JP2010100743A - Method for producing phosphor-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a phosphor-containing composition whose cured product hardly contains air bubbles and which can uniformly disperse a phosphor. <P>SOLUTION: There is provided a method for producing a phosphor-containing composition containing a filler (A), a phosphor (B), and a liquid medium (C). The filler (A), the phosphor (B), and the liquid medium (C) are stirred and mixed in a vessel having a shape in which a cylindrical internal surface is connected to the bottom surface with a smooth curved surface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a phosphor-containing composition. More specifically, the present invention relates to a method for producing a phosphor-containing composition in which phosphors are not aggregated and bubbles are less likely to be mixed in a cured product.

  A semiconductor light-emitting device usually applies a phosphor-containing composition containing a phosphor and a liquid medium onto a semiconductor light-emitting element (hereinafter also referred to as “LED” as appropriate), and dries and cures the LED. Manufactured by sealing. In addition, the LED may be sealed with a multilayer structure in which a liquid medium containing no phosphor is applied, dried, and cured on the LED, and further, a phosphor-containing composition containing the phosphor and the liquid medium is applied and dried. . In any case, the phosphor is used for the purpose of uniformly dispersing the phosphor in the phosphor-containing composition, or for the purpose of imparting the scattering effect in the cured product of the phosphor-containing composition or the conductivity to the cured product. A filler may be included in the phosphor-containing composition. In addition, a drying process is abbreviate | omitted when a fluorescent substance containing composition does not contain a solvent. For such a phosphor-containing composition, various compositions are disclosed in consideration of the physical properties and properties of the phosphor and the liquid medium (see Patent Documents 1 to 4).

JP 2006-77234 A JP 2006-294821 A JP 2002-338833 A International Publication 2006/090804 Pamphlet

However, when a sealing material or the like is produced using the phosphor-containing composition, bubbles remain in the cured product of the phosphor-containing composition, light is refracted or scattered, and the cured product has low adhesion. In some cases, the bubbles expand due to heat and cracks occur.
Therefore, it has been desired to provide a method for producing a phosphor-containing composition that contains less bubbles in the cured product and that can uniformly disperse the phosphor.

  The present invention was devised in view of the above problems, and provides a method for producing a phosphor-containing composition that is less likely to contain bubbles in a cured product and can uniformly disperse a phosphor. With the goal.

  When the present inventors diligently researched about the manufacturing method of the fluorescent substance containing composition which can satisfy said objective, the bubble of the hardened | cured material of a fluorescent substance containing composition contains each material of fluorescent substance containing composition. It has been found that gas, moisture, and bubbles entrained by the mixing operation of materials are the cause.

  From these things, it is less likely that the cured product contains bubbles by separating the gas and moisture contained in each material of the phosphor-containing composition from the material, and further reducing the entrained bubbles by the mixing operation of the materials. In addition, the inventors have found that a method for producing a phosphor-containing composition capable of uniformly dispersing the phosphor can be provided, and the present invention has been completed.

  That is, the gist of the present invention is a method for producing a phosphor-containing composition containing (A) a filler, (B) a phosphor, and (C) a liquid medium, wherein (A) the filler, (B) the phosphor And (C) a method of producing a phosphor-containing composition, wherein the liquid medium is mixed and stirred in a container having a shape in which a cylindrical inner surface is connected to the bottom surface with a smooth curved surface (claims). 1).

  In addition, it is preferable that the mixing and stirring is performed in a container in which the central portion of the bottom surface is formed in a shape that rises smoothly and concentrically with respect to the cylindrical inner surface (Claim 2).

  According to the present invention, by separating the gas contained in each material of the phosphor-containing composition from the material, and further reducing the entrained bubbles by the mixing operation of the material, the cured product is less likely to contain bubbles, Moreover, the manufacturing method of the fluorescent substance containing composition which can disperse | distribute fluorescent substance uniformly can be provided.

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

The present invention is a method for producing a phosphor-containing composition comprising (A) a filler, (B) a phosphor, and (C) a liquid medium, wherein (A) the filler, (B) the phosphor, and (C ) A method for producing a phosphor-containing composition, wherein a liquid medium is mixed and stirred in a container having a shape in which a cylindrical inner surface is connected to a bottom surface with a smooth curved surface.
In the following description, first, materials used in the method for producing the phosphor-containing composition of the present invention will be described in order, and then the method for producing the phosphor-containing composition will be described focusing on each of the above steps.

[1. material]
<1-1. (A) Filler>
The phosphor-containing composition produced by the production method of the present invention (hereinafter sometimes referred to as “the phosphor-containing composition according to the present invention”) contains (A) a filler. The filler (A) referred to in the present invention is a phosphor-containing composition such as a thixo material, a light diffusing material, a refractive index adjusting material, an aggregate, a linear expansion coefficient control material, a stress relaxation material, a heat conduction material, and a conductive material. It is a fine particle that is mixed in order to impart functionality.
As the (A) filler, arbitrary fine particles can be used as long as the effects of the present invention are not significantly impaired. For example, the filler may be an inorganic filler (hereinafter also referred to as “inorganic particles”). Further, it may be composed of an organic / inorganic hybrid component such as an organosilicon compound filler. Furthermore, (A) In addition to the dispersibility and wettability of the filler, any surface treatment may be performed to improve the target functional expression. (A) A filler may use only 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Among those mentioned above, inorganic particles are preferred as the (A) filler.
Examples of the inorganic particles include inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and diamond particles, depending on the purpose. However, the present invention is not limited to these. In addition, inorganic particle | grains may use only 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The form of the inorganic particles may be any form depending on the purpose, such as powder form, slurry form, etc., but when it is necessary to maintain transparency, the phosphor-containing composition of the present invention has the same refractive index, It is preferable to add to the phosphor-containing composition as a solvent-based transparent sol.

(Effect of inorganic particles)
(A) The phosphor-containing composition according to the present invention containing inorganic particles as a filler can be used as a semiconductor light-emitting device member forming liquid for forming a semiconductor light-emitting device member. The semiconductor light emitting device using the member can improve the optical characteristics and workability, and can obtain any of the following effects [1] to [5].

[1] By mixing inorganic particles as a light scattering material in the semiconductor light emitting device member and scattering the light of the semiconductor light emitting device, the light amount of the semiconductor light emitting element that hits the phosphor is increased, and the wavelength conversion efficiency is improved. The directivity angle of light emitted from the semiconductor light emitting device to the outside can be widened.
[2] Generation of cracks can be prevented by blending inorganic particles as a binder in the semiconductor light emitting device member.
[3] By blending inorganic particles as a viscosity modifier in the member forming liquid for a semiconductor light emitting device, the viscosity of the forming liquid can be increased.
[4] By adding inorganic particles to the semiconductor light-emitting device member, the shrinkage can be reduced.
[5] By blending inorganic particles into the semiconductor light emitting device member, the refractive index can be adjusted, and the light extraction efficiency can be improved.

  What is necessary is just to adjust the mixing ratio of the inorganic particle in the member formation liquid for semiconductor light-emitting devices according to the objective of an inorganic particle. In this case, the effect obtained depends on the type and amount of the inorganic particles to be mixed.

  For example, when the inorganic particles are ultrafine silica particles having a particle size of about 10 nm to 100 nm (made by Nippon Aerosil Co., Ltd., trade names: AEROSIL # 200 or AEROSIL # RX200), the thixotropic property of the member forming liquid for semiconductor light emitting devices is high. Since it increases, the effect [3] is great.

  Further, when the inorganic particles are crushed silica or spherical silica having a particle size of about several μm, there is almost no increase in thixotropic property, and the function as an aggregate of a member for a semiconductor light emitting device is the center. And the effect of [4] is great.

  Further, when inorganic particles having a particle size of about 0.1 μm to 10 μm having a refractive index different from that of the semiconductor light emitting device member are used, light scattering at the interface between the semiconductor light emitting device member and the inorganic particles becomes large. ] Has a great effect.

  Further, when inorganic particles having a particle diameter of 1 nm to 10 nm, specifically a light emitting wavelength or less, having a refractive index larger than that of the semiconductor light emitting device member are used, the refractive index is maintained while maintaining the transparency of the semiconductor light emitting device member. Therefore, the effect [5] is great.

  Accordingly, the type of inorganic particles to be mixed may be selected according to the purpose. Moreover, the kind may be single and may combine multiple types. Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.

((A) Filler shape)
Median particle diameter D ₅₀ of the (A) Filler (primary particles) is not limited as long as the effect does not significantly impair the of the present invention, usually below (B) the degree 1/10 median particle diameter D ₅₀ of the phosphor It is. Specifically, it may be appropriately selected according to the purpose. For example, when the (A) filler is used as a light scattering material, the median particle size is preferably from 0.1 μm to 10 μm. For example, if the (A) filler is used as an aggregate, the median particle size is preferably 1 nm or more and 10 μm or less. For example, if (A) filler is used as a thickener (thixotropic agent), the median particle size is preferably 10 nm or more and 100 nm or less. Further, for example, if the (A) filler is used as a refractive index adjusting agent, the median particle size is preferably 1 nm or more and 10 nm or less.

  (A) The particle size distribution (QD) of the filler is preferably small in order to align the dispersion state of the (A) filler in the phosphor-containing composition, but in order to reduce the particle size distribution, the classification yield is lowered and the cost is reduced. Because of this tendency, it is usually 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more, and usually 0.4 or less, preferably 0.3 or less, more preferably 0.2 or less. is there.

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) Filler is disperse | distributed to solvents, such as ethylene glycol, in the environment of temperature 25 degreeC and 70% of humidity. The dispersion is measured with a laser diffraction particle size distribution measuring device (Horiba LA-300) in a particle size range of 0.1 μm to 600 μm, and a weight-based particle size distribution curve is created. Integrated value in the resulting 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.

  (A) The shape of the filler is not limited as long as the effects of the present invention are not significantly impaired, and can take any shape. For example, when (A) the filler is filled with high density as an aggregate or a heat conductive material, the shape of the (A) filler is preferably close to a true sphere. Specifically, the aspect ratio (minimum length / maximum length) of the particle projection image is usually 0.75 or more, preferably 0.8 or more, and more preferably 0.85 or more. Moreover, it is 1.0 or less normally, Preferably it is 0.98 or less, More preferably, it is 0.95 or less. On the other hand, the tensile strength of the cured product can be increased by increasing the aspect ratio of the filler (A). In this case, the aspect ratio is usually 0.1 or more, preferably 0.2 or more, more preferably 0.25 or more, and usually 0.75 or less, preferably 0.7 or less, more preferably 0.5 or less. It is. When fumed silica or the like is contained as a thixo material, primary particles of several nm gather and aggregate to form an aggregated amorphous aggregated particle, and the maximum diameter of the aggregated particle is usually 1 μm or less, preferably 500 μm or less. The thickness is preferably 100 μm or less in order to maintain transparency and uniformity and to exhibit appropriate thixotropy. (A) When the filler is a nanoparticle such as an inorganic oxide that imparts high refraction, it is preferably a single crystal of a high refractive index inorganic oxide for higher refraction, among which cubic and rectangular solids The shape is preferably a plate or plate.

((A) Filler content)
The content of the inorganic particles in the phosphor-containing composition of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but can be freely selected depending on the application form. For example, when the (A) filler is used as a light scattering agent, the content is preferably 0.01% by weight or more and 10% by weight or less. For example, when (A) a filler is used as an aggregate, the content is preferably 1% by weight or more and 50% by weight or less. For example, when (A) a filler is used as a thickener (thixotropic agent), the content is preferably 0.1% by weight or more and 20% by weight or less. For example, when (A) a filler is used as a refractive index adjusting agent, the content is preferably 10% by weight or more and 80% by weight or less. (A) If the amount of the filler is too small, the desired effect may not be obtained, and if it is too large, various properties such as adhesion, transparency and hardness of the cured product may be deteriorated.

  Moreover, when using the fluorescent substance containing composition of this invention as a member formation liquid for semiconductor light-emitting devices, the content rate of (A) filler is such that the content rate of (A) filler in the member for semiconductor light-emitting devices is within the above range. Should be set. Therefore, when the weight of the semiconductor light emitting device member forming liquid does not change in the drying step, the content of the (A) filler in the semiconductor light emitting device member forming liquid is the same as the content of the (A) filler in the semiconductor light emitting device member. Become. In addition, when the weight of the semiconductor light emitting device member forming liquid changes in the drying process, such as when the semiconductor light emitting device member forming liquid contains a solvent, the semiconductor light emitting device member forming liquid excluding the solvent, etc. (A) The content rate of the filler may be the same as the content rate of the (A) filler in the semiconductor light emitting device member.

(Other)
The phosphor-containing composition of the present invention is used as a highly heat-dissipating wavelength conversion layer material capable of providing a higher-luminance light-emitting device by using a heat conductive filler in combination and efficiently dissipating heat generated from the phosphor and the light-emitting element to the outside. You can also.

<1-2. (B) Phosphor>
Next, the type and physical properties of the phosphor used in the present invention will be described.
<1-2-1. Types of phosphors>
The phosphor used in the present invention is not particularly limited. For example, generally known inorganic phosphors and organic phosphors can be used, and one or more of these are used in any ratio and combination. be able to. Hereinafter, specific examples of the phosphor are illustrated, but in the illustrated general formula, phosphors that are different only in a part of the structure are appropriately omitted. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “ “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are collectively shown as “(La, Y) ₂ O ₂ S: Eu”. ing. Omitted parts are shown separated by commas (,).

