, the viscosity of the phosphor-containing composition is increased to prevent the phosphor from being precipitated. A method has been proposed (Patent Document 3). However, when the viscosity of the phosphor-containing composition is high, (i) it is likely to cause troubles such as blockage of the pipe at the time of injection, (ii) bubbles are difficult to escape, (iii) the lead wire of the semiconductor element is likely to break, It may cause adverse effects such as.

Therefore, there has been a demand for a phosphor-containing composition in which the phosphor does not settle during injection until it is cured after injection without increasing the viscosity. In order to solve this problem, a proposal has been made to prevent sedimentation of the phosphor by adding a thixotropic agent, a part of which is at least nanoparticles, to the phosphor-containing composition (Patent Document 4). .
Japanese Patent Laid-Open No. 10-190066 Japanese Patent Laid-Open No. 10-247750 JP 2003-64358 A JP 2005-524737 A

  However, the phosphor-containing composition has thixotropic properties, depending on the structure of the light-emitting device, if the injection speed becomes low at the final stage of filling (injection) into the device, the viscosity increases and the filling becomes insufficient. was there. For this reason, there has been a demand for a phosphor-containing composition that does not have thixotropic properties or that does not have a problem of insufficient filling in the above-described apparatus. In addition, among thixotropic agents disclosed in many in the prior art, there has been a demand for a further excellent antisedimentation effect of the phosphor. In addition, there has been a demand for an appropriate composition according to the combination of the phosphor and the liquid medium in order to make the phosphor sedimentation preventing effect effective.

As a result of intensive studies in view of the above problems, the present inventors have increased the viscosity of the phosphor-containing composition by adding specific silica fine particles to the phosphor-containing composition comprising a liquid medium and a phosphor. Thus, the present inventors have found that the sedimentation of the phosphor is suppressed even when the thixotropic property is not exhibited, and the present invention has been completed. That is, when a phosphor-containing composition containing silica fine particles having a hydroxyl group concentration of 0.3 / nm ² or more and 2 / nm ² or less, preferably pH 4.5 or more and 7 or less is used. The present inventors have found that the phosphor contained therein does not substantially settle, and as a result, found that a semiconductor light emitting device having a uniform light emission distribution can be obtained.

That is, the gist of the present invention resides in the following <1> to <7>.
<1> A phosphor-containing composition containing silica fine particles, a phosphor, and a liquid medium, wherein the hydroxyl concentration of the silica fine particles measured by the following hydroxyl concentration measurement method (I) is 0.3 / nm. ^2. A phosphor-containing composition characterized by being ² or more and 2 / nm ² or less.
Hydroxyl concentration measurement method (I)
(1) The specific surface area a (m ² / g) per 1 g of the silica fine particles is measured by the BET method. (2) 1 g of silica fine particles is dried at 100 ° C. for 1 hour in a vacuum of 10 ⁻² hPa, then reacted with 10 g of LiAlH _{4 in} 1 L of diethylene glycol dimethyl ether, and the amount of generated H ₂ b (ml) is quantified.
(3) The hydroxyl group concentration is calculated by the following formula.
Hydroxyl concentration (pieces / nm ² ) = (6 × 10 ²³ × b) / (22400 × a × 10 ¹⁸ )
<2> The phosphor-containing composition according to <1>, wherein the silica fine particles measured by the following pH measurement method (II) have a pH of 4.5 or more and 7 or less.
pH measurement method (II)
4 g of silica fine particles are added to 0.1 L of water: methanol = 1: 1 solution, and after sufficiently stirring for 5 minutes at a liquid temperature of 20 to 25 ° C., the pH is measured with a pH meter.

<3> The phosphor-containing composition according to <1> or <2>, wherein the liquid medium is a silicone resin.
<4> The phosphor containing one or more phosphors selected from Eu-activated nitride phosphors, and one or more phosphors selected from Ce-activated silicate phosphors and Ce-activated oxide phosphors The phosphor-containing composition according to any one of <1> to <3>.

<5> A light-emitting device formed using the phosphor-containing composition according to any one of <1> to <4>.
<6> An image display device formed using the light emitting device according to <5>.
<7> An illuminating device formed using the light emitting device according to <5>.

  The phosphor-containing composition of the present invention can suppress the sedimentation of the phosphor even when the viscosity does not increase and the thixotropic property is not exhibited. In addition, the light emitting device of the present invention has a uniform light emission distribution of the phosphor and high quality. Further, since the phosphor is effectively used, it is useful for manufacturing a light emitting device. Further, an image display device and an illumination device using such a light emitting device have a uniform light emission distribution and high quality. Further, since the phosphor is effectively used, it is useful for manufacturing an image display device and a lighting device.

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.
[1] Phosphor-containing composition
It is essential that the phosphor-containing composition of the present invention contains silica fine particles having specific physical properties, a phosphor, and a liquid medium. Moreover, you may contain other arbitrary components if needed.
[1-1] Silica fine particles
The phosphor-containing composition of the present invention must contain silica fine particles having specific physical properties. When the silica fine particles used in the present invention are used, there is no increase in the viscosity of the phosphor-containing composition, and even when the thixotropic property is not exhibited, filling (injection) into the light-emitting device, and precipitation of the phosphor in the curing process occurs. It is suppressed. The reason why the silica fine particles of the present invention exert the above effect is not clear, but is presumed as follows. That is, when silica fine particles are generally added to the composition system, a network is formed by hydrogen bonding between the hydroxyl groups of the silica fine particles. The reason for the thixotropic property is described as a network that maintains a high viscosity when the stress is small, but is low and exhibits a low viscosity when the stress is large. Since the present invention uses silica fine particles having a low hydroxyl group concentration, it is presumed that the network as described above is not easily formed and the thixotropic property may not be exhibited. Even in such a case, the sedimentation of the phosphor is suppressed because the added silica fine particles interact with the phosphor surface to form a buffer structure that is loosely bonded to the phosphor surface. It is presumed that aggregation between each other is prevented and the apparent specific gravity of the phosphor in the phosphor-containing composition is reduced.

Hereinafter, the silica fine particles used in the present invention will be described in detail.
[1-1-1] Hydroxyl concentration
Silica fine particles used in the present invention, the hydroxyl group concentration of the silica fine particles measured by the hydroxyl group concentration measurement method (I) below is 0.3 pieces / nm ² or more, two / nm ² or less. This indicates that silica fine particles having a specific amount of SiOH groups present on the surface of the fine particles are suitable as a material for the phosphor-containing composition of the present invention.
Hydroxyl concentration measurement method (I)
(1) The specific surface area a (m ² / g) per 1 g of the silica fine particles is measured by the BET method. (2) 1 g of silica fine particles is dried at 100 ° C. for 1 hour in a vacuum of 10 ⁻² hPa, then reacted with 10 g of LiAlH _{4 in} 1 L of diethylene glycol dimethyl ether, and the amount of generated H ₂ b (ml) is quantified.
(3) The hydroxyl group concentration is calculated by the following formula.
Hydroxyl concentration (pieces / nm ² ) = (6 × 10 ²³ × b) / (22400 × a × 10 ¹⁸ )

