JP2008260930A - Composition containing fluorescent substance, light emitter, lighting apparatus and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition containing a highly efficient fluorescent substance showing a highly thixotropic property where a settlement of the fluorescent substance is suppressed at the time of loading into an apparatus. <P>SOLUTION: The composition containing the fluorescent substance is characterized by containing (A) silica fine particles, (B) a metal oxide containing at least one selected from the group consisting of Al, Zr and Ti, (C) the fluorescent substance and (D) a liquid medium. Preferably, the content of (B) to that of (A) is not more than 95 wt.% but at least 5 wt.%, preferably the composition containing the fluorescent substance contains (E) inorganic fine particles, (C) the fluorescent substance and (D) a liquid medium in which (E) the inorganic fine particles contain at least two selected from Si, Al, Zr and Ti. <P>COPYRIGHT: (C)2009,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 does not settle between filling and curing of the light-emitting device, the light-emitting device formed using the phosphor-containing composition, and the light-emitting device are formed. The present invention relates to an illumination device and an image display device.

  A phosphor as a wavelength conversion material is a gallium nitride (GaN) light emitting diode with high luminous efficiency, which is attracting attention as a semiconductor light emitting device emitting blue light from the near ultraviolet region as a material of a white light emitting device. Hereinafter, the light emitting device is used in combination with a laser diode (semiconductor laser diode, hereinafter abbreviated as “LD” as appropriate). Used as a light source.

The phosphor is required to have a high efficiency with respect to blue excitation light from the near ultraviolet 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 arrange the phosphor at a desired position of the light-emitting device, a step of filling (injecting) the phosphor-containing composition in which the phosphor is dispersed in a liquid medium is usually performed. Is included. However, during this step, the phosphor settles while the injected phosphor-containing composition is cured, and the distribution of the phosphor within the phosphor-containing composition is biased, resulting in non-uniform emission and fluorescence. There was a problem in the use efficiency of the body. 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 that has a low viscosity when injected and in which the phosphor does not settle between injection and post-curing. 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

Silica fine particles are generally used for thixotropic agents, but silica fine particles have a low bulk density and require a large amount of volume to develop the desired thixotropic properties, and special measures are required for mixing with a liquid medium. It was. In addition, when the excitation wavelength is in the near ultraviolet region shorter than blue, the emission intensity may be reduced due to scattering or absorption.
Therefore, it has been desired to develop a thixotropic agent that exhibits thixotropic properties when added in a smaller amount than conventionally used silica fine particles.

In view of the above-mentioned problems, the present inventors have conducted extensive research and as a result, have made a fluorescent medium comprising a liquid medium and a phosphor.
The inventors have found that by adding a specific thixotropic agent to the light-containing composition, the phosphor-containing composition exhibits high thixotropic properties and the precipitation of the fluorescent material is suppressed, thereby completing the present invention. That is, the gist of the present invention is as follows.
[1] Fluorescence comprising (A) silica fine particles, (B) a metal oxide containing one or more selected from Al, Zr and Ti, (C) a phosphor, and (D) a liquid medium Body-containing composition (hereinafter sometimes referred to as "the phosphor-containing composition of the first invention").
[2] The phosphor according to [1], wherein (B) the metal oxide containing one or more selected from Al, Zr, and Ti is 5% by weight or more and 95% by weight or less based on (A) silica fine particles. Containing composition.
[3] A phosphor-containing composition containing (E) inorganic fine particles, (C) phosphor, and (D) a liquid medium, wherein (E) inorganic fine particles are selected from Si, Al, Zr and Ti A phosphor-containing composition containing the above (hereinafter sometimes referred to as “the phosphor-containing composition of the second aspect of the present invention”).
[4] The phosphor-containing composition according to [3], wherein (E) the content of one or more selected from Al, Zr and Ti in the inorganic fine particles is 0.1 mol% or more and 95 mol% or less.
[5] The phosphor-containing composition according to any one of [1] to [4], wherein (D) the liquid medium is a silicon-containing compound.
[6] The phosphor-containing composition according to any one of [1] to [5], which contains a silane coupling agent.
[7] A light emitting device formed using the phosphor-containing composition according to any one of [1] to [6].
[8] An illumination device formed using the light emitting device according to [7].
[8] An image display device formed using the light emitting device according to [7].

  According to the present invention, it is possible to provide a high-performance phosphor-containing composition that exhibits high thixotropic properties and that suppresses sedimentation of the phosphor during filling into the apparatus. In addition, the light emitting device formed using the phosphor-containing composition of the present invention does not cause unevenness in the distribution of the phosphor in the filling portion, and therefore has high performance without light emission unevenness. In addition, the illumination device and the image display device formed using the light emitting device have high performance without light emission unevenness.

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
The phosphor-containing composition of the present invention is characterized by containing a specific thixotropic agent. When the thixotropic agent used in the present invention is used, the phosphor-containing composition exhibits high thixotropic properties, and in the filling process to the light emitting device, the viscosity is low in the flowing state and is filled to every corner. On the other hand, in a stationary state after filling, the viscosity increases, and the sedimentation of the phosphor is suppressed.

In the phosphor-containing composition of the first present invention, (A) silica fine particles and (B) a metal oxide containing one or more selected from Al, Zr and Ti correspond to the thixotropic agent.
In the phosphor-containing composition of the second aspect of the present invention, (E) inorganic fine particles containing two or more selected from Si, Al, Zr and Ti correspond to the thixotropic agent.