As a phosphor preferably used in the present invention, for example, a group consisting of M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ Si ₅ N ₈ , MSi ₂ N ₂ O _{2 as} a host crystal (however, M represents at least one selected from the group consisting of Ca, Sr, and Ba), and Cr, Mn, Fe, Bi, Ce, Pr, Nd as an activator , Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb.

Specific examples of the phosphor include, for example, Ba ₃ SiO ₅ : Eu, (Sr _1-a Ba _a ) ₃ SiO ₅ : Eu, Sr ₃ SiO ₅ : Eu, CaS: Eu, SrS: Eu, BaS: Eu. _{, CaS: Ce, SrS: Ce} , BaS: Ce, CaGa 2 S 4: Eu, SrGa 2 S 4: Eu, BaGa 2 S 4: Eu, CaGa 2 S 4: Ce, SrGa 2 S 4: Ce, BaGa 2 _{S 4: Ce, CaAlSiN 3:} Eu, SrAlSiN 3: Eu, (Ca 1-a Sr a) AlSiN 3: Eu, CaAlSiN 3: Ce, SrAlSiN 3: Ce, (Ca 1-a Sr a) AlSiN 3: Ce _{, Ca 2 Si 5 N 8:} Eu, Sr 2 Si 5 N 8: Eu, Ba 2 Si 5 N 8: Eu, (Ca 1-a Sr a) 2 Si _{5 N 8: Eu, Ca 2} Si 5 N 8: Ce, Sr 2 Si 5 N 8: Ce, Ba 2 Si 5 N 8: Ce, (Ca 1-a Sr a) 2 Si 5 N 8: Ce, CaSi ₂ N ₂ O ₂ : Eu, SrSi ₂ N ₂ O ₂ : Eu, BaSi ₂ N ₂ O ₂ : Eu, CaSi ₂ N ₂ O ₂ : Ce, SrSi ₂ N ₂ O ₂ : Ce, BaSi ₂ N ₂ O ₂ : Ce, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Ba ₃ Si ₆ O ₉ N ₄ : Eu (in relation to the above, a satisfies 0 ≦ a ≦ 1) and the like.

Among them, CaS, CaGa ₂ S ₄ : Eu, SrGa ₂ S ₄ : Eu, (Sr _0.8 Ca _0.2 ) AlSiN ₃ : Eu, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Ba ₃ Si ₆ Preferred examples include O ₉ N ₄ : Eu and (Sr, Ca) AlSiN ₃ : Eu.

In addition to the above phosphors, other phosphors can be used depending on the purpose, such as improved durability and improved dispersibility. The composition of such a phosphor is not particularly limited, but a metal oxide represented by Y ₂ O ₃ , Zn ₂ SiO _4, etc., which is a crystal matrix, metal nitridation represented by Sr ₂ Si ₅ N _8, etc. , Phosphates such as Ca ₅ (PO ₄ ) ₃ Cl, and sulfides such as ZnS, SrS, CaS, etc., Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho It is preferable to combine ions of rare earth metals such as Er, Tm and Yb and ions of metals such as Ag, Cu, Au, Al, Mn and Sb as activators or coactivators.

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. 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.

(Orange to red phosphor)
Examples of phosphors that emit orange to red fluorescence (hereinafter referred to as “orange to red phosphors” as appropriate) include the following. The emission peak wavelength of the orange to red phosphor is preferably in the wavelength range of usually 580 nm or more, preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less. Examples of such orange to red phosphors include europium represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. The activated alkaline earth silicon nitride phosphor is 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) ₂ O ₂ S: Examples include europium activated rare earth oxychalcogenide phosphors represented by 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 No. 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 the present invention. These are phosphors containing oxynitride and / or oxysulfide.

Other red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, etc. 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 tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO ₃ : Eu-activated aluminate phosphors such as Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ Ba-activated silicate phosphor such as BaSiO ₅ : Eu, Ce-activated aluminate phosphor such as (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce, _{(Mg, 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 such as Eu Phosphors, Ce-activated nitride phosphors such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn, etc. Eu, Mn-activated halophosphate phosphor, Ba ₃ MgSi 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 · Ge _2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride 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, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi activated vanadate phosphors such as Eu, Bi, etc., SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, etc., Ce activated sulfide fluorescence such as CaLa ₂ S ₄ : Ce, etc. (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn-activated phosphate phosphors such as Eu and Mn , (Y, Lu) ₂ WO ₆ : Eu, Mo-activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y Nz: Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH) ₂ : Eu, Mn activated halophosphorus such as Eu, Mn Acid salt phosphor, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Siz _-q Ge _q O _{12 + δ} It is also possible to use a Ce-activated silicate phosphor or the like.

  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 cyanine pigments, dioxazine pigments, and the like.

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, (Sr, Ba, Ca)} 3 SiO 5: Eu, Sr 2 BaSiO 5: Eu -activated silicate phosphors such as _{Eu, (Sr, Mg) 3} (PO 4) ₂ : Sn-activated phosphate phosphors such as Sn ^{2+ and the} like.

Any one of the red phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.
Among the above examples, as the red phosphor, (Ca, Sr, Ba) AlSiN ₃ : Eu, (Ca, Sr, Ba) AlSiN ₃ : Ce, (La, Y) ₂ O ₂ S: Eu are preferable, (Sr, Ca) AlSiN ₃ : Eu and (La, Y) ₂ O ₂ S: Eu are particularly preferable.
Moreover, among the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

(Green phosphor)
Examples of phosphors that emit green fluorescence (hereinafter referred to as “green phosphors” as appropriate) include the following. The emission peak wavelength of the green phosphor is usually in the wavelength range of 490 nm or more, preferably 510 nm or more, more preferably 515 nm or more, and usually 560 nm or less, preferably 540 nm or less, more preferably 535 nm or less. .

As such a green phosphor, for example, a europium-activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _2. Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb-activated silicate phosphors such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu-activated borate phosphate phosphors such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as _Eu, Zn 2 _SiO 4: M such as Mn Activated silicate _{phosphors, CeMgAl 11 O 19: Tb,} Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga ₅ SiO ₁₄ : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, 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 activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, SrSi ₂ O ₂ N ₂ : Eu, (Mg, Sr, B a, Ca) Si ₂ O ₂ N ₂ : Eu, Eu-activated oxynitride phosphors such as Eu-activated β sialon, BaMgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphors such as Eu and Mn, Eu-activated aluminate phosphors such as SrAl ₂ O ₄ : Eu, Tb-activated oxysulfide phosphors such as (La, Gd, Y) ₂ O ₂ S: Tb, and Ce such as LaPO ₄ : Ce, Tb , Tb-activated phosphate phosphors, sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphor such as K, Ce, Tb, 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 thioaluminate phosphor such as Eu, thiogallate phosphor, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, etc., MSi ₂ O ₂ N ₂ : Eu, M ₃ Si ₆ O ₉ N ₄ : Eu, M ₂ Si ₇ O ₁₀ N ₄ : Eu , M represents an alkaline earth metal element. It is also possible to use Eu-activated oxynitride phosphors such as

  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.

(Blue phosphor)
Examples of phosphors emitting blue fluorescence (hereinafter referred to as “blue phosphors” as appropriate) include the following. The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 470 nm or less, more preferably 460 nm or less. .

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting 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 substantially cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu Consists of alkaline earth chloroborate phosphors, fractured particles with fractured surfaces, and light emission in the blue-green region (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.

Other blue phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba). ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphor such as Eu, SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce-activated such as Ce Thiogallate phosphor, (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-activated halophosphate phosphors such as Eu, Mn, Sb, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu-activated silicic acid such as Eu Salt phosphors, Eu-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Eu, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, and Ce-activated such as Y ₂ SiO ₅ : Ce Silicate phosphor, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ .nB ₂ O ₃ : Eu, 2SrO. 0.84P ₂ O ₅ .0.16B ₂ O ₃ : Eu, Mn-activated borate phosphate phosphor such as Eu, Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu Etc. can also be used.

Further, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based fluorescent dyes, organic phosphors such as thulium complexes, and the like can be used. . Among the above examples, as the blue phosphor, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Ca, Mg) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu is preferred, and BaMgAl ₁₀ O ₁₇ : Eu is particularly preferred.

(Yellow phosphor)
Examples of phosphors that emit yellow fluorescence (hereinafter appropriately referred to as “yellow phosphors”) include the following. The emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. .

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 selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And M ^a ₃ M ^b ₂ M ^c ₃ O ₁₂ : Ce (where M ^a is a divalent metal element and M ^b is a trivalent metal element) , ^{M c} represents a tetravalent metal element) garnet phosphor having a garnet structure represented by ^{_{like, AE 2 M d O 4:}} . Eu ( where, AE is, Ba, Sr, Ca, Mg , and An orthosilicate phosphor represented by at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge, and the like. Acid in which a part of Compound phosphor, AEAlSiN _3: Ce (., Where, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn) nitride having CaAlSiN ₃ structures such as system Examples thereof include phosphors activated with Ce such as phosphors.

In addition, as yellow phosphors, sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu, etc. It is also possible to use a phosphor activated by Eu, such as an oxynitride phosphor having a SiAlON structure such as a body, Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu. Examples of yellow phosphors include brilliant sulfoflavine FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45Gd) Etc. can also be used.

<1-2-2. Physical properties of phosphors>
The particle size of the phosphor (B) 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 25 micrometers or less. If the median particle size (D ₅₀ ) is too small, the brightness of the cured product of the phosphor-containing composition may decrease, or the phosphor may aggregate in the phosphor-containing composition. On the other hand, if the median particle size (D ₅₀ ) is too large, there may be cases where coating unevenness or blockage of a dispenser occurs.

In addition, (B) the particle size distribution (QD) of the phosphor is preferably smaller in order to align the dispersed state of the particles in the phosphor-containing composition. Since it connects, it is 0.03 or more normally, Preferably it is 0.05 or more, More preferably, it is 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. Moreover, the shape of (B) fluorescent substance is not specifically limited, The thing of arbitrary shapes can be used. Incidentally, the median particle size (D _50), and particle size distribution (QD) can be measured by a measuring method similar to that described above (A) a filler.

  The amount of the phosphor (B) used in the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but can be freely selected depending on the application form. The example of the fluorescent substance containing composition used for the semiconductor light-emitting device of white light emission used for uses, such as white LED and white illumination, is given. For example, when (B) the phosphor is uniformly dispersed and potted by filling the entire recess of the package including the semiconductor light emitting device, the content of (B) the phosphor in the solid content of the phosphor-containing composition is: Usually, it is 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more. Moreover, it is 35 weight% or less normally, Preferably it is 30 weight% or less, More preferably, it is 28 weight% or less.

Further, for example, in the same application, a package in which the phosphor (B) is dispersed at a high concentration is distant from the light emitting surface of the semiconductor light emitting device of the semiconductor light emitting device (for example, a recess including the semiconductor light emitting device is filled with a transparent sealing agent. (B) in the solid content of the phosphor-containing composition when it is applied in a thin film shape to an opening surface, a glass lid for LED hermetic sealing, a light exit surface of an external optical member such as a lens, a light guide plate, etc.
The content of the phosphor is usually 5% by weight or more, preferably 7% by weight or more, more preferably 10% by weight or more. Moreover, it is 90 weight% or less normally, Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less.

In general, when obtaining a white color by mixing the emission color of the semiconductor light-emitting element and the emission color of (B) the phosphor, a part of the emission color of the semiconductor light-emitting element is transmitted. The concentration is low, and the region is near the lower limit of the above range. On the other hand, in the case where white light is obtained by converting all the light emission of the semiconductor light emitting element into the phosphor emission color, since the phosphor (B) having a high concentration is preferable, the phosphor content is a region near the upper limit of the above range. . If the phosphor content is higher than this range, the coating performance may be lowered, or the utilization efficiency of the phosphor may be lowered due to optical interference, and the luminance of the semiconductor light emitting device may be lowered. On the other hand, if the phosphor content is less than this range, wavelength conversion by the phosphor (B) becomes insufficient, and the intended emission color may not be obtained.
The application of the white light emitting semiconductor light emitting device has been illustrated above, but the specific phosphor content varies depending on the target color, (B) phosphor luminous efficiency, color mixture type, phosphor specific gravity, coating film thickness, and device shape. Yes, this is not the case.

  The phosphor used in the present invention may be subjected to surface treatment for the purpose of further improving water resistance. As an example of the above-mentioned surface treatment, for example, as described in JP-T-2006-523245, a coating material is obtained by chemically modifying the original components of the phosphor by performing a heat treatment or the like on the phosphor. Well-known surface treatments, such as forming, are mentioned.

A surface treatment for coating a metal phosphate is also effective. Specifically, for example, a surface treatment method that proceeds in the following procedures (i) to (iii) can be given.
(I) a predetermined amount of a water-soluble phosphate such as potassium phosphate and sodium phosphate and at least one of alkaline earth metals such as calcium chloride, strontium sulfate, manganese chloride and zinc nitrate, Zn and Mn A water-soluble metal salt compound is mixed in the phosphor suspension and stirred.
(Ii) The phosphate of at least one metal among alkaline earth metals, Zn and Mn is generated in the suspension, and the generated metal phosphate is deposited on the phosphor surface.
(Iii) Remove moisture.

<1-3. (C) Liquid medium>
Next, the (C) liquid medium used in the present invention will be described. (C) The liquid medium is a liquid medium capable of uniformly dispersing the above (A) filler and (B) phosphor, and carries the phosphor when the phosphor-containing composition is cured. It can be composed of only a binder component having a function to perform the above, or one containing the binder component and a solvent, or one containing an additive necessary for the binder component. Hereinafter, each component will be described.

