JP4923728B2 - Phosphor-containing composition, light emitting device, lighting device, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor composition which is not deteriorated with time and in which light emitting properties are not changed even when the composition uses a phosphor having low humidity resistance in which deterioration is caused by moisture, a light emitting device, an illuminating device and an image display. <P>SOLUTION: This phosphor-containing composition comprises: (A) a phosphor having a deterioration degree of 1% or more as measured according to the following phosphor deterioration degree measuring test (I); and (B) a silicone-based compound containing substantially no aromatic group. The phosphor deterioration degree measuring test (I) comprises: (a) measuring the brightness of a powder of the phosphor to report the measured value as x; (b) allowing the powder of the phosphor of which brightness has been measured in (a) to stand still in air having a temperature of 60&deg;C and a relative humidity of 90% for one day; (c) measuring the brightness of the phosphor powder which has been obtained in (b) in substantially the same manner as in (a) to report the measured value as y; and (d) acquiring fluorescent substance deterioration degree (%)=(1-y/x)&times;100. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a phosphor-containing composition, a light emitting device, a lighting device, and an image display device. Specifically, the present invention relates to a phosphor-containing composition with little deterioration over time, a light-emitting device formed using the phosphor-containing composition, and an illumination device and an image display device formed using the light-emitting device.

A phosphor as a wavelength conversion material is a gallium nitride (GaN) light emitting diode (light emitting diode) having high luminous efficiency, which is attracting attention as a near-ultraviolet to blue light emitting semiconductor light emitting device as a material for a white light emitting device. And a semiconductor laser diode (hereinafter abbreviated as “LD” where appropriate), and the light emitting device emits light from an image display device or a lighting device. Used as a source.

The phosphor is required to have a high efficiency with respect to blue excitation light from the near ultraviolet region where the luminous efficiency of the semiconductor light emitting device is high.
However, some of these phosphors have low moisture resistance and deteriorate due to moisture, unlike phosphors conventionally used in fluorescent lamps and the like. When a semiconductor light emitting device is manufactured using such a phosphor, there is a problem that the light emission characteristics change with time. In order to hold the phosphor used in such a light emitting device, an epoxy resin, a general silicone resin or the like has been conventionally used (Patent Documents 1 to 3), but an epoxy resin generally has a high water absorption rate. Moreover, since a silicone resin generally has high moisture permeability, it has not been a practically sufficient solution.
Japanese Patent No. 3241338 JP 7-25987 A Japanese Patent Laid-Open No. 2005-42099

  The present invention has been made in view of the above-described prior art, and is a phosphor composition that has low moisture resistance and does not deteriorate over time even when a phosphor that deteriorates due to moisture is used, and whose light emission characteristics do not change, The object is to provide a light emitting device, a lighting device, and an image display device.

As a result of intensive investigations to solve the above problems, the present inventors have found that a specific silicone compound is effective in preventing deterioration over time of a light emitting device in a specific phosphor having low moisture resistance, and reached the present invention. did.
That is, the gist of the present invention resides in the following (1) to (7).
(1) A phosphor-containing composition containing (A) a phosphor and (B) a silicone compound, wherein the phosphor (A) has a degradation degree of 1 according to the following phosphor degradation degree measurement test (I). % And 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 base crystal (where M is Ca, Sr , Ba represents at least one selected from the group consisting of Ba, and Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Ho as activators , Er, Tm, those that contain at least one of Yb, the (B) silicone-based compound, a phosphor-containing composition characterized by having no free aromatic group.
Phosphor degradation test (I)
a) The brightness of the phosphor powder is measured, and the measured value is defined as x.
b) The phosphor powder whose luminance was measured in a) is left in air at a temperature of 60 ° C. and a relative humidity of 90% for one day.
c) The luminance of the phosphor powder obtained in b) is measured by the same method as in a), and the measured value obtained is y.
d) The phosphor deterioration degree (%) = (1−y / x) × 100 is obtained.
(2) (A) the phosphor, an alkaline earth metal, and the temperature 60 ° C., with a phosphor to produce an alkaline earth metal carbonate when allowed to stand for 1 day in a relative humidity of 90% air it Oh Ru and wherein phosphor-containing composition according to (1).
(3) The phosphor (A) is (Sr _1-a Ba _a ) ₃ SiO ₅ : Eu (a satisfies 0 ≦ a ≦ 1).
Fulfill. The phosphor-containing composition according to (1) or (2), wherein
(4) A light-emitting device formed using the phosphor-containing composition according to any one of (1) to (3).
(5) A light emitting device formed using the semiconductor light emitting element and the phosphor-containing composition according to any one of (1) to (3), wherein the deterioration is caused by the following semiconductor light emitting device deterioration test (II) A light emitting device having a degree of 5% or less.
Semiconductor light emitting device degradation measurement test (II)
e) A semiconductor light emitting device is fabricated by sealing the semiconductor light emitting element with the phosphor-containing composition.
f) For the semiconductor light emitting device fabricated in e), let φ _{1 be} the total luminous flux of the semiconductor light emitting device when the rated current of the semiconductor light emitting element is applied.
g) The semiconductor light emitting device whose luminous flux has been measured in f) is left in an unpowered state for 3 days in air at a temperature of 60 ° C. and a relative humidity of 90%.
The total flux of when the rated current for the semiconductor light-emitting device obtained in h) g) and phi _2.
i) Deterioration degree (%) = (1−φ ₂ / φ ₁ ) × 100 is obtained.
(6) A lighting device formed using the light emitting device according to (4) or (5).
(7) An image display device formed using the light emitting device according to (4) or (5).