In addition, any phosphor-containing composition of the present invention is characterized by containing (C) a phosphor and (D) a liquid medium.
Furthermore, if any phosphor-containing composition of the present invention is required, it may contain other optional components. Hereinafter, each component will be described.
[1-1] (A) Silica fine particles
As described above, the silica fine particles (A) of the present invention guarantee the role as a thixotropic agent, and specific examples 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 addition effect of silica fine particles is not recognized, and if it is too large, dispersion treatment in the resin becomes difficult.
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. When the average particle diameter is d, the surface area of a 1 g powder is S, and the shape factor is φ.
d = 6 / Sφ
(Source: University of Chemistry Dictionary)

As the silica fine particles used in the present invention, commercially available ones can be used. Specific examples include “Aerosil” (registered trademark) manufactured by Nippon Aerosil Co., Ltd. or Degussa.
[1-2] Metal oxide
(B) The metal oxide containing one or more selected from Al, Zr, and Ti is used in combination with the (A) silica fine particles to secure a role as a thixotropic agent. As the metal oxide of (B), a commercially available one can be used, and specifically, for example, “AEROXIDE Alu C” (registered trademark), “AEROXIDE TiO ₂ P25” (registered trademark), “AEROXIDE TiO” manufactured by Degussa. ₂ P25S ”(registered trademark),“ AEROXIDE TiO ₂ PF2 ”(registered trademark),“ VP Zirconium Oxide 3-YSZ ”,“ VP Zirconium Oxide PH ”.

  The content of (B) is usually 5% by weight or more, preferably 10% by weight or more, more preferably 12% by weight or more, and usually 95% by weight or less, preferably 50% by weight or less based on (A). More preferably, it is 30% by weight or less. If the content of (B) is too small, the sedimentation suppressing effect is insufficient, and if it is too large, the light emission efficiency decreases due to the scattering effect, the ultraviolet absorption effect, and the like.

[1-3] (E) Inorganic fine particles
As described above, the (E) inorganic fine particles of the present invention secure the role as a thixotropic agent, and it can be considered that (A) silica fine particles and (B) metal oxide are integrated. (E) Inorganic fine particles can be manufactured using the same manufacturing method as fumed silica. For example, in the case of an oxide containing Si and Al, the SiCl ₄ gas and AlCl ₃ gas are co-burned with a flame of 1100 to 1400 ° C. in which a mixed gas of H ₂ and O ₂ is burned to be oxidized and hydrolyzed. It is produced by. The same applies when Ti and Zr are contained. (E) The content of one or more selected from Al, Zr and Ti in the inorganic fine particles is usually 0.1 mol% or more, preferably 0.3 mol% or more, more preferably, relative to (E) inorganic fine particles. Is 0.5 mol% or more, usually 95 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less. If the content of one or more selected from Al, Zr, and Ti is too small, the sedimentation suppressing effect is insufficient, and if it is too large, the light emission efficiency decreases due to the scattering effect, the ultraviolet absorption effect, and the like.

(E) Commercially available inorganic fine particles can be used, and specific examples include “AEROSIL MOX 80” (registered trademark) and “AEROSIL MOX 170” (registered trademark) manufactured by Degussa.
[1-4] Thixotropic property and sedimentation inhibiting effect
The reason why the thixotropic agent of the present invention exhibits the above effect is not clear, but is presumed as follows. That is, the phosphor-containing composition of the present invention comprises a thixotropic agent ((A) + (B) or (E)), a phosphor (C), and a liquid medium (D). When (A) silica fine particles or (E) inorganic fine particles, which are one component of a thixotropic agent, are added to the composition system, a network is formed by hydrogen bonding between the hydroxyl groups of (A) silica fine particles or (E) inorganic fine particles. Is done. On the other hand, the reason for the thixotropic property is described as that the network is maintained and exhibits a high viscosity when the stress is small, but the network is disconnected and exhibits a low viscosity when the stress is large. On the other hand, the surface of the phosphor often has hydroxyl groups such as Si—OH, N—OH, and C—OH. When silica fine particles are added to the phosphor-containing composition, the phosphor is incorporated in the network of silica fine particles by hydrogen bonding between the hydroxyl groups of (A) silica fine particles or (E) inorganic fine particles and the hydroxyl groups on the phosphor surface, and the thixotrope. It is presumed to show sex.

However, the present invention adds thixotropic properties by adding inorganic particles such as other metal oxides in addition to the silica fine particles, and the incorporation of the phosphor fine particles into the network composed of the silica fine particles and the liquid medium as compared with the case where the silica fine particles are alone. It is presumed that factors other than the above are acting because it increases extremely. In general, even if a single oxide has a small acid point or has only weak acid strength, there are many examples in which the acid point is increased or the strength is increased by mixing other oxides. For example, SiO ₂ has only a weak acid point, but is known to show strong acidity when mixed with Al ₂ O ₃ (powder material chemistry, Yasuo Arai, Bafukan). The high sedimentation suppression effect in the present invention is considered to be because Coulomb force works between the acid point of the thixotropic agent and the basicity of the surface of the phosphor, and an interaction stronger than the interaction between hydroxyl groups is generated. It is presumed to be the cause of thixotropic and sedimentation-inhibiting effects.

From the above viewpoint, (A) silica fine particles or (E) inorganic fine particles preferably have many hydroxyl groups. From the viewpoint of acid strength, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —ZrO _2. A combination of TiO ₂ —ZrO _{2 and the} like that can provide an acidic point with strong acid strength is preferable. These two metals may be substituted and dissolved. The type of acid varies depending on the reaction, but it may be a brain acid or a Lewis acid. The structure may be crystalline or amorphous.

[1-5] 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, Ca) (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 , aluminate such as Y ₃ Al ₅ O ₁₂ , Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( F, Cl ₂ include _{(Sr, Ca, Ba, Mg} ) 10 halophosphate of _{(PO 4)} or the like _{6 Cl 2, Sr 2 P 2} O 7, the (La, Ce) phosphate PO _4, etc. etc. .

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 separated by commas (,).