<1-3-1. Binder component>
As the binder component contained in the liquid medium (C), 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 the organic material contained in (C) the liquid medium 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 the present invention, the inorganic material and / or the organic material can be used alone, or two or more can be used in any ratio and combination.
(C) The content of the binder component in the liquid medium is usually 60% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more. Moreover, it is 100 weight% or less normally. Moreover, since the solvent may lead to distortion and foaming of the cured product, it is preferable to use a minimum amount, and among these, it is particularly preferable to use no solvent.

  Among the above, particularly when the phosphor-containing composition produced by the present invention is used for a member for a semiconductor light-emitting device of a high-power semiconductor light-emitting device such as a lighting device, the cured product of the phosphor-containing composition In consideration of heat resistance and light resistance, it is preferable to use a silicon-containing compound.

  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. Of these, silicone materials are preferred from the viewpoint of ease of handling. Hereinafter, this silicone material will be described.

(Silicone material)
The silicone material usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include compounds represented by the following general composition formula and / or mixtures thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q
Here, R ¹ to R ⁶ may be the same or different and are selected from the group consisting of an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are 0 to less than 1, and M + D + T + Q = 1.

  For example, when a phosphor-containing composition containing a silicone-based material is used for sealing a semiconductor light-emitting device, the semiconductor light-emitting device is sealed with a liquid phosphor-containing composition and then cured by heat or light. it can.

  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.

a. 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. As a typical example, a silicon-containing compound having a (C1) alkenyl group such as vinyl silane and a silicon compound containing a (C2) hydrosilyl group such as hydrosilane are reacted in the presence of an addition catalyst such as a Pt catalyst. The compound etc. which have Si-C-C-Si bond obtained by making it a crosslinking point can be mentioned.

(C1) As a silicon-containing compound having an alkenyl group, the following general formula R _n SiO _{[(4-n) / 2]}
(In the formula, R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group, and n is a positive number satisfying 1 ≦ n <2.) And organopolysiloxanes having alkenyl groups bonded to at least two silicon atoms.
In R of the above formula, an alkenyl group is 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, it is selected from alkyl groups such as methyl group and ethyl group, monovalent hydrocarbon groups having 1 to 20 carbon atoms such as vinyl group and phenyl group. Preferably, they are a methyl group, an ethyl group, and a phenyl group. Each may be different, but when UV resistance is required, 80% or more of R is preferably a methyl group. R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 3% or less of the weight of the silicon-containing compound having (C1) alkenyl group. Further, n is a positive number satisfying 1 ≦ n <2, but if this value is 2 or more, there is a possibility that sufficient strength cannot be obtained when the phosphor-containing composition is used as a sealing agent, If it is less than 1, synthesis of this organopolysiloxane may be difficult in the synthesis.

  Examples of the silicon-containing compound having an alkenyl group include vinyl silane and vinyl group-containing polyorganosiloxane. These may be used alone or in combination of two or more in any ratio and combination. Among these, a vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule is preferable.

Specific examples of the vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule include, for example, both-end vinyl polydimethylsiloxane DMS-V00 manufactured by Gelest,
DMS-V03,
DMS-V05,
DMS-V21,
DMS-V22,
DMS-V25,
DMS-V31,
DMS-V33,
DMS-V35,
DMS-V41,
DMS-V42,
DMS-V46,
DMS-V52,
Both end vinyldimethylsiloxane-diphenylsiloxane copolymer PDV-0325,
PDV-0331,
PDV-0341,
PDV-0346,
PDV-0525,
PDV-0541,
PDV-1625,
PDV-1631,
PDV-1635,
PDV-1641,
PDV-2331,
PDV-2335,
Both end vinylphenylmethylsiloxane PMV-9925,
Trimethylsilyl-blocked vinylmethylsiloxane-dimethylsiloxane copolymer VDT-123,
VDT-127,
VDT-131,
VDT-153,
VDT-431,
VDT-731,
VDT-954,
Vinyl T-structure polymer VTT-106,
MTV-124,
Etc.

  In addition, examples of the (C2) silicon-containing compound having a hydrosilyl group include hydrosilane and hydrosilyl group-containing polyorganosiloxane, and these may be used alone or in combination of two or more in any ratio and combination. Can do. Of these, hydrosilyl group-containing polyorganosiloxane having two or more hydrosilyl groups in the molecule is preferred.

Specific examples of the polyorganosiloxane containing two or more hydrosilyl groups in the molecule include, for example, both-end hydrosilyl polydimethylsiloxane DMS-H03 manufactured by Gelest,
DMS-H11,
DMS-H21,
DMS-H25,
DMS-H31,
DMS-H41,
Both terminal trimethylsilyl blocked methylhydrosiloxane-dimethylsiloxane copolymer HMS-013,
HMS-031,
HMS-064,
HMS-071,
HMS-082,
HMS-151,
HMS-301,
HMS-501,
Etc.

  The amount of the silicon compound having the (C2) hydrosilyl group used in the present invention is usually 0.5 mol or more, preferably 0.7 mol or more, more preferably 0, relative to 1 mol of the silicon compound having (C1) vinylsilyl group. .8 mol or more. Moreover, it is 2.0 mol or less normally, Preferably it is 1.8 mol or less, More preferably, it is 1.5 mol or less. Thereby, the residual amount of unreacted end groups after curing can be reduced, and a cured product with little change over time such as coloring or peeling at the time of lighting can be obtained.

  The (C3) addition condensation catalyst is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group in the component (C1) and the hydrosilyl group in the component (C2). As an example of the addition condensation catalyst, Are platinum black, secondary platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, a platinum-based catalyst such as platinum bisacetoacetate, a palladium-based catalyst, Examples include platinum group metal catalysts such as rhodium catalysts. The amount of the (C3) addition condensation catalyst can be a catalytic amount. Usually, the platinum group metal is usually 1 ppm or more, preferably 2 ppm relative to the total weight of the (C1) component and the (C2) component. These are usually 500 ppm or less, preferably 100 ppm or less. Thereby, catalyst activity can be made high.

b. 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 (1) and / or (2) and / or oligomers thereof.

M ^{m +} X _n Y ¹ _m-1 (1)

(In the formula (1), 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 (2)

(In Formula (2), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. Y ² represents a u-valent organic group, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, and u is 2 or more. Represents an integer.)
Moreover, as a curing catalyst, a metal chelate compound etc. can be used suitably, for example. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr.

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

c. UV curable liquid silicone rubber There are several types of UV curable liquid silicone rubber depending on its curing mechanism. Among them, an acrylic group is introduced into silicone and polymerized under a radical initiator; A salt that decomposes to generate a strong acid, which is then crosslinked by opening an epoxy group; a product obtained by crosslinking a thiol to vinyl siloxane; and the like can be cured by low energy irradiation. It is highly productive and useful. These ultraviolet curable liquid silicone rubbers can be cured in a short time without requiring a high temperature for curing, and do not deteriorate the member even when cured together with a heat-sensitive member. On the other hand, when containing a high concentration of (A) filler or (B) phosphor or when the cured thickness is thick, the irradiation light is difficult to reach the deep part and hard to cure, so the transparency and cured thickness of the phosphor-containing composition can be reduced. There are limitations. The UV curable liquid silicone rubber desirably reaches the target hardness within 1 hour, preferably within 30 minutes, more preferably within 20 minutes, depending on the transparency, thickness, and polymerization initiator.

d. Particularly preferred silicone materials Among the silicone materials, particularly preferred materials will be described below.
Silicone materials generally have poor adhesion to semiconductor light emitting elements, substrates on which semiconductor elements are arranged, packages, and the like when used in semiconductor light emitting devices. To make silicone materials highly adhesive to these materials In particular, a silicone material having one or more features among the following [1] to [3] is preferable.

[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 tetramethoxysilane, 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 tetramethoxysilane, 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 features [1] and [2] is preferable. Particularly preferably, a silicone material having all of the above features [1] to [3] is preferable. Among the silicone materials having the above characteristics, a condensation type silicone material is preferable from the viewpoint of the heat resistance, light resistance, etc. of the cured product of the phosphor-containing composition produced according to the present invention.
In addition, among silicone materials having the above characteristics, when used for large-sized devices and ultraviolet light-emitting devices, the condensation type silicone material is a heat-resistant, light-resistant material of the phosphor-containing composition produced according to the present invention. From the viewpoint of properties and the like.

  In addition, when the light emitting element is a small size of 20 mA or less or the light emitting color of the light emitting element is blue and heat resistance and light resistance are not required to be large, any of an addition type, a condensation type, and an ultraviolet curing type Silicone materials can also be used. In particular, when it is necessary to maintain the luminance over a long period of time, a condensation type and an addition type that are less likely to cause yellowing or a decrease in transmittance due to coloring are preferable.

<1-3-2. (C) Solvent used for liquid medium>
The (C) liquid medium may contain a solvent. The solvent referred to in the present invention refers to a solvent capable of dispersing or dissolving the binder component.

  The solvent is not particularly limited, and examples thereof include lower alcohols having 1 to 3 carbon atoms, hydrocarbons having 6 to 10 carbon atoms, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and dimethylformamide. And polar solvents such as dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, N-methyl-2-pyrrolidone, and aromatic solvents such as toluene and xylene. The said solvent may be used individually by 1 type, and can use 2 or more types by arbitrary ratios and combinations. Among them, a solvent having an unsaturated bond and a boiling point of 150 ° C. or lower is preferable from the viewpoint that foaming during curing and coloring during lighting can be suppressed.

  The amount of the solvent contained in the (C) liquid medium is usually greater than 0% by weight, preferably 40% by weight or less, more preferably 30% by weight or less, and more preferably 20% by weight or less. By containing a solvent in the (C) liquid medium, the viscosity of the (C) liquid medium can be adjusted, or the reactivity during storage can be controlled.

<1-3-3. Other ingredients>
(C) In the liquid medium, in addition to the binder component and the solvent, as long as the effects of the present invention are not impaired, one or more other components are contained in any ratio and combination as necessary. Can be made. Examples of such components include thermosetting resins such as epoxy resins. The content of the thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less, based on the binder component.

  In the liquid medium (C), for example, anti-aging agent, radical inhibitor, ultraviolet absorber, adhesion improver, flame retardant, surfactant, storage stability improver, ozone deterioration inhibitor, light stabilizer , Thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposing agent, lubricant, pigment, metal An activator, a physical property modifier, and the like can be mixed within a range that does not impair the object and effect of the present invention. In addition, as a coupling agent, a silane coupling agent is mentioned, for example. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity. Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- (Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes having can be exemplified.

<1-3-4. (C) Amount of liquid medium used>
The amount of the (C) liquid medium used in the present invention is usually 40% by weight or more, preferably 45% by weight or more, and more preferably 50% by weight or more in the phosphor-containing composition to be produced. . Moreover, it is 90 weight% or less normally, Preferably it is 85 weight% or less, More preferably, it is 80 weight% or less.

  (C) When the amount of the liquid medium is large, no particular problem occurs, but in order to improve the chromaticity, color rendering, luminous efficiency and the like of the cured product of the phosphor-containing composition, Within the above range. On the other hand, if it is too small, it may be difficult to handle due to lack of fluidity.

<1-4. (D) Other ingredients>
In the present invention, in addition to the above-mentioned (A) filler, (B) phosphor, and (C) liquid medium, as long as the effects of the present invention are not impaired, (D) one or more other components as necessary, or Two or more kinds can be contained in any ratio and combination. Examples of such components include thixotropic agents such as fumed silica, pigments, antioxidants, stabilizers (processing stabilizers such as phosphorus-based processing stabilizers, oxidation stabilizers, heat stabilizers, ultraviolet rays, etc. 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.

[2. Production method]
If bubbles are generated in the cured product of the phosphor-containing composition, light refraction or scattering may occur, the adhesiveness of the cured product may be reduced, or the bubbles may expand due to heat and cracks may occur. there were. As one of the causes of air bubbles, there are gas contained in each material of the phosphor-containing composition, air bubbles entrained by the mixing operation of the materials, moisture absorption, and the like.
According to the method for producing a phosphor-containing composition of the present invention, these gases and bubbles can be separated from the phosphor-containing composition (hereinafter sometimes referred to as “degassing”). The method for producing the phosphor-containing composition of the present invention will be specifically described below.

<2-1. Production method of the present invention>
The method for producing a phosphor-containing composition of the present invention is a method for producing a phosphor-containing composition containing (A) a filler, (B) a phosphor, and (C) a liquid medium, wherein (A) a filler, (B) The phosphor and (C) the liquid medium are mixed and stirred in a container having a shape in which the cylindrical inner surface is connected to the bottom surface with a smooth curved surface (hereinafter, referred to as “mixing and stirring step”). ). At this time, (D) other components may be contained.
FIG. 47 is a diagram illustrating an example of the container, and is a schematic cross-sectional view on a vertical plane passing through the center of the bottom surface of the container. In FIG. 47, the part represented by the symbol a represents the inner surface, the part represented by the symbol b represents a smooth curved surface connecting the inner surface and the bottom surface, and the part represented by the symbol c represents the bottom surface.