The lower limit of the hydroxyl group concentration of the silica fine particles is preferably 0.5 / nm ² or more. Moreover, an upper limit becomes like this. Preferably it is 1.5 piece / nm < ² > or less. If the hydroxyl group concentration is too low, the interaction with the phosphor surface is weakened, and the force for holding the phosphor particles in the phosphor-containing composition may be weakened. If the hydroxyl group concentration is too high, the interaction with the phosphor surface becomes strong, and the silica fine particles form a bridge structure between the phosphor particles, so that precipitation due to aggregation of the phosphor may occur.
[1-1-2] pH
Furthermore, the silica fine particles used in the present invention preferably have a pH measured by the following pH measurement method (II) of 4.5 or more and 7 or less.

pH measurement method (II)
4 g of silica fine particles are added to 0.1 L of water: methanol = 1: 1 solution, and after sufficiently stirring for 5 minutes at a liquid temperature of 20 to 25 ° C., the pH is measured with a pH meter.
The lower limit of the pH of the silica fine particles is preferably 4.8 or more, and the upper limit is preferably 6.5 or less. Since pH affects the interaction between phosphor particles, if the pH is too high, the force for holding the phosphor in the phosphor-containing composition may be weakened. If the pH is too low, precipitation due to aggregation of the phosphor may occur.

[1-1-3] Hydrophobicity
As described above, the silica fine particles used in the present invention are preferably hydrophobic because they are less likely to form a network due to hydrogen bonding between hydroxyl groups.
The surface of the silica fine particles can be hydrophobized by reacting, for example, a silanol group present on the surface of the hydrophilic silica fine particles and a surface modifier added separately.
Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

The method for confirming that the silica fine particles have reacted with the surface modifier can be confirmed by measuring the carbon content. For example, the following method can be employed for measuring the carbon content.
Silica fine particles are placed in an induction furnace under conditions of 1000 to 1100 ° C. for 10 to 60 minutes, and the contained carbon is oxidized to generate carbon monoxide. Next, it is re-oxidized at 300 to 600 ° C. to carbon dioxide in the presence of a catalyst. The amount of carbon dioxide produced is measured with a carbon analyzer (for example, a carbon analyzer “C-244 type” manufactured by LECO), and the carbon content is calculated.

[1-1-4] Other physical properties
Examples of the silica fine particles of the present invention include fumed silica. Fumed silica is produced by oxidizing and hydrolyzing SiCl ₄ gas with a flame of 1100 to 1400 ° C. in which a mixed gas of H ₂ and O ₂ is burned. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle size of about 5 to 50 nm. Secondary particles that are several hundred nm are formed. Since fumed silica is an ultrafine particle and is produced by rapid cooling, the surface structure is in a chemically active state.

The silica fine particles used in the present invention have a specific surface area by the BET method of usually 50 m ² / g or more, preferably 80 m ² / g or more, more preferably 100 m ² / g or more. Moreover, it is 300 m < ² > / g or less normally, Preferably it is 200 m < ² > / g or less. If the specific surface area is too small, the effect of suppressing the precipitation of the phosphor particles is not observed even if silica particles are added, and if it is too large, it is difficult to disperse the silica particles in the resin.

The average particle diameter of the primary particles of the silica fine particles used in the present invention is obtained from the above specific surface area by calculation. The average particle diameter is d (nm), and the surface area of 1 g of powder is S (m ² / g
), The shape factor is φ
Then
d = 6 / Sφ
Is established (Source: University of Chemistry Dictionary)
For example, when the true specific gravity of silica fine particles is 2.2 and the shape is a true sphere, d can be obtained by setting φ = 2.2 × 10 ⁻³ . As the silica fine particles used in the present invention, commercially available ones can be used. Specific examples include hydrophobic “Aerosil” (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophobic “Aerosil” (registered trademark) include “R8200”, “R972”, “R972V”, “R972CF”, “R974”, “R202”, “R805”, “R812”, “R812S”, "RX200""RY200
And “RY200S”.

[1-2] Phosphor
The phosphor used in the phosphor-containing composition of the present invention generally refers to a substance that emits visible light when irradiated with light.
There is no particular limitation on the composition of the phosphor, _Y 2 _O 3 is a host _crystal, Zn 2 metal oxide represented by SiO ₄ and the _like, a metal nitride typified by Sr 2 _Si 5 _{N 8} such, Ca ₅ (PO ₄ ) ₃ Cl etc. and phosphates such as ZnS, SrS, CaS etc., Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, A combination of rare earth metal ions such as Tm and Yb and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators is preferred.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, C
a) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉
, (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O _12, etc., aluminates such as Y ₂ SiO ₅ Silicate such as Zn ₂ SiO ₄ , oxide such as SnO ₂ and Y ₂ O ₃ , borate such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ (F, Cl ) ₂ , halophosphates such as (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ , phosphates such as Sr ₂ P ₂ O ₇ , (La, Ce) PO _4, etc. it can.
However, the crystal matrix 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, phosphors that differ only in part of the structure are omitted as appropriate. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “ “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are collectively shown as “(La, Y) ₂ O ₂ S: Eu”. ing. Omitted parts are shown separated by commas (,).

[1-2-1] Orange to red phosphor
The phosphor-containing composition of the present invention may contain a phosphor emitting orange to red fluorescence (hereinafter referred to as “orange to red phosphor” as appropriate).
When the specific wavelength range of the fluorescence emitted by the red phosphor is exemplified, the peak wavelength is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less, preferably 680 nm or less.
Examples of the orange or red phosphor other than the phosphor according to the present invention include, for example, broken particles having a red fracture surface and emit light in a red region (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Europium-activated alkaline earth silicon nitride-based phosphor represented by Eu, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) Examples include europium activated rare earth oxychalcogenide phosphors represented by ₂ O ₂ S: Eu.

  Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphor, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, Mn, (Ba, Mg) 2 SiO 4: Eu, Eu such as Mn, Mn-activated silicate phosphor, (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO ₃ : Eu-activated aluminate phosphors such as Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ ( SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu-activated silicate phosphor such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce , (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, (Ca, Sr, Ba) ₂ Si _{5 N 8: Eu, (Mg,} Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride phosphor such as Eu, (Mg, Ca, Sr , Ba ) AlSiN ₃ : Ce-activated nitride phosphor such as Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, 2. Ba ₃ Mg) Si ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphor such as Eu, Mn 5MgO · 0.5MgF ₂ · GeO ₂ : Mn-activated germanate phosphor such as Mn, Eu-activated oxynitride phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi activated oxide phosphor such as Eu, Bi, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi Eu, Bi-activated oxysulfide phosphor such as (Gd, Y, Lu, La) VO ₄ : Eu, Bi-activated vanadate phosphor such as Eu, Bi, SrY ₂ S ₄ : Eu, Ce, etc. Eu, Ce activated sulfide phosphors, CaLa ₂ S ₄ : Ce activated sulfide phosphors such as Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo , (Ba, Sr, Ca) x Si y N z: Eu, Ce ( provided that, x, y, z are an integer of 1 or more) Eu, Ce-activated nitride phosphor such as, (Ca, Sr, Ba _{, Mg) 10 (PO 4)} 6 (F, Cl, Br, OH): Eu, Eu such as Mn, Mn-activated halophosphate phosphor, ((Y, Lu, d, Tb) can also be used such as _{1-x Sc x Ce y)} 2 (Ca, Mg) 1-r (Mg, Zn) 2 + r Si z-q GeqO Ce -activated silicate phosphors _{12 + [delta],} etc. .