[1-5-1] 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, and Y ₂ O ₃ : Eu. 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, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : 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 phosphors such as Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn such as Eu, Mn Activated halophosphate phosphor, (Ba ₃ Mg) Si ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. Activated silicate phosphor, 3.5MgO · 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, etc. Eu, Bi-activated oxide _{Phosphor, (Gd, Y, Lu,} La) 2 O 2 S: Eu, Eu Bi, etc., Bi Tsukekatsusan sulfide phosphor, (Gd, Y, Lu, La) VO 4: Eu, Bi, etc. Eu, Bi activated vanadate phosphors, SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, etc., Ce activated sulfide phosphors such as CaLa ₂ S ₄ : 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 is 1 or more) integer), such as Eu, Ce-activated nitride _{phosphor, (Ca, Sr, Ba,} Mg) 10 (PO 4) 6 (F, C , Br, OH): Eu, Eu such as Mn, Mn-activated halophosphate _{phosphor, ((Y, Lu, Gd} , Tb) 1-x Sc x Ce y) 2 (Ca, Mg) 1-r ( It is also possible to use Ce-activated silicate phosphors such as Mg, Zn) _{2 + r} Si _z-q GeqO _{12 + δ} .

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

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.
[1-5-2] Green phosphor
The phosphor-containing composition of the present invention may contain a phosphor emitting 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 earth silicon oxynitride-based phosphors, broken particles having fractured surfaces, and emitting in the green region (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

In addition, as the green phosphor, Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (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 borate phosphate phosphor, Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu, Zn ₂ SiO ₄ : Mn-activated silicate phosphor such as Mn, CeMgAl ₁₁ O _{19: Tb, Y 3 Al 5} O 12: Tb and Tb such Activated aluminate _{phosphors, Ca 2 Y 8 (SiO 4} ) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4 : Eu, Tb, Sm activated thiogallate phosphor such as Eu, Tb, Sm, etc. Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al , Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, etc. Ce-activated silicate 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 Eu-activated oxynitride such as activated β-sialon and Eu-activated α-sialon Object _{phosphor, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu-activated aluminate phosphor such as Eu, (La, Gd, Y ) 2 Tb activated oxysulfide phosphors such as O ₂ S: Tb, LaPO ₄ : Ce, Tb activated phosphate phosphors such as Ce, Tb, ZnS: Cu, Al, ZnS: Cu, Au, Al, etc. sulfide _{phosphor, (Y, Ga, Lu,} Sc, La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphor such as K, Ce, Tb, etc., Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, (Sr , Ca, Ba) (Al, Ga, in) 2 S 4: Eu activated thiophosphorous such as Eu Laminate-phosphor or thiogallate _{phosphor, (Ca, Sr) 8 (} Mg, Zn) (SiO 4) 4 Cl 2: are possible Eu, Eu such as Mn, the use of the Mn-activated halo-silicate phosphors such .

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.
[1-5-3] Blue phosphor
The phosphor-containing composition of the present invention may contain a phosphor that emits blue fluorescence (hereinafter, referred to as “blue phosphor” as appropriate).

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 growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a 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-based phosphors and fractured particles with fractured surfaces. (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Europium activated alkaline earth aluminate-based phosphor represented by Eu.

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 Salt 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 phosphoric acid such as Eu Salt phosphors, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, Ce activated silicate phosphors such as Y ₂ SiO ₅ : Ce, tungstate phosphors such as CaWO ₄ , (Ba, Sr) , Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, such as Eu, It is also possible to use a Mn-activated borate phosphate phosphor, a Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu, or the like.

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

[1-5-4] 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, and M4 is a tetravalent metal element). 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 At least one element representative of a.) Fluorescent material activated with Ce, such as nitride-based phosphor having a CaAlSiN ₃ structure, and the like.

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.
[1-5-5] 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 in particular, 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.

[1-5-6] 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.

[1-5-7] Phosphor surface treatment
The phosphor used in the present invention preferably has a large number of hydroxyl groups on the surface. If necessary, the number of hydroxyl groups can be increased by surface treatment of the phosphor.
Furthermore, surface treatment may be performed for the purpose of increasing water resistance or for 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 metal phosphate on the surface of the phosphor, (i) a predetermined amount of water-soluble phosphate such as potassium phosphate and sodium phosphate, calcium chloride, strontium sulfate, An alkaline earth metal such as manganese chloride and zinc nitrate, and at least one water-soluble metal salt compound in Zn and Mn are 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.
[1-6] Liquid medium
As the liquid medium to be used, an inorganic material and / or an organic material can be used.

As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having
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. In particular, when a high-power light-emitting device such as illumination is required, it is preferable to use a silicon-containing compound for the purpose of heat resistance and light resistance.

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.

[1-6-1] Silicone material
The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the general composition formula (1) 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 Formula (1)
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 silyl 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 device, it can be used after being sealed with a liquid silicone material and then cured by heat or light.
[1-6-2] 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 material), condensation curing type (condensation type silicone material), and ultraviolet curing type are preferable. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

[1-6-2-1] 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. Commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd.

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

(A) The alkenyl group-containing organopolysiloxane is an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms in one molecule represented by the following composition formula (1a).
R _n SiO _{[(4-n) / 2]} (1a)
(In the formula (1a), 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. At least one of R is an alkenyl group.)
(B) The hydrosilyl group-containing polyorganosiloxane is an organohydrogenpolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule represented by the following composition formula (2a).

R ′ _a H _b SiO [ _{(4-ab) / 2} ] (2a)
(In the formula (2a), R ′ is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding the alkenyl group, and a and b are 0.7 ≦ a ≦ 2.1, 0. (It is a positive number satisfying 001 ≦ b ≦ 1.0 and 0.8 ≦ a + b ≦ 2.6.)
Hereinafter, the addition type silicone material will be described in more detail.

  In R of the above formula (1a), the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group. When R is a hydrocarbon group, those selected from alkyl groups such as a methyl group and an ethyl group, monovalent hydrocarbon groups having 1 to 20 carbon atoms such as a vinyl group and a phenyl group are preferable, and more preferable. Is a methyl group, an ethyl group, or a phenyl group. R may be the same or different from each other, 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).