The larger the area of the smooth curved surface b with respect to the inner surface area of the container, the more preferable it is because convection easily occurs when mixing and stirring, and the efficiency of deaeration is improved. Productivity tends to decrease.
Specifically, when the height from the bottom surface of the container is 100, the height from the bottom surface of the portion having a smooth curved surface is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually It is 40 or less, preferably 35 or less, and more preferably 30 or less. Below this range, a blind spot portion that is difficult to convect at the boundary portion between the inner side surface and the bottom surface is generated, and foaming may occur when the phosphor-containing composition is applied and cured. Moreover, when it exceeds this range, there is a possibility that the internal volume becomes small and the productivity decreases.

Further, the container is more preferably a container in which the central portion of the bottom surface is formed in a shape (so-called hat shape) that is smoothly raised concentrically with respect to the cylindrical inner surface.
FIG. 48 is a diagram illustrating an example of the container, and is a schematic cross-sectional view on a vertical plane passing through the center of the bottom surface of the container. In FIG. 48, the portion represented by the symbol d is a portion that is smoothly raised concentrically with respect to the cylindrical inner surface, the symbol H ₁ is the height of the raised portion d, and the symbol H ₂ is the inside of the container. The height (height from the bottom surface to the mouth of the container), the symbol W represents the size (bore diameter) of the mouth of the container. In addition, the same code | symbol is attached | subjected about the part which has a structure common with FIG.

At this time, it is preferable that the center portion is raised so that the center of the bottom surface c is the highest, not the entire bottom surface c. That is, it is preferable that a bottom surface c that does not protrude like a donut exists.
The height H _{1 of the} ridge is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 50 or less, preferably 40 or less, more preferably, when the height H ₂ inside the container is 100. Is 30 or less. Below this range, there is a possibility that mixing and deaeration may become insufficient because a blind spot portion in which convection hardly occurs is formed in the central portion. On the other hand, if it exceeds this range, the mixing efficiency cannot be remarkably improved, and the internal volume is reduced and the productivity may be lowered.

  The material of the container is preferably a phosphor-containing composition and a material that does not cause chemical reaction or impurity elution with each material. Specific examples include paper, polyethylene, polypropylene, polystyrene, Teflon, stainless steel, and glass.

  The inner volume of the container is not limited as long as the effect of the present invention is not significantly impaired, but is usually 3 mL or more, preferably 4 mL or more, more preferably 5 mL or more, and usually 5 L or less, preferably 3 L or less, more preferably 1 L. It is as follows. Below this range, the weight of the phosphor-containing composition is so small that stirring may become impossible. Moreover, when it exceeds this range, there is a possibility that the content liquid tends to overflow from the container during mixing, or the gas-liquid interface is reduced and mixing defoaming tends to be insufficient.

  In addition, if the container has a wide opening, the workability is improved, but if it has a narrow opening, foreign matter can be avoided, and the degree of vacuum increases when the mixing and stirring step is performed under reduced pressure. Therefore, the size of the mouth of the container is such that the ratio of the opening diameter to the depth of the container (opening diameter / depth) is usually 0.25 or more, preferably 0.4 or more, more preferably 0.5 or more, Usually, it is 2.0 or less, preferably 1.9 or less, more preferably 1.8 or less.

  Specific examples of the container include ointment jars (for example, those manufactured by Umano Chemical Co., Ltd., MI Chemical Co., Ltd., Sun Chemical Co., Ltd., Shinto Chemical Co., Ltd., Shinryo Co., Ltd., KM Chemical Co., Ltd., and Kinshi Co., Ltd.). Is preferred. This is because the gas of each material can be more efficiently separated by stirring in the vessel.

  In the mixing and stirring step, there is no restriction on the mixing order of each material ((A) filler, (B) phosphor, (C) liquid medium, and (D) other components when mixing), and all materials are in a container. Mixing and stirring may be started after entering, or mixing and stirring may be performed while sequentially adding materials.

  The stirring speed is usually 30 rpm or more, preferably 40 rpm or more, more preferably 50 rpm or more, and usually 3000 rpm or less, preferably 2500 rpm or less, more preferably 2000 rpm or less, although it depends on the liquid amount, viscosity, and stirring device. Below this range, the movement of the light boiling component to the gas-liquid interface becomes rate limiting, and there is a possibility that it takes time to remove. In addition, if it exceeds this range, bubbles are entrained by stirring and the degassing efficiency is increased, or in a liquid medium with high viscosity, it is difficult to continue stirring due to the rise in liquid level, and the specific gravity between the liquid medium and the filler and phosphor If the difference is large, particles with a large specific gravity may settle. The stirring speed is not necessarily constant, and may include steps such as alternately repeating high speed and low speed, gradually increasing or decreasing the speed, and temporarily stopping stirring.

  The stirring time is usually 1 minute or longer, preferably 5 minutes or longer, more preferably 10 minutes or longer, and usually 3 hours or shorter, preferably 2 hours or shorter, more preferably 1 hour or shorter. Below this range, defoaming and degassing may be insufficient and foaming may occur during curing. Moreover, when it exceeds this range, the productivity is inferior, and the temperature of the phosphor-containing composition is increased by the heat of stirring, and the liquid medium may be thickened or decomposed. In addition, when fumed silica is used as a filler and a high-shear stirring device is used or a high-concentration filler is added and stirred, excessive dispersion of the filler when stirring for a long time exceeding the above range is performed. In some cases, the target thixotropy cannot be obtained by inducing surface alteration.

  The mixing and stirring step is usually performed at a temperature of 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 25 ° C. or higher, and usually 200 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. Below this range, condensation due to moisture in the atmosphere or icing due to moisture contained in the liquid medium may occur during mixing, and defoaming and degassing efficiency may not be improved. Further, if it exceeds this range, the liquid medium may be decomposed or the phosphor-containing composition may increase in viscosity over time.

The mixing and stirring step is usually performed under a pressure of 0 kPa or more, preferably 0.1 kPa or more, more preferably 0.5 kPa or more, and usually 40 kPa or less, preferably 30 kPa or less, more preferably 20 kPa or less. Below this range, it may be difficult to maintain the degree of decompression and require a highly accurate device, which may not be economical. Also, if it exceeds this range, the contained gas and moisture will remain and foaming will occur at the time of curing, which may cause a decrease in adhesion and cracks with the object to be applied, or when used in a light emitting device There is a possibility that luminance cannot be obtained.
The atmosphere preferably does not react with the phosphor-containing composition, and is preferably carried out in an environment such as air; an inert gas such as nitrogen or a rare gas.

  Further, it is preferable to perform centrifugal operation simultaneously with stirring (centrifugal stirring using a rotation / revolution mixer, rotation / revolution vacuum mixer, or the like). This is because the gas in each material is more efficiently separated by centrifugal stirring, and the entrainment of bubbles due to the stirring operation can be prevented.

  Examples of the stirring device include a rotation / revolution type vacuum mixer (specifically, AR-100, ARE300, AR-500, ARV310, V-mini300V manufactured by EME, Mazerustar manufactured by Kurabo Industries, etc., manufactured by Sinky). preferable. A conventionally known method such as mixing with a mixer, a high-speed disper, a homogenizer, a three-roller, a kneader, a bead mill or the like can also be used. However, when stirring is performed by any of these methods, rotation / revolution after the stirring is performed. Centrifugal stirring is preferably performed using a rotary mixer or a rotating / revolving vacuum mixer. In addition, when (A) filler and (B) phosphor are easy to aggregate, bead mill or three rolls before centrifugal stirring with a rotation / revolution mixer, rotation / revolution vacuum mixer, etc. It is preferable to disperse and disperse the agglomerated particles using, for example.

  (A) When the filler is easily agglomerated like fumed silica, a master batch prepared by mixing and stirring the high concentration filler (B) with the liquid medium (C) excluding the phosphor is prepared, and then ( C) A method in which a liquid medium is added and (A) the filler is diluted to a target concentration may be used. By adopting such a mixing method, the agglomerated particles are efficiently crushed by the collision between the agglomerated particles of fumed silica, and the transparency of the liquid finally obtained is higher than when mixed and dispersed in a single step. There is an advantage that mixing and dispersion can be completed in a short time. The masterbatch method is particularly effective when a centrifugal defoaming apparatus that is difficult to apply a shearing force is used as a mixer, and there is an advantage that mixing and stirring can be performed while defoaming. In this case, the required amount of fumed silica in the masterbatch depends on the initial viscosity of the liquid medium, but is usually 15% by weight or more, preferably 17% by weight or more, more preferably 20% by weight or more based on the liquid medium excluding the solvent. Further, it is usually 35% by weight or less, preferably 33% by weight or less, and more preferably 30% by weight or less. If the concentration is higher than this range, the liquid medium containing the filler has a very high viscosity, and the fluidity is lowered, so that stirring and mixing may not be possible. Also, when the concentration is lower than this range, the frequency of collision between the fillers decreases, so that even if mixing and stirring for a long time, many coarse aggregated particles exceeding 1 μm remain, and the transparency of the resulting liquid may be lowered. There is sex.

  Others (A) When the filler is mixed and stirred using a centrifugal defoamer, beads such as zirconia may be enclosed in a mixing container and stirred as necessary. In this case, since heat of stirring is more likely to occur compared to the case where beads are not used, the stirring time and the stirring temperature are within a range in which the liquid medium does not cause excessive viscosity increase or decomposition during stirring, usually 150 ° C. or less, The temperature is preferably controlled to 100 ° C. or lower, more preferably 80 ° C. or lower.

<2-2. Other processes>
In the manufacturing method of this invention, if it has at least the above-mentioned mixing stirring process, you may have another process.

  For example, in the case where (A) filler, (B) phosphor, and (D) other components become materials in a solid state, they are dried (hereinafter sometimes referred to as “drying steps” as appropriate). It is preferable to perform the centrifugal stirring step after passing through.

  The amount of moisture in the phosphor-containing composition affects the thickening effect of the composition. Therefore, if the (A) filler adsorbs moisture or brings moisture from other materials in the mixing and stirring step, the thickening effect varies. If the viscosity increases, the discharge amount may change when using the dispenser, or it may take time until thread breakage and thread breakage, and productivity may decrease. ) There is a possibility that the phosphor settles out, and there is a daily error or a daily error in the phosphor concentration. On the other hand, water once adsorbed to (A) filler is difficult to separate. From this point of view, it is preferable not to bring moisture into the mixing and stirring step.

  When the step of drying the filler (A) is performed before mixing and stirring, the method is not limited, and any known method such as natural drying, heat drying, reduced pressure drying, and aeration drying can be used. Of these, heat drying is preferred. In addition, one of the above methods may be performed alone, or two or more may be performed in any combination and ratio.

  (A) When heating and drying the filler, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Dry with. Below this range, drying may take a long time. Moreover, when it exceeds this range, there is a possibility that the particle structure of the filler (A) may change or the dry state may be uneven.

  (A) The relative humidity of the atmosphere when heating and drying the filler is usually 0% or more, preferably 5% or more, and usually 90% or less, preferably 80% or less, more preferably at 25 ° C. before heating. Dry at 70% or less. Below this range, a special desiccant device is required although the water removal efficiency is increased, which may be uneconomical and inferior in productivity. In addition, if it exceeds this range, the removal of moisture becomes insufficient, and there is a possibility that local re-adsorption of moisture occurs in a large-sized device or that a long time is required for dehydration.

  (A) The filler drying time is usually 1 minute or more, preferably 5 minutes or more, more preferably 10 minutes or more, and usually 6 hours or less, preferably 4 hours or less, more preferably 3 hours or less. Below this range, drying may be insufficient. Further, if it exceeds this range, the productivity may decrease, and the particle structure may change or the particles may be chemically modified.

  In addition, (A) the filler is dried until the mass change during drying is 1 wt% / hour or less. Of these, drying to 0.7% by weight / hour or less is preferable, and drying to 0.5% by weight / hour or less is more preferable.

  Although the drying process has been described mainly with respect to the (A) filler, it may be applied to each material of the phosphor-containing composition such as (B) a phosphor, or may be applied to a cup or the like used in a semiconductor light emitting device described later. Good. By performing a drying process on these materials and the like, the above-described effects tend to be obtained more remarkably. In the case of drying a material including a member that easily deteriorates such as a resin material, the heating temperature may not exceed 200 ° C. to prevent the resin deterioration, and the drying temperature may be lowered by reducing the pressure as necessary.

  What is necessary is just to perform a drying process before a mixing stirring process. However, it is preferable to move to the mixing and stirring step before the dried material absorbs moisture again.

  In addition to the mixing and stirring step and the drying step, other steps may be performed as long as the effects of the present invention are not significantly impaired.

[3. Phosphor-containing composition]
The phosphor-containing composition produced by this step will be described below.

<3-1. Physical properties>
The phosphor-containing composition produced according to the present invention is not particularly limited as long as it contains the above-mentioned components, but the viscosity is usually 500 mPa · s or more, preferably 1000 mPa · s or more, more preferably 2000 mPa · s. These are usually 15000 mPa · s or less, 10000 mPa · s or less, preferably 8000 mPa · s or less. When the viscosity is too high, troubles such as blockage of piping may occur when the phosphor-containing composition is filled in the coating apparatus. If the viscosity is too low, (B) the phosphor may precipitate.

  The phosphor-containing composition produced according to the present invention is preferably one that exhibits thixotropic properties in view of handleability and the like, and (C) the phosphor does not settle before the liquid medium is cured. 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.

<3-2. Application>
Although the fluorescent substance containing composition manufactured by this invention can be used for formation of the member for semiconductor light-emitting device of a well-known semiconductor light-emitting device, it is not this limitation. Further, it can be flexibly adapted to various coating methods such as potting, spin coating and printing.