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

Of the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn, and the like.

[1-2-2] Green phosphor
The phosphor-containing composition of the present invention may contain a phosphor that emits green fluorescence (hereinafter, referred to as “green phosphor” as appropriate).
When the specific wavelength range of the fluorescence emitted from the green phosphor is exemplified, the peak wavelength is usually 490 nm or more, preferably 500 nm or more, and usually 570 nm or less, preferably 550 nm or less.
As such a green phosphor, for example, a europium-activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting in the green region (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

In addition, examples of the green phosphor include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _2. Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Tb activated silicate phosphor such as Ce, Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu such as Eu Activated boric acid phosphor, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu activated halosilicate phosphor such as Eu, Zn ₂ SiO ₄ : Mn activated silicate phosphor such as Mn, CeMgAl ₁₁ O ₁₉ : Tb, Y ₃ Al ₅ O ₁₂ : Tb-activated aluminate firefly such as Tb Light body, Tb activated silicate phosphor such as Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Tb, La ₃ Ga ₅ SiO ₁₄ : Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb Eu, Tb, Sm activated thiogallate phosphor such as Sm, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ Ce-activated silicic acid such as O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce Salt phosphor, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu activated β sialon Eu activated oxynitride phosphors such as Eu activated α sialon, BaMgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn, SrAl ₂ O ₄ : Eu activated aluminate phosphor such as Eu, (La, Gd, Y) ₂ O ₂ S: Tb such as Tb Activated oxysulfide phosphor, LaPO ₄ : Ce, Tb activated phosphate phosphor such as Ce, Tb, Sulfide phosphor such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6: K, Ce, Ce, Tb activated borate phosphor such as Tb, Eu, Mn activated halosilicate phosphor such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphor such as Eu, thiogallate phosphor, (Ca, Sr) ₈ (M g, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn-activated halosilicate phosphors such as Eu and Mn can also be used.

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

[1-2-3] Blue phosphor
The phosphor-containing composition of the present invention may contain a phosphor emitting blue fluorescence (hereinafter appropriately referred to as “blue phosphor”).
When the specific wavelength range of the fluorescence emitted from the blue phosphor is exemplified, the peak wavelength is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less.
As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu, which is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emits light in a blue region. Europium-activated halo represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of phosphors and grown particles having a substantially spherical shape as a regular crystal growth shape and emits light in the blue region. Calcium phosphate phosphor, composed of growing particles having a cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu Consists of alkaline earth chloroborate phosphors and fractured particles with fractured surfaces, and emits light in the blue-green region. _{(Sr, Ca, Ba) Al} 2 O 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: activated alkaline earth with europium aluminate-based phosphor such as represented by Eu and the like.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu activation such as Eu, Mn, Sb Halophosphate phosphor, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu-activated silicate phosphor such as Eu, Sr ₂ P ₂ O ₇ : Eu-activated phosphate phosphor such as Eu, ZnS : Ag, ZnS: Sulfide phosphors such as Ag, Al, Y ₂ SiO ₅ : Ce-activated silicate phosphors such as Ce, Tungsten phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn activated phosphorus borate such as Eu It is also possible to use an acid activated phosphor, an Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu, or the like.

Further, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based fluorescent dyes, organic phosphors such as thulium complexes, and the like can be used. .
In addition, the above-mentioned fluorescent substance may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

[1-2-4] Yellow phosphor
The phosphor-containing composition of the present invention may contain a phosphor that emits yellow fluorescence (hereinafter appropriately referred to as “yellow phosphor”).
Illustrating the specific wavelength range of the fluorescence emitted by the yellow phosphor, it is usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. It is preferable to be in the range. If the emission peak wavelength of the yellow phosphor is too short, there is a possibility that the yellow component will be reduced and the light emitting device will be inferior in color rendering, and if it is too long, the luminance of the light emitting device may be reduced.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element of Y, Tb, Gd, Lu, and Sm, and M represents at least one element of Al, Ga, and Sc) Or a garnet structure represented by M2 ₃ M3 ₂ M4 ₃ O ₁₂ : Ce (where M2 is a divalent metal element, M3 is a trivalent metal element, M4 is a tetravalent metal element), etc. Garnet-based phosphor having AE ₂ M5O ₄ : Eu (where AE represents at least one element of Ba, Sr, Ca, Mg, Zn, and M5 represents at least one element of Si, Ge) Orthosilicate phosphors represented by, etc., oxynitride phosphors obtained by substituting part of oxygen of the constituent elements of these phosphors with nitrogen, AEAlSiN ₃ : Ce (where AE represents , Ba, Sr, Ca, Mg, Zn Both activated and phosphor can be mentioned in one element represents a.) Of the nitride-based fluorescent material or the like having a CaAlSiN ₃ structure, such as Ce.

In addition, examples of yellow phosphors include sulfide phosphors such as CaGa ₂ S ₄ : Eu (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a SiAlON structure such as Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu.

[1-2-5] Combination of phosphors
Examples of specific preferred combinations of phosphors used in the phosphor-containing composition of the present invention include one or more phosphors selected from Eu-activated nitride phosphors as red phosphors, and Ce as a green phosphor. Examples include phosphor-containing compositions containing one or more phosphors selected from activated silicate phosphors and Ce-activated oxide phosphors.

Eu-activated nitride red phosphors include (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Mg, Ca, Sr, Ba) SiN ₂ : Eu, (Mg, Ca, Sr, Ba) AlSiN. ₃ : Eu etc. Among them, there are CaAlSiN ₃ : Eu (hereinafter sometimes abbreviated as “CASN”) and (Sr, Ca) AlSiN ₃ : Eu (hereinafter sometimes abbreviated as “SCASN”). Is preferred.

Examples of the Ce-activated silicate green phosphor include Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, and among others, Ca ₃ (Sc , Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce (hereinafter sometimes abbreviated as “CSMS”) is preferable.
Examples of the Ce-activated oxide green phosphor include a combination of CaSc ₂ O ₄ : Ce (hereinafter sometimes abbreviated as “CSO”). Combinations of these phosphors may be appropriately combined according to desired chromaticity coordinates, color rendering index, luminous efficiency, and the like.

[1-2-6] Physical properties of other phosphors
The particle size of the phosphor used in the present invention is not particularly limited, but the median particle size (D ₅₀ ) is usually 0.1 μm or more, preferably 2 μm or more, more preferably 10 μm or more. Moreover, it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 20 micrometers or less. If D ₅₀ is too small, and the luminance decreases, there is a possibility that phosphor particles tend to aggregate. On the other hand, when D ₅₀ is too large, there is a possibility that clogging of such coating unevenness or dispenser may occur.