In the composition formula (1a), 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, Furthermore, the synthesis of this organopolysiloxane becomes difficult.
In addition, (A) alkenyl group containing organopolysiloxane may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Next, the (B) hydrosilyl group-containing polyorganosiloxane acts as a crosslinking agent for curing the composition by performing a hydrosilylation reaction with the (A) alkenyl group-containing organopolysiloxane.
In the composition formula (2a), R ′ represents a monovalent hydrocarbon group excluding an alkenyl group. Here, examples of R ′ include the same groups as those of R in the composition formula (1a) (excluding alkenyl groups). Further, when used for applications requiring UV resistance, at least 80% is preferably a methyl group.

In the composition formula (2a), a is usually a positive number of 0.7 or more, preferably 0.8 or more, and usually 2.1 or less, preferably 2 or less. Moreover, b is 0.001 or more normally, Preferably it is 0.01 or more, and is a positive number normally 1.0 or less. However, a + b is 0.8 or more, preferably 1 or more, and 2.6 or less, preferably 2.4 or less.
Furthermore, (B) hydrosilyl group-containing polyorganosiloxane has at least 2, preferably 3 or more SiH bonds in one molecule.

The molecular structure of the (B) hydrosilyl group-containing polyorganosiloxane 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 usually 3 or more, and usually 1000 or less, preferably 300 or less.
In addition, (B) hydrosilyl group containing polyorganosiloxane may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The blending amount of the (B) hydrosilyl group-containing polyorganosiloxane depends on the total amount of alkenyl groups in the (A) alkenyl group-containing organopolysiloxane. Specifically, the total SiH amount of the (B) hydrosilyl group-containing polyorganosiloxane is usually 0.5 mol times or more, preferably 0.8 mol to the total alkenyl groups of the (A) alkenyl group-containing organopolysiloxane. The amount may be at least mol times, and usually at most 2.0 mol times, preferably at most 1.5 mol times.

  The (C) addition reaction catalyst is a catalyst for accelerating the hydrosilylation addition reaction between (A) the alkenyl group in the alkenyl group-containing organopolysiloxane and (B) the SiH group in the hydrosilyl group-containing polyorganosiloxane. Examples of the addition reaction catalyst (C) include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and platinum bisacetoacetate. And platinum group metal catalysts such as platinum-based catalysts, palladium-based catalysts and rhodium-based catalysts.

In addition, (C) addition reaction catalyst may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The addition amount of the addition reaction catalyst can be a catalytic amount, but as a platinum group metal, the total weight of (A) alkenyl group-containing organopolysiloxane and (B) hydrosilyl group-containing polyorganosiloxane is usually It is preferable to blend 1 ppm or more, particularly 2 ppm or more, and 500 ppm or less, particularly 100 ppm or less.

  In addition to the above (A) alkenyl group-containing organopolysiloxane, (B) hydrosilyl group-containing polyorganosiloxane and (C) addition reaction catalyst, the composition for obtaining an addition-type silicone material is curable as an optional component, Addition reaction control agent for giving pot life, linear nonorganopolysiloxane having alkenyl group for adjusting hardness and viscosity, for example, linear non-reactive organopolysiloxane, number of silicon atoms May contain about 2 to 10 linear or cyclic low molecular organopolysiloxanes within the range not impairing the effects of the present invention.

  The curing conditions for the composition are not particularly limited, but are preferably 120 ° C to 180 ° C and 30 ° C to 180 minutes. If the resulting cured product is in a soft gel form after curing, it must be cured at a low temperature near room temperature for 10 to 30 hours because it has a larger coefficient of linear expansion than a rubber resin or hard plastic silicone resin. Therefore, 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 further 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.

[1-6-2-2] 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, 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 at least one of Ti, Ta, Zr, Hf, Zn, and Sn, 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 condensed 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 condensation type 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 whose peak top position is in a region where the chemical shift is −40 ppm or more and 0 ppm or less with respect to polydimethylsiloxane, 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 polydimethylsiloxane, 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. Hereinafter, the features <1> to <3> will be described.
[1-6-2-2-1] Features <1> (Silicon content)
The silicon content of the silicone material suitable for the present invention is usually 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO2 is 47% by weight.

Note that the silicon content of the silicone-based material is calculated based on the results obtained by performing inductively coupled plasma spectroscopy (hereinafter abbreviated as “ICP” as appropriate), for example, using the following method. be able to.
{Measurement of silicon content}
Silicone material is baked in a platinum crucible in the air at 450 ° C. for 1 hour, then at 750 ° C. for 1 hour, and at 950 ° C. for 1.5 hours to remove the carbon component, and then a small amount of residue is obtained. Add more than 10 times the amount of sodium carbonate and heat with a burner to melt, cool this, add demineralized water, and adjust the pH to neutral with hydrochloric acid to a few ppm as silicon. ICP analysis is performed.

[1-6-2-2-2] Features <2> (Solid Si-NMR spectrum)
When a solid Si-NMR spectrum of a silicone-based material suitable for the present invention is measured, at least one peak in the peak region of (a) and / or (b) derived from a silicon atom to which a carbon atom of an organic group is directly bonded, Preferably, a plurality of peaks are observed.
When organized by chemical shift, in the silicone-based material suitable for the present invention, the half width of the peak described in (a) is generally the case of the peak described in (b) described later because molecular motion is less restricted. It is smaller, usually 3.0 ppm or less, preferably 2.0 ppm or less, and usually 0.3 ppm or more.

On the other hand, the full width at half maximum of the peak described in (b) is usually 5.0 ppm or less, preferably 4.0 ppm or less, and usually 0.3 ppm or more, preferably 0.4 ppm or more.
If the half-value width of the peak observed in the chemical shift region is too large, the molecular motion is constrained and strain is large, cracks are likely to occur, and the member may be inferior in heat resistance and weather resistance. For example, in the case where a large amount of tetrafunctional silane is used, or in the state where rapid drying is performed in the drying process and a large internal stress is stored, the full width at half maximum is larger than the above range.