When the phosphor-containing composition is used for forming a semiconductor light-emitting device member, the dispersibility of the phosphor (B) is good, and there are few occurrences of bubbles in the semiconductor light-emitting device member. Compared with the semiconductor light-emitting device member, the light extraction efficiency is high, the adhesiveness and the heat resistance are exhibited, cracks and peeling are unlikely to occur, and the luminance is less decreased. Therefore, a highly reliable member can be provided over a long period of time.
Hereinafter, a semiconductor light emitting device using the phosphor-containing composition produced according to the present invention for forming a member for a semiconductor light emitting device will be described.

<3-2-1. Basic Concept of Semiconductor Light Emitting Device>
The semiconductor light emitting device using the member for a semiconductor light emitting device has the following application examples, for example. The member for a semiconductor light emitting device of the present invention shows excellent light resistance, adhesion and heat resistance in the above application example, compared to the conventional member for a semiconductor light emitting device, is hardly cracked or peeled off, and has a reduced luminance. Less is. Therefore, according to the member for semiconductor light emitting devices using the phosphor-containing composition produced according to the present invention, a highly reliable member can be provided over a long period of time.

  (Example of application) A phosphor-containing member for a semiconductor light emitting device (hereinafter referred to as “phosphor part” as appropriate) is disposed in the vicinity of the light emitting element, and (B) fluorescence in the phosphor part by light from the light emitting element. Semiconductor light-emitting device that emits light of a desired wavelength using fluorescence by exciting a body and phosphor components.

  In this application example, a phosphor part having high durability and high light extraction efficiency can be formed by taking advantage of the high durability, transparency, and sealing material performance of the semiconductor light emitting device member. Furthermore, when the semiconductor light-emitting device member is held together with a transparent high-refractive component in addition to (B) the phosphor and the phosphor component, the refractive index of the semiconductor light-emitting device member is changed to a light-emitting element or (B) By setting the refractive index in the vicinity of the refractive index of the phosphor, interface reflection can be reduced and higher light extraction efficiency can be obtained.

  Hereinafter, a basic concept to which the semiconductor light emitting device member is applied will be described with reference to FIG. FIG. 1 is an explanatory diagram of the basic concept of the above embodiment. A light-emitting device 1B (semiconductor light-emitting device; hereinafter, a semiconductor light-emitting device may be simply referred to as a “light-emitting device”) is arranged in the vicinity of a light-emitting element 2 composed of LED chips and in the vicinity of the light-emitting element 2, as shown in FIG. The semiconductor light emitting device member 3B is provided.

  A semiconductor light emitting device 1B as shown in FIG. 1 includes (B) a phosphor or a phosphor component in a semiconductor light emitting device member 3B. In this case, the semiconductor light emitting device member 3B can exhibit the sealing of the light emitting element 2, the light extraction function, the functional component holding function, and the wavelength conversion function. In the following description, (B) the semiconductor light emitting device member 3B containing the phosphor and the phosphor component is appropriately referred to as “phosphor portion”. Further, the phosphor portion may be appropriately indicated by reference numerals 33 and 34 according to the shape and function thereof.

  The light emitting element 2 is constituted by, for example, an LED chip that emits blue light or ultraviolet light, but may be an LED chip of a light emitting color other than these.

  The phosphor portion 3B can exhibit functions such as a highly durable sealing material, a light extraction film, and various function-added films of the light-emitting element 2, and is excited by light from the light-emitting element 2 to emit light of a desired wavelength. It exhibits a wavelength conversion function for emitting light. The phosphor portion 3B only needs to include at least a fluorescent material that is excited by light from the light emitting element 2 and emits light of a desired wavelength. Examples of such fluorescent materials include the various phosphors (B) exemplified above. As the luminescent color of the phosphor portion 3B, not only the three primary colors of red (R), green (G) and blue (B) but also white such as a fluorescent lamp and yellow such as a light bulb are possible. In short, the phosphor portion 3B has a wavelength conversion function of emitting light having a desired wavelength different from the excitation light.

  In the light emitting device 1B shown in FIG. 1, a part 4a of the light emitted from the light emitting element 2 passes through the phosphor portion 3B as it is and is emitted to the outside of the light emitting device 1B. Further, in the light emitting device 1B, the other part 4b of the light emitted from the light emitting element 2 is absorbed by the phosphor part 3B to excite the phosphor part 3B, and the phosphor particles contained in the phosphor part 3B, Light 5 having a wavelength peculiar to fluorescent components such as fluorescent ions and fluorescent dyes is emitted to the outside of the light emitting device 1B.

  Therefore, from the light emitting device 1B, the combined light 6 of the light 4a emitted from the light emitting element 2 and transmitted through the phosphor portion 3B and the light 5 emitted from the phosphor portion 3B is emitted as wavelength-converted light. Therefore, the light emission color of the light emitting device 1B as a whole is determined by the light emission color of the light emitting element 2 and the light emission color of the phosphor portion 3B. The light 4a emitted from the light emitting element 2 and transmitted through the phosphor portion 3B is not always necessary.

<3-3. Embodiment>
[Embodiment 1]
As shown in FIG. 2A, the light emitting device 1B of the present embodiment includes a light emitting element 2 made of an LED chip, and a mold part 11 formed by molding a translucent transparent material into a bullet shape. The mold part 11 covers the light emitting element 2, and the light emitting element 2 is electrically connected to lead terminals 12 and 13 formed of a conductive material. The lead terminals 12 and 13 are formed of a lead frame.

  The light-emitting element 2 is a gallium nitride LED chip, and an n-type semiconductor layer (not shown) is formed on the lower surface side in FIG. 2A and a p-type semiconductor layer (not shown) is formed on the upper surface side. Since the light output is taken out from the p-type semiconductor layer side, the upper part of FIG. The rear surface of the light emitting element 2 is bonded to a mirror (cup part) 14 attached to the front end of the lead terminal 13 by die bonding. In the light-emitting element 2, conductive wires (for example, gold wires) 15 and 15 are connected to the p-type semiconductor layer and the n-type semiconductor layer by bonding, and the light-emitting element 2 and the light-emitting element 2 are connected via the conductive wires 15 and 15, respectively. The lead terminals 12 and 13 are electrically connected. The conductive wires 15 and 15 have a small cross-sectional area so as not to block the light emitted from the light emitting element 2.

  The mirror 14 has a function of reflecting light emitted from the side surface and the rear surface of the light emitting element 2 forward, and the light emitted from the LED chip and the light reflected forward by the mirror 14 function as a lens. 11 radiates forward from the mold part 11 through the front end part of the part 11. The mold part 11 covers the light emitting element 2 together with the mirror 14, the conductive wires 15 and 15, and part of the lead terminals 12 and 13, and the light emitting element 2 is deteriorated in characteristics due to reaction with moisture in the atmosphere. It is prevented. The rear end portions of the lead terminals 12 and 13 protrude from the rear surface of the mold portion 11 to the outside.

  In the light emitting element 2, as shown in FIG. 2B, the light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the phosphor portion 3B using a semiconductor process, and the phosphor portion 3B. A reflective layer 23 is formed on the rear surface. Although the light emitted from the light emitting layer portion 21 is emitted in all directions, a part of the light absorbed by the phosphor portion 3B excites the phosphor portion 3B and emits light having a wavelength specific to the fluorescent component. . The light emitted from the phosphor portion 3B is reflected by the reflective layer 3 and emitted forward. Therefore, the light emitting device 1B can obtain combined light of the light emitted from the light emitting layer portion 21 and the light emitted from the phosphor portion 3B.

  Thus, the light emitting device 1B of the present embodiment includes the light emitting element 2 and the phosphor portion 3B that is excited by light from the light emitting element 2 and emits light of a desired wavelength. Here, if a phosphor having excellent translucency is used as the phosphor portion 3B, a part of the light emitted from the light emitting element 2 is emitted to the outside as it is, and other light emitted from the light emitting element 2 is used. Since the fluorescent component that becomes the emission center is excited by a part and light due to light emission specific to the fluorescent component is emitted to the outside, the light emitted from the light emitting element 2 and the light emitted from the fluorescent component of the phosphor portion 3B In addition, light color unevenness and light color variation can be reduced as compared with the conventional case, and the light extraction efficiency can be increased. That is, if a phosphor part 3B having high transparency without cloudiness or turbidity is used, the light color uniformity is excellent, there is almost no light color variation between the light emitting devices 1B, and the light from the light emitting element 2 is exposed to the outside. The extraction efficiency can be increased as compared with the conventional case. In addition, the weather resistance of the light-emitting substance can be increased, and the life of the light-emitting device 1B can be extended as compared with the conventional case.

  Further, in the light emitting device 1B of the present embodiment, since the phosphor portion 3B is also used as a substrate on which the light emitting element 2 is formed, a part of the light from the light emitting element 2 becomes a light emission center in the phosphor portion ( B) The phosphor can be excited efficiently, and the brightness of the light due to the emission specific to the fluorescent component can be increased.

[Embodiment 2]
In the light emitting device 1B of the present embodiment, as shown in FIG. 3, the light emitting element 2 is surface-mounted on an insulating substrate 16 provided with a printed wiring 17. Here, the light emitting element 2 has the same configuration as that of the first embodiment, the light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the phosphor portion 3B, and the reflection layer 23 is formed on the rear surface of the phosphor portion 3B. Is formed. In the light emitting element 2, the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to the printed wirings 17 and 17 via the conductive wires 15 and 15, respectively. It is connected.

  Further, a frame-shaped frame member 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the light emitting element 2 is provided inside the frame member 18.

  Thus, the light emitting device 1B of the present embodiment also includes the light emitting element 2 and the phosphor portion 3B that is excited by the light from the light emitting element 2 and emits light of a desired wavelength, as in the first embodiment. Therefore, the combined light of the light from the light emitting element 2 and the light from the phosphor can be obtained. Further, similarly to the first embodiment, light color unevenness and light color variation can be reduced as compared with the prior art, and the light extraction efficiency to the outside can be increased, and the life can be extended. .

[Embodiment 3]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and does not use the frame member 18 (see FIG. 3) described in the second embodiment. As shown in FIG. The shape of the part 19 is different. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  The sealing portion 19 in the present embodiment includes a truncated cone-shaped sealing function portion 19 a that seals the light emitting element 2 and a lens-shaped lens function portion 19 b that functions as a lens at the front end portion of the sealing portion 19. ing.

  Therefore, in the light emitting device 1B of the present embodiment, the number of parts can be reduced as compared with the second embodiment, and the size and weight can be reduced. Moreover, by providing the lens function part 19b functioning as a lens in a part of the sealing part 19, a light distribution with excellent directivity can be obtained.

[Embodiment 4]
The basic configuration of the light-emitting device 1B of this embodiment is substantially the same as that of Embodiment 22, and as shown in FIG. 5, a recess 16a that houses the light-emitting element 2 is provided on one surface of the insulating substrate 16 (upper surface in FIG. 5). The light emitting element 2 is mounted on the bottom of the recess 16a, and the sealing portion 19 is provided in the recess 16a. Here, the printed wirings 17 and 17 formed on the insulating substrate 16 extend to the bottom of the recess 16a, and are electrically connected to the light emitting layer portion 21 made of a gallium nitride based semiconductor of the light emitting element 2 through the conductive wires 15 and 15. It is connected to the. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the sealing portion 19 is formed by filling the recess 16a formed on the upper surface of the insulating substrate 16, and therefore the frame member 18 (FIG. 3) or the molding die described in the third embodiment can be formed, and the sealing process of the light emitting element 2 can be performed more easily than in the second and third embodiments. There are advantages.

[Embodiment 5]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment, and is characterized in that the light emitting element 2 is so-called flip chip mounted on an insulating substrate 16 as shown in FIG. That is, the light emitting element 2 is provided with bumps 24 and 24 made of a conductive material on the surface side of each of the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21. The light emitting layer portion 21 is electrically connected face down with the printed wirings 17 and 17 of the insulating substrate 16 via the bumps 24 and 24. Therefore, in the light emitting element 2 according to the present embodiment, the light emitting layer portion 21 is disposed on the side closest to the insulating substrate 16, the reflection layer 23 is disposed on the side farthest from the insulating substrate 16, and The phosphor portion 3 </ b> B is interposed between the layer 23. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  In the light emitting device 1B of the present embodiment, the light reflected downward (backward) in FIG. 6 by the reflective layer 23 is reflected by the inner peripheral surface of the recess 16a and radiated upward (forward) in FIG. Here, it is desirable to separately provide a reflective layer made of a material having a high reflectivity on the inner peripheral surface of the recess 16a and other than the printed wirings 17 and 17.

  Therefore, in the light emitting device 1B of the present embodiment, the conductive wires 15 and 15 as in the fourth embodiment are not required to connect the printed wirings 17 and 17 provided on the insulating substrate 16 and the light emitting element 2. Compared to the fourth embodiment, the mechanical strength and reliability can be improved.

[Embodiment 6]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth embodiment, and is different in that the reflective layer 23 described in the fifth embodiment is not provided as shown in FIG. In short, in the light emitting device 1B of the present embodiment, the light emitted from the light emitting layer portion 21 and the light emitted from the phosphor portion 3B pass through the sealing portion 19 and are emitted forward as they are. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the number of parts can be reduced as compared with the fifth embodiment, and the manufacture becomes easy.

[Embodiment 7]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the first embodiment, and as shown in FIG. It is characterized in that it is formed. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 1, and description is abbreviate | omitted.