  According to the present invention, there are provided a phosphor composition, a light emitting device, a lighting device, and an image display device that do not deteriorate with time and do not change light emission characteristics even when a phosphor that has low moisture resistance and causes deterioration due to moisture is used. can do.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
[1] Phosphor composition It is essential that the phosphor-containing composition of the present invention contains (A) a phosphor and (B) a silicone compound which is a liquid medium. Moreover, you may contain other arbitrary components if needed.

[1-1] (A) phosphor The phosphor (A) contained in the phosphor-containing composition of the present invention comprises:
(I) Deterioration degree by phosphor degradation degree measurement test (I) described later (I) is 1% or more (Claim 1), or (ii) Alkaline earth metal is contained, and immediately after production, the temperature is 60 ° C. Producing alkaline earth metal carbonates when left in air at 90% relative humidity for a day (claim 2)
Is a feature.
This means that the phosphor constituting the phosphor-containing composition of the present invention has low moisture resistance. That is, the phosphor-containing composition of the present invention has the technical significance that it can be used stably in phosphors with low moisture resistance.
Hereinafter, (A) the phosphor will be described.

[1-1-1] Deterioration degree by phosphor deterioration degree measurement test (I) The phosphor contained in the first phosphor-containing composition of the present invention is deteriorated by the following phosphor deterioration degree measurement test (I). The degree is characterized by being 1% or more.
Phosphor degradation test (I)
a) The brightness of the phosphor powder is measured, and the measured value is defined as x.
b) The phosphor powder whose luminance was measured in a) is left in air at a temperature of 60 ° C. and a relative humidity of 90% for one day.
c) The luminance of the phosphor powder obtained in b) is measured by the same method as in a), and the measured value obtained is y.
d) The phosphor deterioration degree (%) = (1−y / x) × 100 is obtained.

  That is, a phosphor with low moisture resistance that is found to have a luminance decrease of 1% or more as measured by a luminance meter is used as a constituent of the phosphor contained in the first phosphor-containing composition of the present invention. And When the phosphor-containing composition of the present invention exhibits the effect of preventing deterioration with time, the degree of deterioration of the phosphor is preferably 5% or more, more preferably 10% or more, particularly preferably 20% or more, and particularly preferably 50%. That's it. Further, the upper limit of the degree of deterioration is usually 90%, preferably 70%. If the degree of deterioration is too high, deterioration of the light emitting device may be observed even when a later-described (B) silicone compound is used.

  The x value in the phosphor degradation degree measurement test (I) preferably measures the luminance of the phosphor powder immediately after production. This is because the phosphor is measured in a state where it is not deteriorated by contact with moisture. Therefore, even if it is not phosphor powder immediately after production, it is stored in a desiccator after production of the phosphor so that it does not affect deterioration, or it is enclosed and stored in an aluminum laminate pack with high humidity barrier properties, etc. You may measure quickly through the state.

[1-1-2] Deterioration degree due to generation of alkaline earth metal carbonate The phosphor contained in the second phosphor-containing composition of the present invention has a deterioration degree defined in [1-1-1]. Or in place of this, an alkaline earth metal carbonate is produced when it is left in air at a temperature of 60 ° C. and a relative humidity of 90% for 1 day immediately after production. It is a feature.