In addition, if the half width of the peak is too small, Si atoms in the environment will not be involved in siloxane crosslinking, and heat resistance is higher than substances formed mainly from siloxane bonds, such as examples where trifunctional silane remains in an uncrosslinked state. -It may be a member inferior in weather resistance.
However, in a silicone material containing a small amount of Si component in a large amount of organic component, good heat resistance / light resistance and coating performance can be obtained even if the peak of the above-mentioned half width range is observed at -80 ppm or more. There may not be.

The chemical shift value of the silicone material suitable for the present invention can be calculated based on the results of solid Si-NMR measurement using the following method, for example. In addition, analysis of measurement data (half-width or silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.
{Solid Si-NMR spectrum measurement and silanol content calculation}
When performing a solid Si-NMR spectrum about a silicone type material, a solid Si-NMR spectrum measurement and waveform separation analysis are performed on condition of the following. Further, from the obtained waveform data, the half width of each peak is determined for the silicone material. Also, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Ask.

{Device conditions}
Apparatus: Chemmagnetics Infinity CMX-400 Nuclear magnetic resonance spectrometer
29Si resonance frequency: 79.436 MHz
Probe: 7.5mmφCP / MAS probe
Measurement temperature: room temperature
Sample rotation speed: 4 kHz
Measurement method: Single pulse method
1H decoupling frequency: 50 kHz
29Si flip angle: 90 °
29Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 times
Observation width: 30 kHz
Broadening factor: 20Hz
Reference sample Polydimethylsiloxane
For silicone-based materials, 512 points are taken as measurement data, zero-filled to 8192 points, and Fourier transformed.

{Waveform separation analysis method}
For each peak of the spectrum after Fourier transform, optimization calculation is performed by a non-linear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.
The peak is identified by AIChE Journal, 44 (5), p. 1141,
Refer to 1998 and so on.

[1-6-2-2-3] Features <3> (Silanol content)
In the silicone material suitable for the present invention, the silanol content of the cured product obtained by curing this is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight. In addition, the range is usually 10% by weight or less, preferably 8% by weight or less, and more preferably 5% by weight or less. By reducing the silanol content, there is little change over time, excellent long-term performance stability, and excellent performance with low moisture absorption and moisture permeability. However, since a member containing no silanol is inferior in adhesion, there exists an optimum range for the silanol content as described above.

  In addition, the silanol content rate of a silicone type material performs solid Si-NMR spectrum measurement, for example using the method demonstrated in (Solid Si-NMR spectrum measurement and calculation of silanol content rate) of (Solid Si-NMR spectrum), From the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms can be obtained and compared with the silicon content analyzed separately.

In addition, since the silicone material suitable for the present invention contains an appropriate amount of silanol, the silanol hydrogen bonds to the polar portion present on the device surface, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.
In addition, the silicone material suitable for the present invention forms a covalent bond by dehydration condensation with the hydroxyl group on the device surface by heating in the presence of an appropriate catalyst, and exhibits stronger adhesion. Can do.

On the other hand, if there is too much silanol, the inside of the system will thicken and it will be difficult to apply, or it will become more active and solidify before the light-boiling components volatilize by heating, leading to increased foaming and internal stress. It may occur and induce cracks.
[1-6-3] 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.

The viscosity of the liquid medium is usually 100 mPa.s. s or more, preferably 800 mPa · s or more, more preferably 1500 mPa · s or more.
[1-7] Silane coupling agent
Silane coupling agent used in the present invention is not particularly limited, specifically, it may be mentioned compounds represented by e.g. X～SiR ¹ Formula of R ² R ^3. Silane coupling agents have two or more different reactive groups in the molecule. That is, for example, X is a group that reacts with or has affinity with organic substances such as an alkyl group, an amino group, a vinyl group, and an epoxy group. On the other hand, R ¹ , R ² and R ³ are hydrolyzable groups such as a methoxy group and an ethoxy group. Such a silane coupling agent exhibits an action as a binder of an organic material and an inorganic material which are usually difficult to bond. In the present invention, it is presumed that a bond is formed between the phosphor and the liquid medium to suppress the precipitation of the phosphor.

In addition, as a silane coupling agent, Preferably, the compound which has a structure of X-Si (OR) ₃ is mentioned. In the formula, X represents an organic group, preferably an alkyl group having usually 1 or more carbon atoms, preferably 3 or more, more preferably 5 or more. If the number of carbon atoms is small, it may be difficult to bond the phosphor and the active resin portion spatially because it is rigid. R usually represents an alkyl group having 1 or more carbon atoms, and specific examples thereof include a methyl group and an ethyl group.

Commercially available silane coupling agents can be used, and specific examples include silane coupling agents manufactured by Toray Dow Corning, Shin-Etsu silane coupling agents, and the like.
The amount of the silane coupling agent added to the phosphor composition is usually 0.1 to 30% by weight, preferably 0.2 to 3% by weight. If the amount is too small, sufficient bonding cannot be obtained, and if the amount is too large, it is conceivable that an excess part not used for bonding is separated from the liquid medium.

[1-8] 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 light diffusing material, and a filler can be used.

[1-9] Method for producing phosphor-containing composition
The method for producing the phosphor-containing composition of the present invention is not particularly limited, and is a thixotropic agent (component (A) and component (B) or (E)), (C) phosphor, silane coupling agent, and as necessary. The additive to be added according to the method (D) may be any method that uniformly disperses in the liquid medium.
The amount of the thixotropic agent (component (A) and component (B) or component (E)) 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 (D). is there. Moreover, it is 20 parts weight or less normally, Preferably it is 10 parts weight or less, More preferably, it is 5 parts weight or less. If the amount of the thixotropic agent is too small, the effect is not exhibited, and if it is too large, dispersion becomes difficult.