  In the manufacture of the light emitting device 1B of the present embodiment, a work product that is not provided with the mold part 11 is immersed in a molding die in which the phosphor-containing composition is stored, and the phosphor-containing composition is cured. Mold part 11 is formed.

  Therefore, in this embodiment, since the mold part 11 is formed integrally with the phosphor part, the light resistance of the mold part 11 can be obtained by using the semiconductor light emitting device member as described later as the phosphor part. It becomes possible to improve adhesiveness, sealing performance, transparency, heat resistance, etc., and to suppress cracks and peeling associated with long-term use.

[Embodiment 8]
The basic configuration of the light emitting device 1B of this embodiment is substantially the same as that of the first embodiment, and as shown in FIG. There is a feature in that. That is, in this embodiment, instead of providing the phosphor portion 3B in the light emitting element 2 as in the first embodiment, the phosphor portion 3B having a shape along the outer periphery of the mold portion 11 is provided. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 1, and description is abbreviate | omitted.

  The phosphor portion 3B in the present embodiment may be formed as a thin film by the method of curing the phosphor-containing composition described in the seventh embodiment, or a member in which a solid phosphor portion is previously molded into a cup shape. May be attached to the mold part 11.

  Therefore, in the light emitting device 1B of the present embodiment, the amount of material used in the phosphor portion is reduced compared to the case where the entire mold portion 11 is formed integrally with the phosphor portion as in the light emitting device 1B of the seventh embodiment. It is possible to reduce the cost.

[Embodiment 9]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and is arranged so as to surround the light emitting element 2 on one surface (upper surface in FIG. 10) side of the insulating substrate 16 as shown in FIG. The frame-shaped frame member 18 is provided, and the sealing portion 19 inside the frame member 18 is formed by a phosphor portion similar to the phosphor portion 3B described in the second embodiment. is there. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  In this embodiment, since the sealing portion 19 is formed of a phosphor portion, the light resistance of the sealing portion 19 is obtained by using the semiconductor light emitting device member as described later as the phosphor portion. It becomes possible to improve adhesiveness, sealing performance, transparency, heat resistance, etc., and to suppress cracks and peeling associated with long-term use.

[Embodiment 10]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. The frame-shaped frame member 18 is provided, and the sealing portion 19 inside the frame member 18 is formed by a phosphor portion similar to the phosphor portion 3B described in the second embodiment. is there. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  In this embodiment, since the sealing portion 19 is formed of a phosphor portion, the light resistance of the sealing portion 19 is obtained by using the semiconductor light emitting device member as described later as the phosphor portion. It becomes possible to improve adhesiveness, sealing performance, transparency, heat resistance, etc., and to suppress cracks and peeling associated with long-term use.

  In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the ninth embodiment.

[Embodiment 11]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 12, the phosphor previously molded into a lens shape on the upper surface of the sealing portion 19 made of a translucent material. It is characterized in that the portion 33 is provided. Here, the phosphor part 33 is made of the same material as the phosphor part 3B described in the second embodiment, and is excited by light from the light emitting element 2 to emit light having a desired wavelength. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed.

[Embodiment 12]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. It is characterized in that the portion 33 is provided. Here, the phosphor part 33 is made of the same material as that of the phosphor part 3B described in the second embodiment, and is excited by light from the light emitting element 2 to emit light having a desired wavelength. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed. In the present embodiment, since the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, excitation and light emission of the phosphor portion can be performed more efficiently than in the eleventh embodiment. There is an advantage.

[Embodiment 13]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. The stop portion 19 is characterized by being formed of a phosphor portion. Here, as in the third embodiment, the sealing portion 19 has a truncated cone-shaped sealing function portion 19 a for sealing the light emitting element 2 and a lens-like lens function that functions as a lens at the front end portion of the sealing portion 19. It consists of a part 19b. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 sealing and protecting the light emitting element 2, but also the wavelength conversion function for converting the wavelength of the light from the light emitting element 2 and the directivity of light emission. It has a lens function to control. Moreover, the weather resistance of the sealing part 19 can be improved and lifetime improvement can be achieved. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the twelfth embodiment.

[Embodiment 14]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 15, the sealing portion 19 that covers the light emitting element 2 on the one surface (upper surface in FIG. 15) side of the insulating substrate 16. And the sealing portion 19 is characterized by being formed of the phosphor portion 3B. Here, as in the third embodiment, the sealing portion 19 has a truncated cone-shaped sealing function portion 19 a for sealing the light emitting element 2 and a lens-like lens function that functions as a lens at the front end portion of the sealing portion 19. It consists of a part 19b. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 sealing and protecting the light emitting element 2, but also the wavelength conversion function for converting the wavelength of the light from the light emitting element 2 and the directivity of light emission. It has a lens function to control. Moreover, the weather resistance of the sealing part 19 can be improved and lifetime improvement can be achieved.

[Embodiment 15]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and a dome-shaped phosphor portion 34 that covers the light emitting element 2 is disposed on the upper surface side of the insulating substrate 16 as shown in FIG. However, it is characterized in that the sealing portion 19 made of a translucent resin is formed on the outer surface side of the phosphor portion 34. Here, as in the third embodiment, the sealing portion 19 includes a sealing function portion 19 a that seals the light emitting element 2 and a lens-like lens function portion 19 b that functions as a lens at the front end portion of the sealing portion 19. It is configured. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 3, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the amount of material used for the phosphor portion 34 can be reduced as compared with the thirteenth and fourteenth embodiments. Further, in the present embodiment, since the dome-shaped phosphor portion 34 covering the light emitting element 2 is disposed, a material such as resin or glass that does not easily transmit water vapor is selected for the phosphor portion 32, and the inside thereof is selected. By making the said semiconductor light-emitting device member into a shape, degradation of the light emitting element 2 by the water | moisture content from the outside can be prevented more reliably.

[Embodiment 16]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and a dome-shaped phosphor portion 34 that covers the light emitting element 2 is disposed on the upper surface side of the insulating substrate 16 as shown in FIG. However, the sealing portion 19 is formed on the outer surface side of the phosphor portion 34. Here, as in the third embodiment, the sealing portion 19 includes a sealing function portion 19 a that seals the light emitting element 2 and a lens-like lens function portion 19 b that functions as a lens at the front end portion of the sealing portion 19. It is configured. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 3, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the amount of material used for the phosphor portion 34 can be reduced as compared with the thirteenth and fourteenth embodiments. Further, in the present embodiment, since the dome-shaped phosphor portion 34 covering the light emitting element 2 is disposed, a material such as resin or glass that does not easily transmit water vapor is selected for the phosphor portion 32 and the inside thereof is selected. By making the said semiconductor light-emitting device member into a shape, degradation of the light emitting element 2 by the water | moisture content from the outside can be prevented more reliably. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the fifteenth embodiment.

[Embodiment 17]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment, and as shown in FIG. There is a feature in that a sealing portion 19 for sealing the light emitting element 2 is provided, and the sealing portion 19 is formed of a phosphor portion. Here, the phosphor part is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the sealing portion 19 is used by using the semiconductor light emitting device member as described later as the phosphor portion. It is possible to improve the light resistance, adhesiveness, sealing property, transparency, heat resistance, etc., and to suppress cracks and peeling with long-term use. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed by the phosphor portion 3B. The phosphor portion is present in all directions of the light emitting layer portion 21, and there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the fifteenth embodiment.

[Embodiment 18]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment. As shown in FIG. 19, the light emitting device 1B is disposed at the bottom of the recess 16a provided on one surface of the insulating substrate 16 (upper surface in FIG. 19). There is a feature in that a sealing portion 19 for sealing the light emitting element 2 is provided, and the sealing portion 19 is formed by the phosphor portion 3B. Here, the phosphor portion 3B is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the sealing portion is obtained by using the semiconductor light emitting device member as described later as the phosphor portion 3B. 19 light resistance, adhesion, sealing properties, transparency, heat resistance and the like can be improved, and cracks and peeling associated with long-term use can be suppressed.

[Embodiment 19]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment, and as shown in FIG. 20, the phosphor portion 33 formed in a lens shape on the upper surface (light extraction surface) of the sealing portion 19 in advance. There is a feature in that is provided. Here, the phosphor portion 33 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed.

[Embodiment 20]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment, and as shown in FIG. There is a feature in that is provided. Here, the phosphor portion 33 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed. Further, in the present embodiment, since the phosphor portion 3B is also disposed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, excitation and emission of the phosphor portion are more efficiently performed than in the nineteenth embodiment. There is an advantage of being done.

[Embodiment 21]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth embodiment. As shown in FIG. 22, the light emitting device 1B is disposed at the bottom of the recess 16a provided on one surface of the insulating substrate 16 (upper surface in FIG. 22). There is a feature in that a sealing portion 19 for sealing the light emitting element 2 is provided, and the sealing portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 23, the sealing portion 19 has a recess 19 c for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. Since what was processed into the shape which it has is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the sealing portion is obtained by using the semiconductor light emitting device member as described later as the phosphor portion 3B. 19 light resistance, adhesion, sealing properties, transparency, heat resistance and the like can be improved, and cracks and peeling associated with long-term use can be suppressed. In the present embodiment, the light emitted forward from the light emitting layer portion 21 of the light emitting element 2 is once reflected by the reflective layer 23 toward the inner bottom surface of the recess 16a. If a reflective layer is provided on the inner peripheral surface, it is further reflected on the inner bottom surface and the inner peripheral surface of the recess 16a and radiated forward, so that the optical path length can be increased and the phosphor portion 3B is more efficient. There is an advantage that excitation and emission can be performed.

[Embodiment 22]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth embodiment. As shown in FIG. 24, the light emitting device 1B is disposed at the bottom of the recess 16a provided on one surface of the insulating substrate 16 (upper surface in FIG. 24). There is a feature in that a sealing portion 19 for sealing the light emitting element 2 is provided, and the sealing portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 25, the sealing portion 19 has a concave portion 19c for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16a. Since what was processed into the shape which it has is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by the phosphor portion 3B, by using the semiconductor light emitting device member as described later as the phosphor portion 3B, sealing is performed. It becomes possible to improve the light resistance, adhesiveness, sealing property, transparency, heat resistance, etc. of the part 19 and to suppress cracks and peeling due to long-term use.

[Embodiment 23]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the sixth embodiment, and as shown in FIG. There is a feature in that. Here, a sealing portion 19 made of a translucent material is formed around the light emitting element 2 and the phosphor portion 3B, and the phosphor portion 3B has one end surface (lower end surface in FIG. The other end surface (the upper end surface in FIG. 26) is exposed in close contact with the light emitting layer portion 21. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 6, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor portion 3B whose one end face is in close contact with the light emitting layer portion 21 of the light emitting element 2 is formed in a rod shape, so that the light emitted from the light emitting layer portion 21 is emitted. The phosphor part 3B can be efficiently taken into the phosphor part 3B through the one end face of the phosphor part 3B, and the light emission of the phosphor part 3B excited by the taken-in light is efficiently transmitted to the outside through the other end face of the phosphor part 3B. Can be radiated. In this embodiment, only one phosphor portion 3B is formed in a relatively large-diameter rod shape. However, as shown in FIG. 27, the phosphor portion 3B is formed in a relatively small-diameter fiber shape. Then, a plurality of phosphor portions 3B may be arranged side by side. In addition, the cross-sectional shape of the phosphor portion 3B is not limited to a circular shape, and may be, for example, a quadrangular shape or other shapes.

[Embodiment 24]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the twenty-third embodiment, and includes a sealing portion 19 provided in the recess 16a of the insulating substrate 16 as shown in FIG. Is characterized by being formed by the phosphor portion 3B. Here, as shown in FIG. 29, the sealing portion 19 has a through hole 19 d for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. Since the thing processed into the shape which has this is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the first embodiment. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 23, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is also formed by the phosphor portion 3B, it is possible to extend the life and increase the efficiency of light emission. In this embodiment, only one phosphor portion 3B is formed in a relatively large-diameter rod shape. However, as shown in FIG. 30, the phosphor portion 3B is formed in a relatively small-diameter fiber shape. Then, a plurality of phosphor portions 3B may be arranged side by side. In addition, the cross-sectional shape of the phosphor portion 3B is not limited to a circular shape, and may be, for example, a quadrangular shape or other shapes.

[Embodiment 25]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and includes a frame member 18 disposed on one surface (upper surface in FIG. 31) of the insulating substrate 16 as shown in FIG. The light-emitting layer portion 21 of the light-emitting element 2 is an AlGaN-based light emitting device that emits near-ultraviolet light. It is characterized in that YAG: Ce ³⁺ phosphor powder that emits yellow light when excited is dispersed. Further, in the present embodiment, as the phosphor portion 3B, a fluorophosphate glass (for example, P ₂ O ₅ · AlF ₃ · MgF · CaF ₂ · SrF ₂ · BaCl that emits blue light when excited by near ultraviolet light) is used. ₂ : Eu ²⁺ ). In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 2, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19, so the light emitted from the light emitting element 2 and the phosphor A light output composed of the combined light of the light emitted from the portion 3B and the light emitted from the phosphor powder is obtained.

  Therefore, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor powder in the sealing portion 19 are emitted by the light emitted from the light emitting element 2. Both of them are excited and each emits a unique light emission, and the combined light is obtained. In the present embodiment, blue light is emitted from the phosphor portion 3B and yellow light is emitted from the phosphor powder, and white light different from any of the emission colors can be obtained.