Formation of metal carbonate can be confirmed by a known qualitative analysis method using an X-ray diffraction method.
For example, when X-ray diffraction is performed with CuKα rays before and after leaving Sr ₂ BaSiO ₅ ; Eu (hereinafter sometimes referred to as “SBS”) in air at a temperature of 60 ° C. and a relative humidity of 90% for one day. As shown in FIG. 4 before leaving and in FIG. 5 after leaving, Sr ₂ BaSiO ₅ ; Eu
It can be seen that (Sr, Ba) CO ₃ is generated. [1-1-3] Particle Size and Shape of Phosphor Particles The particle size of the phosphor used in the present invention is not particularly limited, but the larger the phosphor particle size, the smaller the specific surface area and the reaction with moisture. Is preferable because of a small amount. The particle diameter of the phosphor is usually 0.1 μm to 100 μm, preferably 2 μm to ₅₀ μm, and more preferably 10 μm to 20 μm, as the median particle diameter (D ₅₀ ). The particle size distribution (QD) of the phosphor particles is preferably small in order to align the dispersed state of the particles in the phosphor-containing composition, but in order to reduce the particle size, the classification yield decreases, leading to an increase in cost. Usually, it is 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more. Moreover, it is 0.4 or less normally, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. Further, the shape of the phosphor particles is not particularly limited as long as the phosphor part formation is not affected.

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

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

[1-1-4] Types of phosphor The phosphor used in the present invention is a phosphor that easily reacts with moisture as described above.
As such a phosphor, 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 (where M is Ca, Sr , Ba represents at least one selected from the group consisting of Ba), and Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho as activators , Er, Tm, and Yb.

As a specific example of the phosphor, 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 S4: 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 ) AlSi
N 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, B
_{a 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
(With respect to the above, a satisfies 0 ≦ a ≦ 1).
Among _{them, Sr 2 BaSiO 5: Eu,} CaS, CaGa 2 S 4: Eu, SrGa 2 S 4: Eu, (Sr 0.8 Ca 0.2) AlSiN 3: Eu, SrAlSiN 3 -: mentioned as preferred the Eu I can do it.

[1-1-5] Surface treatment of phosphor The phosphor used in the present invention is subjected to a surface treatment for the purpose of enhancing water resistance or preventing unnecessary aggregation of the phosphor in the phosphor-containing composition. It may be done. Examples of such surface treatment include surface treatment using an organic material, an inorganic material, a glass material (Japanese Patent Laid-Open No. 2002-223008), and the like. However, the treatment performed in an aqueous solution is not preferable because the phosphor according to the present invention may be deteriorated.

[1-1-6] Compounding amount of phosphor The phosphor according to the present invention may be used alone or in combination of two or more in any combination and ratio. Also, other phosphors described later in [2-2] can be used in combination.
The blending amount of the phosphor (A) is usually determined by the emission color to be obtained when the light emitting device is used, but is usually 0.01 parts by weight with respect to 100 parts by weight of the (B) silicone compound described later. Above, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and usually 100 parts by weight or less, 80 parts by weight or less, more preferably 60 parts by weight or less. (A) There is no particular problem when the amount of the phosphor blended is too small. However, when the amount is too large, the fluidity of the phosphor-containing composition is deteriorated. The coating process or filling process becomes difficult.

[1-2] (B) Silicone Compound The (B) silicone compound contained in the phosphor-containing composition of the present invention is characterized by substantially not containing an aromatic group. (B) Although the mechanism by which the silicone compound prevents the deterioration of the light emitting device of the present invention is not sufficiently clear, the following reasons (i) and (ii) are presumed.
(I) A silicone resin having an aromatic group is generally brittle and not sticky when subjected to a mechanical load, and therefore follows volume shrinkage during cooling after heat curing or volume expansion during heating such as soldering. However, it is presumed that microcracks are likely to occur, moisture is likely to enter the inside through the cracks, and the deterioration of the phosphor with low moisture resistance is assumed to be promoted. Such a problem does not occur when the silicone resin is not contained.
(Ii) Since the silicone resin having an aromatic group generally has low affinity with the phosphor surface, the effect of preventing moisture from approaching the phosphor surface is not sufficient, whereas the aromatic group according to the present invention Such a problem does not occur in a silicone resin that substantially does not contain.