The blending amount of the phosphor (C) 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 (D). 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.
(D) When a silicone resin is used as the liquid medium, for example, a silicone resin, a phosphor, a thixotropic agent, a crosslinking agent, a curing catalyst, an extender, and other additives are blended, and a mixer, a high-speed disper, a homogenizer It can manufacture by a conventionally well-known method, such as mixing with 3 rolls, 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.

[1-10] Physical properties of phosphor-containing composition
[1-10-1] 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, usually 30000 mPa · s or less, preferably 20000 mPa · s or less, more preferably. Is 15000 mPa · s or less, particularly preferably 10,000 mPa · s or less, and particularly preferably 8000 mPa · s or less. When potting a container having a recess, a level of 20000 mPa · s or less, which is easy to level, is easy to handle and defoaming is desirable. When maintaining the shape of the coating solution is important, such as coating on a light-emitting device of a chip-on-board type without a reflector, it is preferable to have a thixotropic property of 15000 mPa · s or higher. If the viscosity is too high, it may cause trouble such as blockage of pipes at the time of injection, and bubbles may be difficult to escape, and further, lead wires of semiconductor elements 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 has thixotropic properties so that the phosphor-containing composition can be sufficiently filled (injected) into the light emitting device, and the phosphor does not settle before the liquid medium is cured after filling. . The thixotropic property can be confirmed by the fact that the viscosity at 1 rpm is larger than the viscosity at 5 rpm in the B-type viscometer 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 the present invention emits light that excites the phosphor. 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 GaN-based LEDs, those having an InxGayN light-emitting layer are particularly preferred because the emission intensity is very strong, and in GaN-based LDs, those having a multiple quantum well structure of an InxGayN layer and a GaN layer have an emission intensity. It is particularly preferred because it is very strong.

In the above, the value of x + y is usually in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light emitting layer, p layer, n layer, electrode, and substrate as basic components, and the light emitting layer is 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 arbitrary modifications.
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. Also with these colors
It may be an intermediate color between white. Further, the transparent resin is a sealing material for the phosphor-containing portion 4, and here, the above-described sealing material is 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. Part of the emitted light is absorbed in the phosphor-containing portion 4 by the phosphor of the present invention, which is a wavelength conversion material, and another phosphor added as necessary, and converted into light having a longer wavelength. Light emission with high luminance is obtained by mixing with blue light or the like that has not been absorbed. 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.

[3] Applications of light emitting devices
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 22 lm / W or higher, more preferably 25 lm / W or higher, particularly preferably 28 lm / W or higher, and an average color rendering index Ra of 80. Above, preferably 85 or more, more preferably 88 or more.

The average color rendering index Ra is calculated according to JIS Z 8726.
The light emission efficiency is calculated as follows by the product of the quantum absorption efficiency αq and the internal quantum efficiency ηi.
First, a phosphor sample to be measured (for example, powder) is packed in a cell with a sufficiently smooth surface so that measurement accuracy is maintained, and is attached to a spectrophotometer with an integrating sphere. Examples of the spectrophotometer include “MCPD2000” manufactured by Otsuka Electronics Co., Ltd. An integrating sphere or the like is used so that all the photons reflected by the sample and the photons emitted from the sample by photoluminescence can be counted, that is, photons that are not counted and fly out of the measurement system are eliminated.

  A light source for exciting the phosphor is attached to the spectrophotometer. This light emission source is, for example, an Xe lamp or the like, and is adjusted using a filter or the like so that the emission peak wavelength is 400 nm. The sample to be measured is irradiated with light from the light source adjusted to have a wavelength peak of 400 nm, and the emission spectrum is measured. In actuality, the measured spectrum includes light emitted from the excitation light source (hereinafter simply referred to as “excitation light”), photons emitted from the sample by photoluminescence, and excitation light reflected from the sample. Minutes of photon contributions overlap.

The quantum absorption efficiency αq is a value obtained by dividing the number of photons Nabs of excitation light absorbed by the sample by the total number of photons N of excitation light.
First, the total photon number N of the latter excitation light is obtained as follows. That is, a reflecting plate such as a substance having a reflectance R of almost 100% with respect to the excitation light, for example, “Spectralon” manufactured by Labsphere (having a reflectance of 98% with respect to 400 nm excitation light) is measured. Is attached to the spectrophotometer and the reflection spectrum Iref (λ) is measured. Here, the numerical value obtained from the reflection spectrum Iref (λ) by the following (formula 1) is proportional to N.

  Here, the integration interval may be substantially only the interval where Iref (λ) has a significant value. The number of photons Nabs of the excitation light absorbed by the former sample is proportional to the amount obtained by the following (formula 2).

  Here, I (λ) is the reflection spectrum when the target sample for which the absorption efficiency αq is to be obtained is attached. The integration range of (Expression 2) is the same as the integration range defined in (Expression 1). By limiting the integration range in this way, the second term of (Equation 2) corresponds to the number of photons generated by the target sample reflecting the excitation light, that is, out of all photons generated from the target sample. This corresponds to the one excluding the photons generated by the photoluminescence by the excitation light. Since an actual spectrum measurement value is generally obtained as digital data divided by a certain finite bandwidth with respect to λ, the integrals of (Equation 1) and (Equation 2) are obtained by the sum based on the bandwidth.

From the above, αq = Nabs / N = (Expression 2) / (Expression 1).
Next, a method for obtaining the internal quantum efficiency ηi will be described. ηi is a value obtained by dividing the number NPL of photons generated by photoluminescence by the number Nabs of photons absorbed by the sample. Here, NPL is proportional to the amount obtained by (Equation 3) below.
∫λ · I (λ) dλ (Formula 3)
At this time, the integration interval is limited to the wavelength region of photons generated from the sample by photoluminescence. This is because the contribution of photons reflected from the sample is removed from I (λ). Specifically, the lower limit of the integration of (Expression 3) is the upper end of the integration of (Expression 1), and the upper limit is a range suitable for including a photoluminescence-derived spectrum.