  The particle size distribution (QD) of the phosphor particles is preferably small in order to align the dispersed state of the particles in the phosphor-containing composition, but in order to reduce the particle size, the classification yield decreases, leading to an increase in cost. Usually, it is 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more. Moreover, it is 0.4 or less normally, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. Further, the shape of the phosphor particles is not particularly limited as long as the phosphor part formation is not affected.

In the present invention, the median particle size (D ₅₀ ) and particle size distribution (QD) can be obtained from a weight-based particle size distribution curve. The weight-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method, and specifically, for example, can be measured as follows.
A phosphor is dispersed in a solvent such as ethylene glycol under an environment of an air temperature of 25 ° C. and a humidity of 70%.

Measurement is performed with a laser diffraction particle size distribution measuring apparatus (Horiba, Ltd. LA-300) in a particle size range of 0.1 μm to 600 μm.
Integrated value in the weight particle size distribution curve is denoted a particle size value when the 50% and median particle diameter D _50. Further, the particle size values when the integrated values are 25% and 75% are expressed as D ₂₅ and D ₇₅ , respectively, and defined as QD = (D ₇₅ −D ₂₅ ) / (D ₇₅ + D ₂₅ ). A small QD means a narrow particle size distribution.

[1-2-7] Phosphor surface treatment
The phosphor used in the present invention may be subjected to a surface treatment for the purpose of enhancing water resistance or preventing unnecessary aggregation of the phosphor in the phosphor-containing composition.
Examples of such surface treatments include surface treatments using organic materials, inorganic materials, glass materials, and the like described in JP-A No. 2002-223008, and metal phosphates described in JP-A No. 2000-96045. Known surface treatments such as coating treatment, coating treatment with metal oxide, and silica coating can be used.
Specifically, for example, in order to coat the surface of the phosphor with the metal phosphate, the following coating methods (i) to (iii) are mentioned. (I) A predetermined amount of a water-soluble phosphate such as potassium phosphate and sodium phosphate and at least one of alkaline earth metals such as calcium chloride, strontium sulfate, manganese chloride and zinc nitrate, Zn and Mn A water-soluble metal salt compound is added to the phosphor suspension and stirred. (Ii) A phosphate of at least one metal among alkaline earth metals, Zn and Mn is formed in the suspension, and the generated metal phosphate is deposited on the phosphor surface. (Iii) Remove moisture.

Examples of the silica coat include a method of neutralizing water glass to precipitate SiO ₂ , a method of surface treating a hydrolyzed alkoxysilane (for example, JP-A-3-231987), and the like. From the standpoint of enhancing the properties, a method of surface-treating a hydrolyzed alkoxysilane is preferable.

[1-3] Liquid medium
As the liquid medium to be used, an inorganic material and / or an organic material can be used.
Examples of the inorganic material include a solution obtained by hydrolyzing a solution containing a metal alkoxide, a ceramic precursor polymer, or a metal alkoxide by a sol-gel method (for example, an inorganic material having a siloxane bond). it can.
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. Conventionally, as a phosphor dispersion material for a semiconductor light emitting device, an epoxy resin has been generally used. However, when a high output light emitting device such as an illumination is required, it contains silicon for the purpose of heat resistance and light resistance. It is preferred to use compounds.

  A silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone-based materials), inorganic materials such as silicon oxide, silicon nitride, and silicon oxynitride, and borosilicates and phosphosilicates. Examples thereof include glass materials such as salts and alkali silicates. Among these, silicone materials are preferable from the viewpoint of ease of handling and the point that the cured product has a stress relaxation force. Regarding silicone resins for semiconductor light emitting devices, for example, use as a sealant in JP-A-10-228249, JP-A-2927279, JP-A-2001-36147, etc., and JP-A 2000-123981 to wavelength adjustment coating. The use of is being tried.

[1-3-1] Silicone material
The silicone material generally refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by a general composition formula and / or a mixture thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q
Here, R ¹ to R ⁶ may be the same or different and are selected from the group consisting of an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are 0 to less than 1 and satisfy M + D + T + Q = 1.
When a silicone material is used for sealing a semiconductor light emitting element, it can be used after being sealed with a liquid silicone material and then cured by heat or light.

[1-3-2] Types of silicone materials
When silicone materials are classified according to the curing mechanism, silicone materials such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide vulcanization type can be mentioned. Among these, addition polymerization curing type (addition type silicone resin), condensation curing type (condensation type silicone resin), and ultraviolet curing type are preferable. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

[1-3-2-1] Addition type silicone material
The addition-type silicone material refers to a material in which a polyorganosiloxane chain is crosslinked by an organic addition bond. A typical example is a compound having a Si—C—C—Si bond at a crosslinking point obtained by reacting vinylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst.

  Specifically, the addition-type silicone material includes, for example, an alkenyl group-containing organopolysiloxane (A) represented by the following average composition formula (1a) and a hydrosilyl group-containing organo group represented by the following average composition formula (2a). The polysiloxane (B) is mixed with the total alkenyl group of (A) at a ratio such that the total hydrosilyl group amount of (B) is 0.5 to 2.0 times, and a catalytic amount of (C) addition reaction catalyst It can be obtained by reacting in the presence of.

(A) Alkenyl group-containing organopolysiloxane RnSiO [(4-n) / 2] (1a)
(In the formula, R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group, and n is a positive number satisfying 1 ≦ n <2.) And an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms.

(B) Hydrosilyl group-containing polyorganosiloxane R′aHbSiO [(4-ab) / 2] (2a)
Wherein R ′ is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding the aliphatic unsaturated hydrocarbon group, and a and b are 0.7 ≦ a ≦ 2.1 and 0.001 ≦ b. ≦ 1.0 and 0.8 ≦ a + b ≦ 2.6.) Is a organohydrogenpolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule. .

Hereinafter, the addition type silicone resin will be described in more detail.
In R of the above formula (1a), the alkenyl group is an alkenyl group having 2 to 8 carbon atoms such as vinyl group, allyl group, butenyl group or pentenyl group. When R is a hydrocarbon group, it is selected from alkyl groups such as methyl group and ethyl group, monovalent hydrocarbon groups having 1 to 20 carbon atoms such as vinyl group and phenyl group. Preferably, they are a methyl group, an ethyl group, and a phenyl group. Each may be different, but when UV resistance is required, 80% or more of R is preferably a methyl group. R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 3% or less of the weight of (A).

n is a positive number satisfying 1 ≦ n <2, but if this value is 2 or more, sufficient strength as a sealing material cannot be obtained, and if it is less than 1, synthesis of this organopolysiloxane is not possible. It becomes difficult.
Next, the organohydrogenpolysiloxane (2a) as the component (B) acts as a crosslinking agent for curing the composition by hydrosilylation reaction with the organopolysiloxane (1a) as the component (A). Composition formula (2a)
R'aHbSiO (4-ab) / 2 (2a)
(In the formula, R ′ is a monovalent hydrocarbon group excluding an alkenyl group, and a and b are 0.7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 0.8 ≦ a + b ≦ 2.6, preferably 0.8 ≦ a ≦ 2, 0.01 ≦ b ≦ 1, 1 ≦ a + b ≦ 2.4.) at least two in one molecule An organohydrogenpolysiloxane having 3 or more SiH bonds is preferred.