In addition, in existing phosphor powders and phosphor particles in the phosphor part, materials that can emit light are limited, and a desired light color may not be obtained with only one of them, in such cases This embodiment is extremely effective. That is, when a desired light color characteristic cannot be obtained only by the phosphor part 3B, a desired powder color characteristic lacking in the phosphor part 3B is complemented and complemented. A light emitting device 1B having light color characteristics can be realized. In this embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B. However, if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the phosphor The light emission of the phosphor powder is superimposed on the light emission of the portion 3B, so that the light output can be increased and the light emission efficiency can be increased. Here, when the phosphor portion 3B and the phosphor powder have substantially the same emission color, for example, P ₂ O ₅ · SrF ₂ · BaF ₂ that emits red light as the phosphor particles of the phosphor portion 3B. : Eu ³⁺ and Y ₂ O ₂ S: Eu ³⁺ that emits red light as the phosphor powder can improve the efficiency of red light emission. Of course, the combination of the phosphor portion 3B and the phosphor powder is an example, and other combinations may be adopted.

[Embodiment 26]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. The light emitting layer portion 21 of the light emitting element 2 is an AlGaN-based light emitting device that emits near-ultraviolet light. The YAG: Ce ³⁺ phosphor powder that emits yellow light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Moreover, in this embodiment, fluorophosphate glass (for example, P ₂ that emits blue light when excited by near-ultraviolet light) is used as the phosphor particles of the phosphor portion 3B.
O ₅ · AlF ₃ · MgF · CaF ₂ · SrF ₂ · BaCl ₂ : Eu ²⁺ ). In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 27]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fourth embodiment. As shown in FIG. 33, the light emitting device 2 is sealed by filling the recess 16a formed on the upper surface of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and phosphor powder (for example, near ultraviolet light) is used in the translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder that is excited by light and emits yellow light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 4, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 28]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth embodiment. As shown in FIG. 34, the light emitting device 1B is filled in a recess 16a formed on one surface of the insulating substrate 16 (upper surface in FIG. 34). The light-emitting element 2 is provided with a sealing portion 19, and the light-emitting layer portion 21 of the light-emitting element 2 emits near-ultraviolet light in an AlGaN system, and a phosphor is included in the translucent material used as the sealing portion 19. It is characterized in that powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 5, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 29]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the sixth embodiment. As shown in FIG. 35, the light emitting device 1B is filled in a recess 16a formed on one surface of the insulating substrate 16 (upper surface in FIG. 35). The light-emitting element 2 is provided with a sealing portion 19, and the light-emitting layer portion 21 of the light-emitting element 2 emits near-ultraviolet light using an AlGaN system. It is characterized in that powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 6, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 30]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the first embodiment, and includes a bullet-shaped mold portion 11 as shown in FIGS. The part 21 is an AlGaN-based light emitting near-ultraviolet light, and a phosphor powder (for example, YAG: Ce ³⁺ fluorescent light that emits yellow light when excited by the near-ultraviolet light in the translucent material used as the mold part 11. The body powder) is dispersed, and the mold part 11 functions as a phosphor part. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 1, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited and emitted by the light from the light emitting element 2 is dispersed in the mold part 11 as in the case of the embodiment 25, and thus is emitted from the light emitting element 2. Light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3 </ b> B and the mold portion 11 are caused by the light emitted from the light emitting element 2. Both of the phosphor powders in the inside are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 31]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the eighth embodiment. As shown in FIG. 37, the light emitting device 1B includes a bullet-shaped mold portion 11 and the light emitting layer portion 21 of the light emitting element 2 (illustrated in FIG. 37). Is an AlGaN-based material that emits near-ultraviolet light, and phosphor powder (for example, YAG that emits yellow light when excited by near-ultraviolet light) in the translucent material used as the mold part 11. : Ce ³⁺ phosphor powder) is dispersed, and the mold part 11 functions as the phosphor part. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 8, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited and emitted by the light from the light emitting element 2 is dispersed in the mold part 11 as in the case of the embodiment 25, and thus is emitted from the light emitting element 2. Light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3 </ b> B and the mold portion 11 are caused by the light emitted from the light emitting element 2. Both of the phosphor powders in the inside are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 32]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the eleventh embodiment, and as shown in FIG. The light emitting layer portion 21 of the light emitting element 2 is an AlGaN-based light emitting device that emits near-ultraviolet light. The YAG: Ce ³⁺ phosphor powder that emits yellow light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 33, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 11, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 33 and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 33 and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 33. However, if the emission color of the phosphor powder is matched with the emission color of the phosphor part 33, the fluorescence color The light emission of the phosphor powder is superimposed on the light emission of the body part 33, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 33]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifteenth embodiment, and as shown in FIG. 39, a sealing portion that seals the light emitting element 2 on the one surface (upper surface in FIG. 39) side of the insulating substrate 16. 19 and the light emitting layer portion 21 of the light emitting element 2 emits near ultraviolet light in an AlGaN system, and the phosphor powder (for example, excited by near ultraviolet light) is used in the translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder that emits yellow light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 34, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 15, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 34 and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light-emitting layer portion 21 of the light-emitting element 2, the phosphor portion 34 and the sealing portion are emitted by the light emitted from the light-emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 34. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 34, the fluorescence color The light emission of the phosphor powder is superimposed on the light emission of the body part 34, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 34]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the nineteenth embodiment, and as shown in FIG. 40, the light emitting device 1B is filled in a recess 16a formed on one surface of the insulating substrate 16 (upper surface in FIG. 40). The light-emitting element 2 is provided with a sealing portion 19, and the light-emitting layer portion 21 of the light-emitting element 2 emits near-ultraviolet light using an AlGaN system. It is characterized in that powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 33, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 19, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 33 and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 33 and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 33. However, if the emission color of the phosphor powder is matched with the emission color of the phosphor part 33, the fluorescence color The light emission of the phosphor powder is superimposed on the light emission of the body part 33, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 35]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the twelfth and twenty-second embodiments, and as shown in FIG. 41, the recess 16a formed on one surface (the upper surface in FIG. 41) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing portion 19 for sealing the light emitting element 2, and the light emitting layer portion 21 of the light emitting element 2 emits near ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 33, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 12, 22, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 33 and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 33 and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 33. However, if the emission color of the phosphor powder is matched with the emission color of the phosphor part 33, the fluorescence color The light emission of the phosphor powder is superimposed on the light emission of the body part 33, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 36]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the twelfth embodiment. As shown in FIG. 42, the light emitting device 1B includes a sealing portion 19 that seals the light emitting element 2 on the upper surface side of the insulating substrate 16. The light emitting layer portion 21 of the element 2 is an AlGaN-based material that emits near-ultraviolet light, and phosphor powder (for example, excited by near-ultraviolet light to emit yellow light) in the translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 12, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 37]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the sixteenth embodiment, and as shown in FIG. The light emitting layer portion 21 of the light emitting element 2 is an AlGaN-based light emitting device that emits near-ultraviolet light. A phosphor powder (for example, excited by near-ultraviolet light) is used in the translucent material used as the sealing portion 19 The YAG: Ce ³⁺ phosphor powder that emits yellow light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 34, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 16, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 34 and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light-emitting layer portion 21 of the light-emitting element 2, the phosphor portion 34 and the sealing portion are emitted by the light emitted from the light-emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 34. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 34, the fluorescence color The light emission of the phosphor powder is superimposed on the light emission of the body part 34, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 38]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the twentieth embodiment. As shown in FIG. 44, the light emitting device 1B is filled in a recess 16a formed on one surface (the upper surface in FIG. 44) of the insulating substrate 16. The light-emitting element 2 is provided with a sealing portion 19, and the light-emitting layer portion 21 of the light-emitting element 2 emits near-ultraviolet light in an AlGaN system, and a phosphor is included in the translucent material used as the sealing portion 19. A feature is that powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 20, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 39]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth and twelfth embodiments, and as shown in FIG. 45, the recess 16a formed on one surface (the upper surface in FIG. 45) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 5, 12, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment 40]
The basic configuration of the light-emitting device 1B of this embodiment is substantially the same as that of Embodiments 20 and 21, and as shown in FIG. 46, fills a recess 16a formed on one surface of the insulating substrate 16 (upper surface in FIG. 46). The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed, and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 20, 21, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19 as in the case of the embodiment 25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B and the light emitted from the phosphor powder is obtained. That is, as in Embodiment 25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the sealing portion are emitted by the light emitted from the light emitting element 2. Both of the phosphor powders in No. 19 are excited and each emits a unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

  In each of the above embodiments, the phosphor portion 3B is processed into a desired shape or formed by a sol-gel method. However, as shown in FIG. 46, the phosphor portion 3B has a diameter slightly larger than the visible wavelength. If a large number of phosphor parts 3B are formed in a large spherical shape and dispersed in a solid medium 35 made of a translucent material and used in place of the phosphor parts in the above embodiments, the fluorescence in the visible wavelength range is obtained. While maintaining the transparency of the body part, the amount of material used in the phosphor part can be reduced, and the cost can be reduced.

  In addition, the light emitting device 1B of each of the above embodiments includes only one light emitting element 2, but a plurality of light emitting elements 2 constitute one unit module, and at least a part of the module is a phosphor as a light emitting substance. Of course, the parts may be arranged close to each other. For example, in the case of a light-emitting device including a shell-shaped mold part 11 as described in the first embodiment, a plurality of light-emitting devices may be mounted on the same printed board to constitute a unit module. . Further, for example, in the surface mount type light emitting device as described in the second embodiment, a plurality of light emitting elements 2 may be arranged on the same insulating substrate 16 to constitute a unit module.

[Application of members for semiconductor light emitting devices]
In the light-emitting device 1B (semiconductor light-emitting device) of each of Embodiments 1 to 40 described above, the location to which the semiconductor light-emitting device member is applied is not particularly limited. In each of the above embodiments, the example in which the semiconductor light emitting device member is applied as a member for forming the phosphor portions 3B, 33, 34 and the like has been shown. 18, can be suitably used as a member for forming the sealing portion 19 and the like. By using the semiconductor light emitting device member as a part or all of these members, the above-described excellent light resistance, adhesion, sealing property, transparency, heat resistance, film formability, cracks associated with long-term use Various effects such as suppression of peeling and peeling can be obtained. Furthermore, it is also possible to combine with other materials such as resin and glass as necessary, and in that case, a highly functional and long-life semiconductor light emitting device can be obtained.

  Moreover, when applying the said semiconductor light-emitting device member, it is preferable to add a deformation | transformation suitably according to the location which applies this invention. For example, when the present invention is applied to the phosphor portions 3B, 33, and 34, the above-described member for a semiconductor light-emitting device is formed with phosphor components such as phosphor ions and fluorescent dyes together with the phosphor (B) described above. You may mix with a fluorescent substance containing composition. As a result, in addition to the various effects mentioned above, it is possible to obtain an effect of further improving the retention of the phosphor (B).

  In addition, for example, if inorganic particles are mixed and used in the phosphor-containing composition used to form the semiconductor light emitting device member, in addition to the various effects listed above, improvement of light extraction efficiency and prevention of cracks, etc. Various effects can be obtained. In particular, a material adjusted to have a refractive index close to that of the light emitting element by using inorganic particles in combination acts as a suitable light extraction film.

[Applications of semiconductor light emitting devices]
The semiconductor light emitting device can be used for a light emitting device, for example. When a semiconductor light emitting device is used for a light emitting device, the light emitting device may be provided with a phosphor portion including a mixture of a red phosphor, a blue phosphor and a green phosphor on a light source. In this case, the red phosphor is not necessarily mixed in the same layer as the blue phosphor and the green phosphor. For example, the red phosphor is placed on the layer containing the blue phosphor and the green phosphor. The layer to contain may be laminated | stacked.

  In the light emitting device, the phosphor portion can be provided on the light source. The phosphor part can be provided, for example, as a contact layer between the light source and the sealing part, as a coating layer outside the sealing part, or as a coating layer inside the outer cap. Moreover, the form which contained (B) fluorescent substance in the sealing material can also be taken.

  As the sealing material used, the semiconductor light emitting device member can be used. Further, other sealing materials can be used in combination. As such a sealing material, a thermoplastic resin, a thermosetting resin, a photocurable resin, etc. are mentioned normally. 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. Further, an inorganic material such as a siloxane bond formed by solidifying a solution obtained by hydrolytic polymerization of a solution containing an inorganic material such as a metal alkoxide, ceramic precursor polymer or metal alkoxide by a sol-gel method, or a combination thereof. An inorganic material can be used. In addition, a melt-processed glass can be used as long as it is a sealing part that can be attached externally without directly touching the LED chip (for example, an external cap, a dome-shaped sealing part). In addition, a sealing material may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the phosphor (B) used with respect to the sealing material is not particularly limited, but is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more with respect to 100 parts by weight of the sealing material. The amount is preferably 1 part by weight or more, and usually 100 parts by weight or less, preferably 80 parts by weight or less, more preferably 60 parts by weight or less.

  Moreover, components other than (B) phosphor and inorganic particles can also be contained in the sealing material. For example, color correction dyes, antioxidants, processing / oxidation and heat stabilizers such as phosphorus-based processing stabilizers, light-resistant stabilizers such as ultraviolet absorbers, and silane coupling agents can be included. In addition, these components may be used by 1 type and may use 2 or more types together by arbitrary combinations and ratios.

  The light source used in the semiconductor light emitting device is not particularly limited, and a light emitter having a wide light emission wavelength region can be used. Usually, a light emitter having an emission wavelength from the ultraviolet region to the blue region is used. In the present invention, it is particularly preferable to use a light source having an emission wavelength from the near ultraviolet region to the blue region.