Thus, ηi = (Expression 3) / (Expression 2) is obtained.
The integration from the spectrum that has become digital data is the same as when αq is obtained.
And the luminous efficiency defined by this invention is calculated | required by taking the product of quantum absorption efficiency (alpha) q calculated | required as mentioned above and internal quantum efficiency (eta) i.

  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] Method for synthesizing phosphor
[1-1] Synthesis Example 1: Synthesis of green phosphor
Barium carbonate (BaCO ₃ ), strontium carbonate (SrCO ₃ ), europium oxide (Eu ₂ O ₃ ), silicon dioxide (SiO ₂ ) as raw material compounds: ratio of 1.39: 0.46: 0.15: 1.0 Weighed so that This was pulverized and mixed with ethanol in an agate mortar, and the ethanol was vaporized and removed. The obtained mixture was packed in an alumina crucible and baked at 1100 ° C. for 8 hours in nitrogen. By thoroughly mixing 2% by weight of strontium chloride (SrCl ₂ ) with the obtained fired product so as to be uniform, it was again packed in an alumina crucible and heated at 1200 ° C. for 6 hours in a nitrogen atmosphere mixed with 4% hydrogen. Reacted. Subsequently, a powder of green phosphor Ba _1.39 Sr _0.46 SiO ₄ : Eu _0.15 (D ₅₀ = 21.0 μm) (hereinafter referred to as “BSS”) was obtained by performing pulverization. .

[1-2] Synthesis Example 2: Synthesis of green phosphor
The green phosphor obtained in Synthesis Example 1 was surface treated as follows.
Ammonia water was manufactured by Kishida Chemical Co., Ltd., and had a special grade purity of 28%.
In a 500 mL flask, put 50 g of tetraethoxysilane (hereinafter referred to as “TEOS”) with a purity of 95% or more and 224 g of ethanol with a purity of 99.5% with a purity of 99.5% from Kishida Chemical Co. An alkoxide solution was prepared.

A jacketed 1 L separable flask was charged with 310 g of ethanol and 100 g of aqueous ammonia and mixed uniformly, and then 50 g of BSS powder was added to prepare a base phosphor-containing solution.
A temperature-controlled cooling water is allowed to flow through the jacket of the separable flask to keep the temperature of the reaction solution constant at 5 ° C., and the substrate phosphor-containing solution is vigorously stirred with a stirring blade equipped with a motor so that the BSS powder does not settle. Then, the metal alkoxide solution was dropped into the BSS powder over about 4 hours using a metering pump.

After the dropping of the metal alkoxide solution was completed, the reaction solution was allowed to stand to settle the green phosphor, and then the liquid phase clouded with silica fine particles was removed by decantation. Then 500 mL
Of ethanol was added, and the mixture was lightly stirred and allowed to stand, and the liquid layer in which white turbidity remained was removed by decantation. This ethanol washing is repeated 4 times until the liquid layer becomes colorless and transparent, and the separable flask is dried under reduced pressure at 50 ° C. for 30 minutes, and then dried at 150 ° C. for 2 hours to obtain a silica adhesion rate of 24.0. A BSS phosphor powder coated with silica on the surface by weight was obtained.

[1-3] Synthesis Example 3: Synthesis of orange phosphor
A surface-treated orange phosphor Sr ₂ BaSiO ₅ : Eu (D ₅₀ = 40.7 μm) (hereinafter referred to as “SBS”) was used. In this phosphor, SrCO ₃ , BaCO ₃ , SiO ₂ , Eu ₂ O ₃ are weighed as raw material compounds so as to have a ratio of Sr: Ba: Si: Eu = 1.98: 1: 1: 0.02. After crushing and mixing with ethanol in an agate mortar and evaporating and removing ethanol, the resulting mixture is molded into tablets and heated at 1450 ° C. for 6 hours in a nitrogen atmosphere mixed with 3% hydrogen on a molybdenum foil. To obtain a powder by subsequent pulverization.

The surface treatment was performed as follows.
Ammonia water was manufactured by Kishida Chemical Co., Ltd., and had a special grade purity of 28%.
3 g of SBS powder is put into a 100 mL flask, 30 g ethanol of special grade 99.5% ethanol and 6 g ammonia water, and tetraethoxysilane with a purity of 95% or more (hereinafter referred to as “TEOS”) manufactured by Tokyo Chemical Industry Co., Ltd. 1.5 g was added and mixed uniformly, and stirred at room temperature for 30 minutes using a magnetic stirrer. Further, 1.5 g of TEOS was added and mixed uniformly, and stirred at room temperature for 30 minutes using a magnetic stirrer. After the reaction solution was allowed to stand and the orange phosphor settled, the liquid phase clouded with silica fine particles was removed by decantation. Thereafter, 30 mL of ethanol was added, and the mixture was lightly stirred and then allowed to stand, and the liquid layer with white turbidity was removed by decantation. This ethanol washing was repeated four times until the liquid layer became colorless and transparent, and the separable flask was dried under reduced pressure at 150 ° C. for 2 hours to obtain an SBS phosphor powder coated with silica at a surface adhesion rate of 10% by weight. It was.

[1-4] Synthesis Example 4: Synthesis of condensation-type silicone liquid medium X
140 g of both-end silanol dimethyl silicone oil “XC96-723” manufactured by GE Toshiba Silicone, 14 g of phenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonate powder as a catalyst were prepared. Was weighed in a three-necked Kolben equipped with a catalyst and stirred at room temperature for 15 minutes until the catalyst was sufficiently dissolved. Thereafter, the reaction solution was heated to 120 ° C. and subjected to initial hydrolysis while stirring at 120 ° C. for 30 minutes under total reflux.