Accordingly, it is desirable that the (B) silicone compound according to the present invention does not allow moisture to permeate in the state of use and does not retain moisture in order to prevent the phosphor and moisture from reacting.
In addition, the (B) silicone compound according to the present invention does not have “substantially” an aromatic group means that the silicone compound does not have an aromatic group or the amount of the aromatic group is very small. In this case, (A) a substance that does not affect the deterioration of the phosphor is shown.

The “aromatic group” substantially not contained in the (B) silicone compound according to the present invention includes, for example, a functional group including a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and derivatives thereof. it can. Among these, a phenyl group and derivatives thereof are preferable.
The detection of the aromatic group can be performed by, for example, the following method.

That is, the infrared absorption spectrum of the silicone compound can be measured, and the presence or absence of an aromatic group can be determined by the presence or absence of characteristic vibration absorption derived from the aromatic group. For example, the upper part of FIG. 6 shows an infrared absorption spectrum of a silicone resin that is preferably used in the present invention, and the lower part of FIG. 6 shows an infrared absorption spectrum of a silicone resin that is not preferably used in the present invention. According to the comparison of FIG. 6 the upper and lower infrared absorption spectrum, undesirable silicone resin wavelength ^{698cm -1, 717cm -1,} infrared absorption by CH out-of-plane bending vibration of the benzene ring to 741cm ^-1, 1593cm ^{- 1} Infrared absorption by C = C stretching vibration of benzene ring, 3026cm
^{-1, 3051cm -1,} since the infrared absorption due to CH stretching vibration of benzene ring 3071Cm ^-1 is observed at the same time, it is confirmed with a benzene ring structure is an aromatic group.

The phosphor-containing composition of the present invention forms part of the light emitting device in a state where (B) the silicone compound is cured by a curing reaction and fluidity is lost. (B) When silicone compounds are classified according to the curing mechanism, silicone compounds such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be mentioned. Among these, addition curing type, condensation curing type, and UV curing type are preferable. Specific product names of the addition polymerization curing type include “LPS-1400”, “LPS-2410”, “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[1-3] Other components In addition to the above components, the phosphor-containing composition of the present invention includes dyes, antioxidants, stabilizers (processing stabilizers such as phosphorus processing stabilizers, oxidation stabilization) Any additive known in the art such as a light-resistant stabilizer such as an agent, a heat stabilizer, and an ultraviolet absorber), a silane coupling agent, a light diffusing material, and a filler can be used.

[1-4] Production method and characteristics of phosphor-containing composition The phosphor-containing composition of the present invention is produced, for example, by the method described below. Moreover, it is preferable that the manufactured fluorescent substance composition has the various characteristics mentioned later in a viscosity and a deterioration degree. [1-4-1] Manufacturing method
(B) When a silicone resin is used as the silicone compound, for example, a silicone resin, a crosslinking agent, a curing catalyst, (A) a phosphor and silica fine particles, an extender, and other additives are blended, a mixer, a high-speed disper, It can manufacture by a conventionally well-known method, such as mixing with a homogenizer, 3 rolls, a kneader.
In this case, (B) a silicone resin, a crosslinking agent, a curing catalyst, (A) a phosphor and silica fine particles, an extender, and other additives are all mixed to produce a liquid silicone resin composition as one liquid form. However, two liquids are prepared: (i) a silicone resin, (A) a silicone resin liquid mainly composed of a phosphor and an extender, and (ii) a crosslinking agent liquid mainly composed of a crosslinking agent and a curing catalyst. In addition, a liquid silicone resin composition may be produced by mixing a silicone resin solution and a crosslinking agent solution immediately before use.

[1-4-2] Physical properties of phosphor-containing composition [1-4-2-1] Viscosity The viscosity of the phosphor-containing composition of the present invention is usually 500 mPa · s or more, preferably 1000 mPa · s or more, and Preferably it is 2000 mPa * s or more, Usually 15000 mPa * s or less, 10000 mPa * s or less, Preferably it is 8000 mPa * s or less. If the viscosity is too high, it may cause trouble such as blockage of pipes at the time of injection, and bubbles may be difficult to escape, and further, lead wires of semiconductor elements are likely to be disconnected. On the other hand, if the viscosity is too low, the phosphor particles settle, which is not preferable.