Here, examples of R ′ include the same groups as R2 in formula (1a), but those having no alkenyl group are preferable. Further, when used for applications requiring UV resistance, at least 80% is preferably a methyl group.
The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is 3 to 1000. In particular, about 3 to 300 can be used.

The blending amount of the organohydropolysiloxane (2a) as the component (B) depends on the total amount of alkenyl groups of the organopolysiloxane (1a) as the component (A) and is based on the total alkenyl groups of the organopolysiloxane (1a). Thus, the total SiH amount may be 0.5 to 2.0 times, preferably 0.8 to 1.5 times.
The addition reaction catalyst for component (C) is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group in component (A) and the SiH group in component (B). Black, platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum catalyst such as platinum bisacetoacetate, palladium catalyst, rhodium catalyst Platinum group metal catalysts such as In addition, although the compounding quantity of this addition reaction catalyst can be made into a catalytic quantity, it is normally mix | blended as 1 to 500 ppm with respect to the total weight of (A) and (B) component as a platinum group metal, especially about 2-100 ppm. It is preferable.

  In addition to the above components (A) to (C), the composition of the present invention has an addition reaction control agent for imparting curability and pot life as an optional component, and has, for example, an alkenyl group for adjusting hardness and viscosity. In addition to the linear diorganopolysiloxane, the linear non-reactive organopolysiloxane, the linear or cyclic low-molecular organopolysiloxane having about 2 to 10 silicon atoms, and the like are effective. You may add in the range which does not impair.

In addition, although the hardening conditions in particular of the said composition are not restrict | limited, It is preferable to set it as the conditions for 120-180 degreeC and 30-180 minutes. When the resulting cured product is in a soft gel state even after curing, the linear expansion coefficient is larger than that of a silicone resin in the form of rubber or hard plastic. Generation of internal stress can be suppressed.
As the addition-type silicone material, known materials can be used, and an additive or an organic group for improving adhesion to metal or ceramics may be introduced. For example, silicone materials described in Japanese Patent No. 3909826, Japanese Patent No. 3910080, Japanese Patent Application Laid-Open No. 2003-128922, Japanese Patent Application Laid-Open No. 2004-221308, and Japanese Patent Application Laid-Open No. 2004-186168 are suitable. Moreover, these can use a commercially available thing, For example, as a specific brand name of addition polymerization hardening type, Shin-Etsu Chemical Co., Ltd. "LPS-1400""LPS-2410""LPS-3400" etc. are mentioned, for example. It is done.

[1-3-2-2] Condensation type silicone material
Examples of the condensation type silicone material include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point.
Specific examples include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (1b) and / or (2b) and / or oligomers thereof.
M ^{m +} X _n Y ¹ _m-1 (1b)
(In the formula (1b), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. M represents one or more integers representing the valence of M, and n represents one or more integers representing the number of X groups, provided that m ≧ n.
_{^{(M s + X t Y 1}} s-t-1) u Y 2 (2b)
(In the formula (2b), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. Y ² represents a u-valent organic group, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, and u represents 2 or more. Represents an integer.)
Moreover, as a curing catalyst, a metal chelate compound etc. can be used suitably, for example. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr.

  A well-known thing can be used for a condensation type silicone type material, for example, Unexamined-Japanese-Patent No. 2006-77234, Unexamined-Japanese-Patent No. 2006-291018, Unexamined-Japanese-Patent No. 2006-316264, Unexamined-Japanese-Patent No. 2006-336010, The semiconductor light-emitting device members described in JP-A-2006-348284 and International Publication No. 2006/090804 are suitable.

Of the silicone materials, particularly preferred materials will be described below.
Silicone-based materials generally have a drawback of poor adhesion to semiconductor light-emitting elements, substrates on which the elements are arranged, packages, and the like, but as silicone-based materials with high adhesion, the following characteristics <1> to A silicone material having one or more of <3> is preferred.
<1> The silicon content is 20% by weight or more.
<2> The solid Si-nuclear magnetic resonance (NMR) spectrum measured by the method described in detail later has at least one peak derived from Si in the following (a) and / or (b).

(A) A peak where the peak top position is in a region where the chemical shift is −40 ppm or more and 0 ppm or less with reference to silicone rubber (−22.333 ppm), and the half width of the peak is 0.3 ppm or more and 3.0 ppm or less.
(B) A peak whose peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm with respect to silicone rubber (−22.333 ppm), and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less.
<3> The silanol content is 0.01% by weight or more and 10% by weight or less.

  In the present invention, among the above features <1> to <3>, a silicone material having the feature <1> is preferable. More preferably, a silicone material having the above characteristics <1> and <2> is preferable. Particularly preferably, a silicone material having all of the above features <1> to <3> is preferable. Of the silicone materials having the above characteristics, a condensation type silicone material is preferable from the viewpoint of heat resistance, light resistance, and the like.

[1-3-3] Content of liquid medium
The liquid medium is usually 50% by weight or more, preferably 75% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less, based on the entire phosphor-containing composition of the present invention.
When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is necessary to add a phosphor. If it is too small, it is difficult to handle due to lack of fluidity.
As described above, the liquid medium mainly has a role as a binder in the phosphor-containing composition of the present invention. Although a liquid medium may be used independently, multiple may be mixed. For example, when a silicon-containing compound is used for the purpose of heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin may be contained to the extent that the durability of the silicon-containing compound is not impaired. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the binder.

[1-4] Other ingredients
In addition to the above components, the phosphor-containing composition of the present invention comprises a dye, an antioxidant, a stabilizer (a processing stabilizer such as a phosphorus processing stabilizer, an oxidation stabilizer, a heat stabilizer, an ultraviolet ray, Any additive known in the art such as a light-resistant stabilizer such as an absorbent), a silane coupling agent, a light diffusing material, and a filler can be used.

[1-5] Method for producing phosphor-containing composition
The method for producing the phosphor-containing composition of the present invention is not particularly limited as long as the phosphor, silica fine particles, and additives to be added as necessary are uniformly dispersed in the liquid medium.
The compounding amount of the silica fine particles is usually 0.1 parts by weight or more, preferably 0.3 parts by weight or more with respect to 100 parts by weight of the liquid medium. The amount is usually 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 15 parts by weight or less, particularly preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less. If the amount of silica fine particles is too small, the effect of suppressing the precipitation of phosphor particles will not be exhibited, and if too large, dispersion of the silica fine particles will be difficult, or the viscosity of the phosphor-containing composition will become too high, resulting in a light emitting device. When filling (injecting) the material, difficulties may occur.