Subsequently, nitrogen was blown in with SV20 and stirred at 120 ° C. while distilling off the generated methanol, moisture and by-product low boiling silicon components, and the polymerization reaction was further advanced for 6 hours. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, then transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa for 20 minutes on an oil bath using a rotary evaporator. The low boiling silicon component was distilled off to obtain a solvent-free condensation-type silicone liquid medium X (viscosity = 0.8 Pa · s).
[2] Method for producing phosphor-containing composition
[2-1] Synthesis Example 5: Production of phosphor-containing composition K
Examples 1 to 3 and 5 described in Table 1 and 3 to 5 parts by weight of Aerosil of Comparative Examples 1 and 2 were added to the condensation type silicone liquid medium X (100 parts by weight) of Synthesis Example 3 and stirred manually. Thereafter, 0.75 parts by weight of a silane coupling agent n-C ₁₀ H ₂₁ —Si (OMe) ₃ manufactured by Toray Dow Corning was added and further stirred by hand. Red phosphor (CaAlSiN ₃ : Eu, median particle size D ₅₀ = 8.2 μm) 0.8 part by weight, green phosphor obtained in Synthesis Example 2 1.5 part by weight and blue phosphor ((Ba _0.7 , Eu _0.3 ) MgAl ₁₀ O ₁₇ , 23.2 parts by weight with a particle size D ₅₀ = 6.0 μm), and knead for 3 minutes with a stirring device (Shintaro Kentaro AR-100, manufactured by Shinky). A phosphor-containing composition K was obtained.

[2-2] Synthesis Example 6: Production of phosphor-containing composition L
Addition-curable silicone resin trade name LPS-2410 (viscosity = 4.7 Pa · s, Type A hardness = 42) manufactured by Shin-Etsu Chemical Co., Ltd. 100 parts by weight (main agent: cross-linking agent = 100: 10) After adding 1 part by weight of Aerosil of Example 4 and stirring manually, 0.75 parts by weight of silane coupling agent n-C ₁₀ H ₂₁ -Si (OMe) ₃ manufactured by Toray Dow Corning Co., Ltd. was added and further stirring was performed. . Add 6.3 parts by weight of the SBS phosphor obtained in Synthesis Example 3 and 5.6 parts by weight of the green phosphor obtained in Synthesis Example 1, and use a stirring device (Shintaro Kentaro AR-100) manufactured by Shinky Corporation. The phosphor-containing composition L was obtained by kneading for 3 minutes.

[3] Method for evaluating phosphor-containing composition
The following tests were conducted on the phosphor-containing compositions of Examples 1 to 5 and Comparative Examples 1 and 2. The results are shown in Table 1.
[3-1] Sedimentation test
After preparing the phosphor-containing composition, it was allowed to stand for 6 hours, and whether or not any of the three phosphors had settled on the bottom of the container was visually observed. The paste mixed in three colors is cream, but when it settles, the bottom color changes to green, red, etc., so the presence or absence of sedimentation can be easily recognized.

Evaluation was made with “Yes” indicating that sedimentation was observed and “No” indicating no sedimentation.
[3-2] Viscosity measurement and thixotropic evaluation
Viscosity at a rotor rotation speed of 1 rpm and 5 rpm was measured using a Proclama full digital viscometer cone plate type (model: RVDV-11) manufactured by Brookfield.

* “-” In the table indicates that the test was not performed.
* Thixotropic agent ((A), (B) and (E))
A agent (Degussa hydrophilic Aerosil "COK84"; _SiO 2 84 _{wt%, Al 2 O 3 16%} )
Agent B (Degussa Hydrophilic Aerosil “MOX80”)
Agent C (Degussa Hydrophilic Aerosil “MOX170”)
Agent D (Degussa Hydrophilic Aerosil “# 200”) 5 parts by weight
Agent E (Degussa Hydrophobic Aerosil “RY200”) 5 parts by weight
* Liquid medium
X: Condensation type silicone liquid medium X of Synthesis Example 3 (viscosity = 0.8 Pa · s)
LPS-2410: Addition-curing silicone resin trade name “LPS-2410” manufactured by Shin-Etsu Chemical Co., Ltd. (viscosity = 4.7 Pa · s, Type A hardness = 42)
* Silane coupling agent: “AY43-210MC” manufactured by Toray Dow Corning

The phosphor-containing composition of the present invention exhibits high thixotropic properties, and can suppress sedimentation of the phosphor during filling into the apparatus. In addition, the light emitting device of the present invention has high performance without uneven light emission because there is no bias in the distribution of phosphors in the filling portion. In addition, an image display device and a lighting device using such a light emitting device have high performance without light emission unevenness.
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 (first light emitter)
4 Phosphor-containing part (second light emitter)
5 Adhesive
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 (9)

  A phosphor-containing composition comprising (A) silica fine particles, (B) a metal oxide containing one or more selected from Al, Zr and Ti, (C) a phosphor, and (D) a liquid medium object. (B) The phosphor-containing composition according to claim 1, wherein the metal oxide containing one or more selected from Al, Zr and Ti is 5 wt% or more and 95 wt% or less with respect to (A) silica fine particles.
  (E) A phosphor-containing composition containing inorganic fine particles, (C) phosphor, and (D) a liquid medium, wherein (E) the inorganic fine particles contain two or more selected from Si, Al, Zr and Ti A phosphor-containing composition characterized by comprising:   (E) The phosphor-containing composition according to claim 3, wherein the content of one or more selected from Al, Zr and Ti in the inorganic fine particles is 0.1 mol% or more and 95 mol% or less.   (D) The phosphor-containing composition according to any one of claims 1 to 4, wherein the liquid medium is a silicon-containing compound.   The phosphor-containing composition according to any one of claims 1 to 5, comprising a silane coupling agent. The light-emitting device formed using the fluorescent substance containing composition of any one of Claims 1-6.
  A lighting device formed using the light emitting device according to claim 7.   An image display device formed using the light emitting device according to claim 7.

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