[2] Light Emitting Device The light emitting device of the present invention is formed by a known method using the phosphor-containing composition described in [1]. Hereinafter, the light emitting device of the present invention will be described.
[2-1] Light Source The light source in the light emitting device of the present invention emits light that excites the phosphor of [1-1] and other phosphors described later. The emission wavelength of the light source is not particularly limited as long as it overlaps with the absorption wavelength of the phosphor, and a phosphor having a wide emission wavelength region can be used. Usually, a phosphor having an emission wavelength from the near ultraviolet region to the blue region is used, and specific values are usually 300 nm or more, preferably 330 nm or more, and usually 500 nm or less, preferably 480 nm or less. A light emitter having the following is used. As this light source, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a semiconductor laser diode (LD), or the like can be used.

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

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

[2-2] Other phosphors The phosphor used in the light-emitting device of the present invention is a phosphor that emits visible light when irradiated with light from the light source described above, and contains the phosphor of [1-1]. In addition, other phosphors which will be described later are appropriately contained according to the use and the like.
There is no particular limitation on the composition of the phosphor, _Y 2 _O 3 is a host _crystal, Zn 2 metal oxide represented by SiO ₄ and the _like, a metal nitride typified by Sr 2 _Si 5 _{N 8} such, Ca ₅ (PO ₄ ) ₃ Cl etc. and phosphates such as ZnS, SrS, CaS etc., Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, A combination of rare earth metal ions such as Tm and Yb and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators is preferred.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, C
a) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉
, (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O _12, etc., aluminates such as Y ₂ SiO ₅ Silicate such as Zn ₂ SiO ₄ , oxide such as SnO ₂ and Y ₂ O ₃ , borate such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ (F, Cl ) ₂ , halophosphates such as (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ , phosphates such as Sr ₂ P ₂ O ₇ , (La, Ce) PO _4, etc. it can.

However, the crystal matrix and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, phosphors that differ only in part of the structure are omitted as appropriate. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “ “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are collectively shown as “(La, Y) ₂ O ₂ S: Eu”. ing. Omitted parts are shown separated by commas (,).

[2-2-1] Orange to red phosphor
As a phosphor emitting orange to red fluorescence (hereinafter referred to as “orange to red phosphor” as appropriate) in the light emitting device of the present invention, in addition to the phosphor of [1-1], one or more other types. These orange or red phosphors may be used in combination.

When the specific wavelength range of the fluorescence emitted by the red phosphor is exemplified, the peak wavelength is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less, preferably 680 nm or less.
The orange or red phosphor other than the phosphor of the present invention is composed of, for example, fractured particles having a red fracture surface and emits light in a red region (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu Europium-activated alkaline earth silicon nitride phosphor expressed by the following formula: growth particles having a substantially spherical shape as a regular crystal growth shape, and emitting light in the red region (Y, La, Gd, Lu) ₂ Examples include europium activated rare earth oxychalcogenide phosphors represented by O ₂ S: Eu.

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

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba,
Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphor such as Eu, Mn, (Ca, Sr) S: Eu attached such as Eu Active sulfide phosphor, Eu-activated aluminate phosphor such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu-activated silicate phosphor such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce-activated aluminate phosphors such as Ce, (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Mg, Ca, Sr, Ba) SiN ₂ : Eu, (Mg, Ca, Sr, Ba) AlSiN _3: Eu-activated nitride phosphor such as Eu, (Mg, Ca, Sr , Ba) AlSiN 3: Ce-activated nitride phosphor such as e, (Sr, Ca, Ba , Mg) 10 (PO 4) 6 Cl 2: Eu, Eu such as Mn, Mn-activated halophosphate phosphor, _(Ba 3 Mg) Si ₂ O ₈ : Eu, Mn, (Ba
, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphors such as Eu and Mn, 3.5MgO · 0.5MgF ₂ · GeO ₂ : with Mn such as Mn Active germanate phosphor, Eu-activated oxynitride phosphor such as Eu-activated α sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated oxide phosphor such as Eu and Bi (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi-activated oxysulfide phosphors such as Eu and Bi, (Gd, Y, Lu, La) VO ₄ : Eu such as Eu and Bi, Bi-activated vanadate phosphors, Eu and Ce-activated sulfide phosphors such as SrY ₂ S ₄ : Eu, Ce, Ce-activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, (Ba, Sr, _{Ca) MgP 2 O 7: Eu} , Mn, (Sr, Ca, Ba, Mg, Zn) 2 P 2 O 7: Eu, Eu such as Mn, M n-activated phosphate phosphor, (Y, Lu) ₂ WO ₆ : Eu, Mo-activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (However, x, y, z are integers of 1 or more) Eu, Ce activated nitride phosphor, (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH) ): Eu, Eu such as Mn, Mn-activated halophosphate phosphor, ((Y, Lu, Gd , Tb) 1-x Sc x Ce y) 2 (Ca, Mg) 1-r (Mg, Zn) It is also possible to use Ce-activated silicate phosphors such as _{2 + r} Si _z-q GeqO _{12 + δ} .