  The specific value of the emission wavelength of the light source is usually preferably 200 nm or more. Among these, when near-ultraviolet light is used as excitation light, the peak emission wavelength is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 410 nm or less, more preferably 400 nm or less. It is desirable to use a light emitter having When blue light is used as excitation light, it is desirable to use an illuminant having a peak emission wavelength of usually 420 nm or more, preferably 430 nm or more, and usually 500 nm or less, preferably 480 nm or less. Both are from the viewpoint of color purity of the light emitting device.

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

Among these, as the light source, a GaN-based LED or LD using a GaN-based 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 a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. GaN-based LEDs and LDs preferably have an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer. Among the GaN-based LEDs, those having an In _X Ga _Y N light-emitting layer are particularly preferable because the emission intensity is very strong, and in the GaN-based LD, the multiple quantum of the In _X Ga _Y N layer and the GaN layer is preferable. A well structure is particularly preferable because the emission intensity is very strong.

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

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like have high luminous efficiency, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.

  The light emitting device emits white light, and the light emission efficiency of the device is 20 lm / W or more, preferably 22 lm / W or more, more preferably 25 lm / W or more, and particularly preferably 28 lm / W or more. The color rendering index Ra is 80 or more, preferably 85 or more, more preferably 88 or more.

  The light-emitting device can be used alone or in combination, for example, as an illumination lamp, a backlight for a liquid crystal panel, various illumination devices such as ultra-thin illumination, and an image display device.

  Furthermore, the member forming liquid for a semiconductor light emitting device is useful for LED element sealing, particularly for blue LED and ultraviolet LED element sealing. Moreover, it can use preferably as a fluorescent substance holding material for high output illumination light sources, such as white LED and light bulb color LED which used blue light emitting element or ultraviolet light emitting element as an excitation light source, and wavelength-converted with the fluorescent substance. In addition, it can be used for applications such as the following display materials because of its excellent heat resistance, ultraviolet resistance, transparency and the like.

  Display materials include, for example, liquid crystal display substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, and other peripheral materials for next-generation flat panels Substrate materials for plasma addressed liquid crystal (PALC) displays, such as sealants for color plasma displays (PDPs), antireflection films, optical correction films, protective films for housing materials and front glass, substitutes for front glass, and adhesives , Light guide plate, prism sheet, deflector plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film, etc., front glass protective film for organic EL (electroluminescence) display, front glass substitute material, adhesive, etc. , Field emission display (FED) Seed film substrate, front glass protective films, front glass substitute material, adhesives and the like.

  The member forming liquid for a semiconductor light emitting device is excellent in adhesion and can be laminated by recoating which is difficult with a known addition condensation type silicone resin. Taking advantage of this property, for example, by forming the above-mentioned member-forming liquid mainly for methyl groups as a low refractive index layer and laminating it with a high refractive index layer into which high refractive organic groups such as phenyl groups or zirconia nanoparticles are introduced. Thus, a layer structure having a difference in refractive index can be formed, and a light guide layer having high durability and excellent adhesion and flexibility can be easily formed.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example, unless it deviates from the summary.

[Example 1]
Momentive Performance Materials Japan G.K., both ends silanol dimethyl silicone oil XC96-723 385g, methyltrimethoxysilane 10.28g, zirconium tetraacetylacetonate powder 0.791g as a stirring blade In a 500 ml three-necked Kolben equipped with a fractionating tube, a Dimroth condenser, and a Liebig condenser, the mixture is stirred at room temperature for 15 minutes until the coarse particles of the catalyst are dissolved. Thereafter, the temperature of the reaction solution is raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis is performed while stirring at 500 rpm for 30 minutes under 100 ° C. total reflux.

Subsequently, the distillate was connected to the Liebig condenser side, nitrogen was blown into the liquid with SV20, and methanol, water, and low-boiling silicon components of by-products were distilled off accompanied with nitrogen for 1 hour at 100 ° C. and 500 rpm. Stir. The polymerization reaction is continued for 5.5 hours while heating and maintaining at 130 ° C. while blowing nitrogen into the liquid with SV20 to obtain a reaction liquid having a viscosity of 389 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Thus, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

  After stopping the blowing of nitrogen and cooling the reaction solution to room temperature, the reaction solution was transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount on an oil bath at 120 ° C. and 1 kPa for 20 minutes using a rotary evaporator, The low boiling silicon component is distilled off to obtain a solvent-free liquid medium (condensation type silicone material) having a viscosity of 584 mPa · s.

As shown in Table 1 below, 1.0 g of the above liquid medium, 0.12 g of hydrophobic fumed silica “Aerosil RX-200” manufactured by Nippon Aerosil Co., Ltd., and red, green, and blue phosphors as an inorganic filler Put in an ointment jar manufactured by Chemical Container Co., Ltd., depressurize to about 0.7 kPa at a liquid temperature of 35 ° C., and perform vacuum centrifugal defoaming using a rotating / revolving vacuum mixer “ARV310” manufactured by Shinky Corp. Is made.

A 900 μm square chip “C405-XB900” (emission wavelength: 405 nm) manufactured by Cree Inc. is fixed on the submount with Au—Sn eutectic solder, and then the submount is made of 9 mmφ MC Sea Corp. with Au—Sn eutectic solder. Secure on metal package. Wire bonding is performed from the electrode on the chip to the pin on the metal package with a gold wire. 40 μl of the phosphor-containing composition obtained above is poured into a package on which this chip is mounted by a manual pipette, and is sealed by curing in a ventilated oven under a slight wind at 150 ° C. for 3 hours.
Since the cured product of the phosphor-containing composition thus obtained has less foaming, a good semiconductor light emitting device can be obtained as a result.

[Example 2]
In place of the liquid medium of Example 1, 1.0 g of a one-component addition type silicone material “JCR6101UP” manufactured by Toray Dow Corning Co., Ltd. is similarly used to prepare a phosphor-containing composition.
As in Example 1, when this phosphor-containing composition is sealed on a package on which a chip is placed, the resulting cured product of the phosphor-containing composition has less foaming, resulting in good semiconductor light emission. A device can be obtained.

[Effects of the present invention]
As in Examples 1 and 2, when the container has a side surface and a bottom surface, such as an ointment bowl, with a smooth curved surface and connected to the bottom surface, convection by stirring of the liquid medium is efficiently performed, and the time is short. It is considered that a cured product with less foaming can be obtained even with stirring. Also, in the rotation / revolution mixer, the center of the bottom of the container is a blind spot where convection does not occur easily, so when using a liquid medium with high viscosity or when the amount of filler and phosphor added is large, It is considered that when a container having a shape in which the center protrudes inward is used, stirring is sufficiently performed and foaming of the cured product can be reduced.

In addition, a foam-free cured product can be obtained by defoaming a phosphor-containing composition containing a liquid medium, a filler, and a phosphor before heating and curing.
The defoaming treatment may be performed simultaneously with the mixing of each component, but may be performed after the mixing. Centrifugal defoaming may be performed using a rotating / revolving vacuum mixer at normal pressure, and if the viscosity is high, centrifugal defoaming may be performed under reduced pressure. When the same vacuum centrifugal defoaming is performed after dispersing various fillers and phosphors, it is easy to generate heat of stirring, so it is thought that thickening and decomposition due to heat can be suppressed by using a stirring device having a cooling function. .

  Normally, the liquid medium has a high viscosity and degassing has a rate of movement of gas components to the gas-liquid interface. Therefore, when degassing and defoaming, the pressure is reduced while stirring using, for example, a rotating / revolving vacuum mixer. Then, a light boiling component can be removed efficiently.

  According to the method for producing a phosphor-containing composition of the present invention, the cured product is less likely to contain bubbles, and the phosphor can be uniformly dispersed. Therefore, it can be suitably used for semiconductor light emitting devices in a wide range of fields such as illumination devices, image display devices, light sources for liquid crystal backlights such as thin televisions. In particular, because of its excellent light extraction efficiency, adhesiveness, heat resistance, and the like, a semiconductor light emitting device that emits near ultraviolet light and ultraviolet light without a conventional suitable sealant, and an illumination device to which it can be applied, and image display The industrial applicability is extremely high in each field such as equipment.

It is explanatory drawing of the basic concept of the semiconductor light-emitting semiconductor light-emitting device which is a use of the fluorescent substance containing composition manufactured by this invention. Embodiment 1 is shown, (a) is a schematic sectional view, (b) is an enlarged view of the main part of (a). FIG. 6 is a schematic cross-sectional view showing a second embodiment. FIG. 6 is a schematic cross-sectional view showing a third embodiment. FIG. 6 is a schematic cross-sectional view showing a fourth embodiment. FIG. 6 is a schematic cross-sectional view showing a fifth embodiment. FIG. 9 is a schematic cross-sectional view showing a sixth embodiment. FIG. 10 is a schematic cross-sectional view showing a seventh embodiment. 10 is a schematic cross-sectional view showing an eighth embodiment. FIG. 10 is a schematic sectional view showing Embodiment 9. FIG. FIG. 10 is a schematic cross-sectional view showing a tenth embodiment. 14 is a schematic cross-sectional view showing Embodiment 11. FIG. FIG. 20 is a schematic sectional view showing Embodiment 12. FIG. 16 is a schematic sectional view showing Embodiment 13. It is a schematic sectional drawing which shows Embodiment 14. FIG. 17 is a schematic sectional view showing Embodiment 15. FIG. 20 is a schematic sectional view showing Embodiment 16; FIG. 20 is a schematic sectional view showing Embodiment 17; FIG. 20 is a schematic sectional view showing Embodiment 18; FIG. 20 is a schematic sectional view showing Embodiment 19; FIG. 20 is a schematic sectional view showing Embodiment 20; FIG. 22 is a schematic sectional view showing Embodiment 21. FIG. 22 is a cross-sectional view showing a main part according to a twenty-first embodiment. FIG. 24 is a schematic sectional view showing Embodiment 22; FIG. 22 is a cross-sectional view of a main part shown in a twenty-second embodiment. FIG. 24 is a schematic sectional view showing Embodiment 23. FIG. 29 is a perspective view of relevant parts shown in Embodiment 23. FIG. 25 is a schematic sectional view showing Embodiment 24. FIG. 22 is a cross-sectional view of a main part shown in Embodiment 24. FIG. 25 is a perspective view showing a main part of a twenty-fourth embodiment. FIG. 26 is a schematic sectional view showing Embodiment 25. FIG. 26 is a schematic sectional view showing Embodiment 26. 42 is a schematic sectional view showing Embodiment 27. FIG. FIG. 29 is a schematic sectional view showing Embodiment 28. FIG. 30 is a schematic sectional view showing Embodiment 29. Embodiment 30 is shown, (a) is a schematic sectional view, and (b) is an enlarged view of a main part of (a). 36 is a schematic sectional view showing Embodiment 31. FIG. FIG. 36 is a schematic sectional view showing Embodiment 32. FIG. 34 is a schematic sectional view showing Embodiment 33. 36 is a schematic sectional view showing Embodiment 34. FIG. FIG. 36 is a schematic sectional view showing Embodiment 35. 36 is a schematic sectional view showing Embodiment 36. FIG. FIG. 38 is a schematic sectional view showing Embodiment 37. FIG. 40 is a schematic sectional view showing Embodiment 38. 40 is a schematic sectional view showing Embodiment 39. FIG. FIG. 42 is a schematic sectional view showing Embodiment 40. It is a figure explaining an example of the container which has the shape where the cylindrical inner surface was connected to the bottom face by the smooth curved surface, and is a typical sectional view in the perpendicular plane passing through the bottom face center of the container. It is a figure explaining an example of the container in which the center part of the bottom is formed in a shape that rises smoothly and concentrically with respect to the cylindrical inner surface, and is a schematic cross section in a vertical plane passing through the center of the bottom of the container FIG.

Explanation of symbols

1,1B Light emitting device (semiconductor light emitting device)
2 Light emitting element 3B Phosphor part (semiconductor light emitting device member)
4a, 4b Part of the light emitted from the light emitting element 5 Light having a wavelength peculiar to fluorescent components such as phosphor particles, fluorescent ions, fluorescent dyes contained in the phosphor part 11 Mold part 12, 13 Lead terminal 14 Mirror ( Cup part)
15 conductive wire 16 insulating substrate 16a recess 17 printed wiring 18 frame material 19 sealing part 19a sealing function part 19b lens function part 19c recess 19d through hole 21 light emitting layer part 23 reflecting layer 24 bump 33, 34 phosphor part 35 solid Medium a Inner surface b Smooth curved surface c connecting the inner surface and the bottom surface Bottom surface d Shape H ₁ that rises smoothly and concentrically with the cylindrical inner surface H ₁ Height of the raised shape d H ₂ Height inside the container Height (height from bottom to container mouth)
W Container mouth size (caliber)

Claims (2)

A method for producing a phosphor-containing composition comprising (A) a filler, (B) a phosphor, and (C) a liquid medium,
A phosphor comprising: (A) a filler, (B) a phosphor, and (C) a liquid medium mixed and stirred in a container having a shape in which a cylindrical inner surface is connected to the bottom surface with a smooth curved surface. The manufacturing method of a containing composition. 2. The phosphor-containing material according to claim 1, wherein the mixing and stirring is performed in a container in which a central portion of a bottom surface is formed in a shape that is smoothly raised concentrically with respect to a cylindrical inner surface. A method for producing the composition.

Images