The blending amount of the phosphor is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the liquid medium. Moreover, it is 100 parts weight or less normally, Preferably it is 80 parts weight or less, More preferably, it is 60 parts weight or less.
When a silicone resin is used as the liquid medium, for example, a silicone resin, a phosphor, silica fine particles, a crosslinking agent, a curing catalyst, an extender, and other additives are blended, and a mixer, a high-speed disper, a homogenizer, and a three roll It can be produced by a conventionally known method such as mixing with a kneader. In this case, all of the above components may be mixed to produce a liquid silicone resin composition in the form of one liquid,
Two liquids, (i) a silicone resin liquid mainly composed of a silicone resin, a phosphor and an extender, and (ii) a crosslinker liquid mainly composed of a crosslinking agent and a curing catalyst are prepared. A liquid silicone resin composition may be produced by mixing a resin solution and a crosslinking agent solution.

[1-6] Physical properties of phosphor-containing composition
[1-6-1] Viscosity
The viscosity of the phosphor-containing composition of the present invention is usually 500 mPa · s or more, preferably 1000 mPa · s or more, more preferably 2000 mPa · s or more, and usually 15000 mPa · s or less, 10000 mPa · s or less, preferably 8000 mPa · s. s or less. If the viscosity is too high, troubles such as blockage of piping are likely to occur when filling (injecting) the light emitting device, bubbles are difficult to escape, and lead wires of the semiconductor element are likely to be disconnected. On the other hand, if the viscosity is too low, the phosphor particles settle, which is not preferable.

The phosphor-containing composition of the present invention preferably does not exhibit thixotropic properties in order to be sufficiently filled (injected) into the light emitting device. The lack of thixotropy can be confirmed by the fact that the viscometers of the B-type viscometer are approximately equal when the rotor rotational speed is 1 rpm and 5 rpm.
[2] Light emitting device
The light emitting device of the present invention is formed by a known method using the phosphor-containing composition described in [1]. Hereinafter, the light emitting device of the present invention will be described.

[2-1] Light source
The light source in the light-emitting device of this invention light-emits the light which excites the said [1-2] fluorescent substance and the other fluorescent substance mentioned later. The emission wavelength of the light source is not particularly limited as long as it overlaps with the absorption wavelength of the phosphor, and a phosphor having a wide emission wavelength region can be used. Usually, a phosphor having an emission wavelength from the near ultraviolet region to the blue region is used, and specific values are usually 300 nm or more, preferably 330 nm or more, and usually 500 nm or less, preferably 480 nm or less. A light emitter having the following is used. As this light source, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a semiconductor laser diode (LD), or the like can be used.

  Among these, as the light source, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for the same current load, a GaN-based LED or LD usually has a light emission intensity 100 times or more that of a SiC-based. A GaN-based LED or LD preferably has an Al x Gay N light emitting layer, a GaN light emitting layer, or an In x Gay N light emitting layer. Among the GaN-based LEDs, those having an InxGayN light emitting layer have a very high light emission intensity, and are more preferable, and those having a multiple quantum well structure of an InxGayN layer and a GaN layer are particularly preferable because the light emission intensity is very high. .

In the above, the value of x + y is usually in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light emitting layer, p layer, n layer, electrode, and substrate as basic components, and the light emitting layer is sandwiched between n-type and p-type AlxGayN layers, GaN layers, or InxGayN layers. Those having the heterostructure are preferably high in luminous efficiency, and those having a heterostructure in the quantum well structure are further preferable because of higher luminous efficiency.

[2-2] Selection of phosphor
In the light emitting device of the present invention, whether or not the above-described phosphors (red phosphor, green phosphor, blue phosphor, etc.) are used and the type thereof may be appropriately selected according to the use of the light emitting device.
When the light emitting device of the present invention is configured as a white light emitting device, one or more phosphors may be appropriately combined so that desired white light is obtained. When a blue light emitting element is used as a light source, it is preferable to use a yellow phosphor having a complementary color relationship of blue as a phosphor, and red and green phosphors to obtain white with higher color rendering properties. When using a semiconductor light emitting device that emits near-ultraviolet light, phosphors of three colors of red, green, and blue are preferably used.

Specifically, in the case where the light emitting device of the present invention is configured as a white light emitting device, examples of preferable combinations of a light source and a phosphor include the following combinations (i) to (iii).
(I) A blue light emitter (blue LED or the like) is used as a light source, and a red phosphor and a green phosphor are used as phosphors.
(Ii) A near-ultraviolet light emitter (near-ultraviolet LED or the like) is used as a light source, and a red phosphor, a green phosphor and a blue phosphor are used in combination as phosphors.
(Iii) A blue light emitter (blue LED or the like) is used as a light source, and an orange phosphor and a green phosphor are used.

[2-3] Configuration of light emitting device
The light-emitting device of the present invention is only required to include the above-described light source and the phosphor-containing composition of the present invention, and other configurations are not particularly limited, but usually the above-described light source and phosphor-containing composition are provided on an appropriate frame. A composition is arranged. At this time, the phosphor is excited by the light emission of the light source to generate light emission, and the light emission of the light source and / or the light emission of the phosphor is arranged to be taken out to the outside. In this case, the red phosphor does not necessarily have to be mixed in the same layer as the green phosphor and the blue phosphor. For example, the blue phosphor and the green phosphor are placed on the layer containing the red phosphor. The layer to contain may be laminated | stacked.

[2-4] 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 any modification.
FIG. 1 is a diagram schematically showing a configuration of a light emitting device according to an embodiment of the present invention. The light emitting device 1 of the present embodiment includes a frame 2, a blue LED 3 that is a light source, and a phosphor-containing portion 4 that absorbs part of light emitted from the blue LED 3 and emits light having a wavelength different from that.

  The frame 2 is a metal or resin base for holding the blue LED 3 and the phosphor-containing portion 4. On the upper surface of the frame 2, a trapezoidal concave section (dent) 2A having an opening on the upper side in FIG. Thereby, since the frame 2 has a cup shape, the light emitted from the light emitting device 1 can have directivity, and the emitted light can be used effectively. Further, the inner surface of the concave portion 2A of the frame 2 is enhanced in the reflectance of light in the entire visible light region by metal plating such as silver. Can be discharged in a predetermined direction.

  A blue LED 3 is installed as a light source at the bottom of the recess 2 </ b> A of the frame 2. The blue LED 3 is an LED that emits blue light when supplied with electric power. Part of the blue light emitted from the blue LED 3 is absorbed as excitation light by the luminescent material (phosphor) in the phosphor-containing portion 4, and another part is directed from the light emitting device 1 in a predetermined direction. To be released.

In addition, the blue LED 3 is installed at the bottom of the recess 2A of the frame 2 as described above. Here, the frame 2 and the blue LED 3 are bonded to each other by the adhesive 5, so that the blue LED 3 is attached to the frame 2. is set up.
Further, a gold wire 6 for supplying power to the blue LED 3 is attached to the frame 2. That is, the electrode (not shown) provided on the upper surface of the blue LED 3 is connected by wire bonding using the wire 6, and when the wire 6 is energized, power is supplied to the blue LED 3. It emits blue light. One or a plurality of wires 6 are attached in accordance with the structure of the blue LED 3.