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

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

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

In addition, as the green phosphor, Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr,
Ca) Al ₂ O ₄ : Eu-activated aluminate phosphor such as Eu, (Sr, Ba) Al ₂ Si ₂ O
₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, etc. Eu-activated silicate _{phosphors, Y 2 SiO 5: Ce,} Ce and Tb such, Tb-activated silicate _{phosphor, Sr 2 P 2 O 7 -Sr} 2 B 2 O 5: Eu -activated borate such as Eu phosphate _{phosphor, Sr 2 Si 3 O 8 -2SrCl} 2: Eu activated halo silicate phosphor such as Eu, Zn ₂ SiO _4: Mn-activated silicate phosphors such as Mn, CeMg
Tb-activated aluminate phosphor such as Al ₁₁ O ₁₉ : Tb, Y ₃ Al ₅ O ₁₂ : Tb, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Tb, La ₃ Ga ₅ SiO ₁₄ : Tb, etc. Tb-activated silicate phosphor, (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, and Ce-activated oxide phosphor such as CaSc ₂ O ₄ : Ce SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu-activated β-sialon, Eu-activated α-sialon and other Eu-activated oxynitride phosphors, BaMgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn, SrAl ₂ O ₄ : Eu activated aluminate phosphor such as Eu, (La, Gd, Y) ₂ O ₂ S: Tb, etc. Tb-activated oxysulfide phosphor, LaPO ₄ : Ce, Tb-activated phosphate phosphor such as Ce, Tb, sulfide phosphor such as ZnS: Cu, Al, ZnS: Cu, Au, Al, Y, Ga, Lu, Sc, La) BO 3: Ce, Tb, Na 2 Gd 2 _{2 O 7: Ce, Tb,} (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6: K, Ce, Ce and Tb such, Tb-activated borate phosphor, _Ca 8 Mg (SiO _{4) 4} Cl ₂ : Eu, Mn activated halosilicate phosphors such as Eu and Mn, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu and other Eu
Activated thioaluminate phosphor and thiogallate phosphor, (Ca, Sr) ₈ (Mg, Zn) (Si
It is also possible to use Eu, Mn activated halosilicate phosphors such as O ₄ ) ₄ Cl ₂ : Eu, Mn.

  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 naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex. is there.

[2-2-3] Blue phosphor As the phosphor emitting blue fluorescence in the light emitting device of the present invention (hereinafter referred to as “blue phosphor” as appropriate), in addition to the phosphor of [1-1], other One or two or more blue phosphors may be used in combination.
When the specific wavelength range of the fluorescence emitted from the blue phosphor is exemplified, the peak wavelength is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less.
As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu, which is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emits light in a blue region. The phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr).
, Ba) ₅ (PO ₄ ) ₃ Cl: Europium-activated calcium halophosphate phosphor represented by Eu, which is composed of grown particles having a cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca , Sr, Ba) ₂ B ₅ O ₉ Cl: a europium-activated alkaline earth chloroborate phosphor represented by Eu, fractured particles having a fracture surface, and emitting light in the blue-green region (Sr, Ca, Examples include europium-activated alkaline earth aluminate-based phosphors represented by Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu.