  Further, the concave portion 2A of the frame 2 is provided with a phosphor-containing portion 4 that absorbs part of the light emitted from the blue LED 3 and emits light having a different wavelength. The phosphor-containing part 4 is formed of a phosphor and a transparent resin. The phosphor is a substance that is excited by blue light emitted from the blue LED 3 and emits light having a wavelength longer than that of the blue light. The phosphor constituting the phosphor-containing portion 4 may be a single type or a mixture of a plurality, and the sum of the light emitted from the blue LED 3 and the light emitted from the phosphor light-emitting portion 4 is a desired color. Choose to be. The color is not limited to white, but may be yellow, orange, pink, purple, blue-green, or the like. Further, it may be an intermediate color between these colors and white. Further, the transparent resin is a sealing material for the phosphor-containing portion 4, and here, the phosphor-containing composition of the present invention is cured and used.

The mold unit 7 functions as a lens for protecting the blue LED 3, the phosphor-containing unit 4, the wire 6 and the like from the outside and controlling the light distribution characteristics. An epoxy resin can be mainly used for the mold part 7.
FIG. 2 is a schematic cross-sectional view showing an embodiment of a surface emitting illumination device incorporating the light emitting device 1 shown in FIG. In FIG. 2, 8 is a surface emitting illumination device, 9 is a diffusion plate, and 10 is a holding case.

This surface-emitting illuminating device 8 has a large number of light-emitting devices 1 on the bottom surface of a rectangular holding case 10 whose inner surface is light-opaque such as a white smooth surface, and a power source for driving the light-emitting device 1 on the outside thereof. And a circuit or the like (not shown). In order to make the light emission uniform, a diffusion plate 9 such as an acrylic plate made of milky white is fixed to a portion corresponding to the lid portion of the holding case 10.
Then, the surface-emitting illumination device 8 is driven to apply blue voltage to the blue LED 3 of the light-emitting device 1 to emit blue light or the like. A part of the emitted light is absorbed by the phosphor that is the wavelength conversion material in the phosphor-containing portion 4, converted into light having a longer wavelength, and mixed with blue light or the like that is not absorbed by the phosphor, resulting in high brightness. Can be obtained. This light passes through the diffusion plate 9 and is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 9 of the holding case 10.

  In the light-emitting device of the present invention, in particular, when a surface-emitting type is used as the excitation light source, it is preferable that the phosphor-containing portion is formed into a film. That is, since the cross-sectional area of the light from the surface-emitting type phosphor is sufficiently large, when the phosphor-containing portion is formed into a film shape in the direction of the cross-section, the irradiation cross-section area of the phosphor from the first phosphor is fluorescent. Since it becomes large per body unit quantity, the intensity | strength of light emission from fluorescent substance can be enlarged more.

  In addition, when a surface-emitting type light source is used as the light source and a film-like one is used as the phosphor-containing portion, it is preferable that the light-emitting surface of the light source is directly in contact with the film-like phosphor-containing portion. . Contact here means creating a state where the light source and the phosphor-containing portion are in perfect contact with each other without air or gas. As a result, it is possible to avoid a light amount loss in which light from the light source is reflected by the film surface of the phosphor-containing portion and oozes out, so that the light emission efficiency of the entire apparatus can be improved.

  FIG. 3 is a schematic perspective view showing an example of a light-emitting device using a surface-emitting type light source as the light source and applying a film-like one as the phosphor-containing portion. In FIG. 3, 11 is a film-like phosphor-containing portion having the phosphor, 12 is a surface-emitting GaN-based LD as a light source, and 13 is a substrate. In order to create a state where they are in contact with each other, the LD of the light source 12 and the phosphor-containing portion 11 may be formed separately, and their surfaces may be brought into contact with each other by an adhesive or other means. The phosphor-containing portion 11 may be formed (molded) on the light emitting surface. As a result, the light source 12 and the second phosphor-containing portion 11 can be brought into contact with each other.

[7] Application of light emitting device
The light-emitting device of the present invention can emit light of various colors depending on the type and amount of the phosphor used. For lighting applications, a light-emitting device that emits white light is useful. The light emitting device of the present invention has a luminous efficiency of usually 20 lm / W or higher, preferably 30 lm / W or higher, more preferably 40 lm / W or higher, particularly preferably 60 lm / W or higher, and an average color rendering index Ra of 80. Above, preferably 90 or more, more preferably 95 or more.

The average color rendering index Ra is calculated according to JIS Z 8726.
The application of the light-emitting device of the present invention is not particularly limited, and can be used in various fields where a normal light-emitting device is used. Moreover, you may use individually or in combination. Specifically, for example, it can be used as a light source for illumination lamps, backlights for liquid crystal panels, various illumination devices such as ultra-thin illumination, and image display devices. In addition, when using the light-emitting device of this invention as a light source of an image display apparatus, you may use together with a color filter.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[1] Phosphor-containing composition
[1-1] Phosphor surface treatment
[1-1-1] Surface treatment of red phosphor (Synthesis Example 1)
1 kg of red phosphor (CaAlSiN ₃ : Eu, median particle size D ₅₀ = 8.2 μm) is added to 10 kg of water, stirred for 10 minutes, and then added with 50 ml of 10% Na ₃ PO ₄ · 12H ₂ O aqueous solution and stirred for 10 minutes. did. Next, 25 ml of 20% Ca (NO ₃ ) ₂ .4H ₂ O aqueous solution was added, stirred for 30 minutes, and allowed to stand. After discharging the supernatant, pure water was introduced and stirring was performed for 10 minutes. The process from standing to pure water introduction was repeated three times, and the electrical conductivity of the supernatant liquid was adjusted to 1.8 mS / m or less, and then dried to obtain a surface-treated red phosphor.

[1-1-2] Surface treatment of green phosphor (Synthesis Example 2)
Surface treatment was performed in the same manner as in Synthesis Example 1 except that the red phosphor of Synthesis Example 1 was replaced with a green phosphor (Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, median particle size D ₅₀ = 11.5 μm). A green phosphor was obtained.
[1-2] Measurement of physical properties of silica fine particles
The following physical properties of the silica fine particles used in Examples 1 to 4 and Comparative Examples 1 to 4 shown in Table 1 were measured.
[1-2-1] Measurement of hydroxyl group concentration
(1) Specific surface area a (m ² / g) per 1 g of silica fine particles was measured by the BET method.
(2) 1 g of silica fine particles was dried at 100 ° C. for 1 hour in a vacuum of 10 ⁻² hPa, then reacted with 10 g of LiAlH _{4 in} 1 L of diethylene glycol dimethyl ether, and the amount of H ₂ generated b (ml) was quantified.
(3) The hydroxyl group concentration was calculated by the following formula.
Hydroxyl concentration (pieces / nm ² ) = (6 × 10 ²³ × b) / (22400 × a × 10 ¹⁸ )
The results are shown in Table 1.

[1-2-2] pH measurement
4 g of each silica fine particle was added to 0.1 liter of water: methanol = 1: 1 solution, and after sufficiently stirring at a liquid temperature of 20 to 25 ° C. for 5 minutes, the pH was measured with a pH meter. The results are shown in Table 1.
[1-3] Production of phosphor-containing composition
Examples described later in Shin-Etsu Chemical Co., Ltd., addition curable silicone resin trade name LPS-2410 (viscosity = 4.7 Pa · s, Type A hardness of cured product = 42) 100 parts by weight (main agent: crosslinking agent = 100: 10) 1 to 4 and 0.5 parts by weight of silica fine particles of Comparative Examples 1 to 4 were added and stirred manually, and then 1 part by weight of the red phosphor obtained in Synthesis Example 1 and the green fluorescence obtained in Synthesis Example 2 were used. 8 parts by weight of the body (Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, median particle size D ₅₀ = 11.5 μm) is added, and the mixture is kneaded for 3 minutes with a stirrer (“Awatori Kentaro” AR-100) manufactured by Shinky Corporation. Thus, a phosphor-containing composition was obtained.

[1-4] Viscosity measurement of phosphor-containing composition
About the fluorescent substance containing composition obtained above, the viscosity in rotor rotation speed 1rpm and 5rpm was measured using the proclamable digital viscometer cone plate type (model | form: RVDV-11) by Brookfield.
The results are shown in Table 1.

[2] Light emitting device
[2-1] Manufacturing of light emitting device
An LED chip “C460-MB290” (emission wavelength = 461 nm) manufactured by CREE was bonded to an SMD LED package “TY-SMD1202B” (2.8 × 3.5 × 1.9 mm thickness) manufactured by Toyo Denpa.
The phosphor-containing compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were filled to the very top of the package with the LED chip, then cured at 150 ° C. for 1 hour and sufficiently cooled to obtain a light emitting device.

[2-2] Evaluation of light emitting device
In a room maintained at a temperature of 25 ° C. ± 1 ° C., an emission spectrum was measured when a drive current of 20 mA was applied. XYZ color specification defined by JIS Z8701 from the wavelength range of 380 nm to 780 nm of the emission spectrum measured using Ocean Optics color / illuminance measurement software and USB2000 series spectrometer (integral sphere specification). Chromaticity values (Cx, Cy, Cz) were calculated as chromaticity coordinates in the system. In this case, the relational expression Cx + Cy + Cz = 1 holds. The results are shown in Table 1.

Further, the distance L = {(Cx ₀ , Cy ₁ ) = (0.33, 0.33) as the target and the chromaticity coordinate point (Cx ₁ , Cy ₁ ) of the completed light emitting device. ^{_{0 -Cx 1) 2 + (Cy}} 0 -Cy 1) 2} was calculated ^1/2.
The results are shown in Table 1.
In the light-emitting device of the present invention, the more the phosphor particles settle in the phosphor-containing composition, the more the wavelength of light emitted from the LED chip by the added phosphor is not sufficiently converted, so L increases. End up.

  In addition, when a blue light emitting LED is used, the more uniformly the phosphor is dispersed, the more efficiently the blue excitation light is absorbed by the phosphor. Therefore, the amount of light emitted from the phosphor increases, so that Cx, Cy On the contrary, Cz becomes a small value. Therefore, since a small Cz value proves that the phosphor is less precipitated, Cz can be used as an index for the degree of sedimentation inhibition of the phosphor.

A: Hydrophobic Aerosil “R8200” manufactured by Nippon Aerosil Co., Ltd.
B: Hydrophobic Aerosil “RY200” manufactured by Nippon Aerosil Co., Ltd.
C: Hydrophobic Aerosil “R972” manufactured by Nippon Aerosil Co., Ltd.
D: Hydrophobic Aerosil "RY200S" manufactured by Nippon Aerosil Co., Ltd.
E: Hydrophilic Aerosil “# 200” manufactured by Nippon Aerosil Co., Ltd.
F: Hydrophilic Aerosil “# 130” manufactured by Nippon Aerosil Co., Ltd.
G: Hydrophilic Aerosil “# 380” manufactured by Nippon Aerosil Co., Ltd.
From the results of Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1, the following was confirmed.

    That is, the phosphor-containing composition to which silica fine particles having a hydroxyl group concentration and a pH within a predetermined range are added has a thixotropic property, but the sedimentation of the phosphor particles is suppressed. The light emitting device produced light emission with a small color shift from the desired white light accompanying the settling of the phosphor particles.

  The phosphor-containing composition of the present invention can suppress the sedimentation of the phosphor even when the viscosity does not increase and the thixotropic property is not exhibited. In addition, the light emitting device of the present invention has a uniform light emission distribution of the phosphor and high quality. Further, since the phosphor is effectively used, it is useful for manufacturing a light emitting device. Further, an image display device and an illumination device using such a light emitting device have a uniform light emission distribution and high quality. Further, since the phosphor is effectively used, it is useful for manufacturing an image display device and a lighting device. Therefore, the phosphor-containing composition, the light-emitting device, the image display device, and the lighting device of the present invention have extremely high industrial applicability in each field.

It is typical sectional drawing which shows one Example of the light-emitting device of this invention. It is typical sectional drawing which shows an example of the surface emitting illumination apparatus using the light-emitting device of this invention. It is a typical perspective view which shows other embodiment of the light-emitting device of this invention.

Explanation of symbols

1 Light-emitting device
2 frames
2A Concave part of the frame
3 Blue LED
4 Phosphor-containing part 5 Silver paste
6 wires
7 Mold part
8 Surface emitting lighting device
9 Diffusion plate
10 Holding case
11 Phosphor content part
12 Light source
13 Substrate

Claims (7)

A phosphor-containing composition containing silica fine particles, a phosphor, and a liquid medium, wherein the hydroxyl concentration of the silica fine particles measured by the following hydroxyl concentration measurement method (I) is 0.3 / nm ² or more, A phosphor-containing composition, wherein the number is ² / nm ² or less.
Hydroxyl concentration measurement method (I)
(1) The specific surface area a (m ² / g) per 1 g of the silica fine particles is measured by the BET method. (2) 1 g of silica fine particles is dried at 100 ° C. for 1 hour in a vacuum of 10 ⁻² hPa, then reacted with 10 g of LiAlH _{4 in} 1 L of diethylene glycol dimethyl ether, and the amount of generated H ₂ b (ml) is quantified.
(3) The hydroxyl group concentration is calculated by the following formula.
Hydroxyl concentration (pieces / nm ² ) = (6 × 10 ²³ × b) / (22400 × a × 10 ¹⁸ ) The phosphor-containing composition according to claim 1, wherein the pH of the silica fine particles measured by the following pH measurement method (II) is 4.5 or more and 7 or less.
pH measurement method (II)
4 g of silica fine particles are added to 0.1 L of water: methanol = 1: 1 solution, and after sufficiently stirring for 5 minutes at a liquid temperature of 20 to 25 ° C., the pH is measured with a pH meter.   The phosphor-containing composition according to claim 1 or 2, wherein the liquid medium is a silicone resin.   The phosphor comprises one or more phosphors selected from Eu-activated nitride phosphors, and one or more phosphors selected from Ce-activated silicate phosphors and Ce-activated oxide phosphors. The phosphor-containing composition according to any one of -3.   The light-emitting device formed using the fluorescent substance containing composition of any one of Claims 1-4.   An image display device formed using the light emitting device according to claim 5.   An illumination device formed using the light emitting device according to claim 5.

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