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

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

[2-2-4] Selection of phosphor In the light-emitting device of the present invention, whether or not the other phosphors described above (red phosphor, green phosphor, blue phosphor, etc.) are used and the type thereof are as follows. What is necessary is just to select suitably according to the use of. For example, when the light-emitting device of the present invention is composed only of the phosphor of [1-1], the use of other phosphors is usually unnecessary.
When the light emitting device of the present invention is configured as a white light emitting device, one or more phosphors may be appropriately combined so that desired white light is obtained. Specifically, when the light-emitting device of the present invention is configured as a white light-emitting device, examples of preferable combinations of the light source and the phosphor include the following combinations (i) to (iii).
(I) A blue light emitter (blue LED or the like) is used as the first light emitter, and a red phosphor and a green phosphor (including any of the phosphors of [1-1] above) as the phosphor. Is used. (Ii) A near-ultraviolet illuminant (near-ultraviolet LED or the like) is used as the first illuminant, and a red phosphor, a green phosphor, or a blue phosphor (including any of the above [1-1]) as the phosphor. (Including phosphors).
(Iii) A blue light emitter (blue LED or the like) is used as the first light emitter, and an orange phosphor and a green phosphor (one of which includes the phosphor of [1-1]). .

[2-2-5] Physical properties of other phosphors
The median particle diameter D ₅₀ of the other phosphors used in the light emitting device of the present invention is preferably in the range of usually 5 μm or more, especially 10 μm or more, and usually 30 μm or less, especially 20 μm or less. When the median particle diameter D ₅₀ is too small, and the luminance decreases tends to phosphor particles tend to aggregate undesirably. On the other hand, if the median particle diameter D ₅₀ is too large, there is a tendency for blockage, such as coating unevenness and dispenser is not preferable.

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

In addition to the above-mentioned light source, phosphor and frame, a sealing material is usually used. Specifically, this sealing material is employed for the purpose of dispersing the above-described phosphor to form a light emitter, or bonding between the light source, the phosphor and the frame.
As a sealing material used, a thermoplastic resin, a thermosetting resin, a photocurable resin, etc. are mentioned normally. Specifically, methacrylic resin such as methyl polymethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; ethyl cellulose, cellulose acetate, cellulose Cellulose resins such as acetate butyrate; epoxy resins; phenol resins; silicone resins and the like. 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, since the phosphor composition of the present invention is configured by dispersing the phosphor in a so-called sealing material, the sealing material in the phosphor composition contains [1-2] (B) silicone compound. It is essential to do.

[2-4] Degree of degradation of light emitting device The light emitting device of the present invention is obtained by combining the specific silicone compound of [1-2] with the phosphor of [1-1] having low moisture resistance. 1-1] deterioration derived from the phosphor can be suppressed. Therefore, the degree of deterioration according to the following semiconductor light emitting device deterioration degree test (II) is usually 5% or less, preferably 3% or less, more preferably 1% or less.
Semiconductor light emitting device degradation measurement test (II)
e) A semiconductor light emitting device is fabricated by sealing the semiconductor light emitting element with the phosphor-containing composition.
f) For the semiconductor light emitting device fabricated in e), let φ _{1 be} the total luminous flux of the semiconductor light emitting device when the rated current is applied.
g) The semiconductor light emitting device whose luminous flux has been measured in f) is left in an unpowered state for 3 days in air at a temperature of 60 ° C. and a relative humidity of 90%.
The total flux of when the rated current for the semiconductor light-emitting device obtained in h) g) and phi _2.
i) Deterioration degree (%) = (1−φ ₂ / φ ₁ ) × 100 is obtained.

In the above f) and h), the rated current means a working voltage / current represented by an effective value specified for the semiconductor light emitting device. That is, the degree of deterioration of the semiconductor light emitting device is measured by measuring the total luminous flux of the semiconductor light emitting device when the semiconductor light emitting device is normally driven at the rated current value.
In f) and h), the semiconductor light beam is measured using a spectroscope and analysis software. Specific examples of the measuring apparatus include color / illuminance measurement software manufactured by Ocean Optics, USB2000 series spectrometer (integral sphere specification), and the like.

In addition, since various causes other than the deterioration of the phosphor are considered as the cause of the deterioration of the light emitting device, the phosphor in which the phosphor is not deteriorated by moisture, such as Y ₃ Al ₅ O ₁₂ : Ce, is used for the fluorescence of the present invention. It is desirable to make a light emitting device instead of the body, measure the degree of deterioration with time, and correct the result of the semiconductor light emitting device deterioration degree measurement test (II).

[2-5] Embodiments of Light Emitting Device Hereinafter, the light emitting device of the present invention will be described in more detail with reference to specific embodiments, but the present invention is not limited to the following embodiments. Any modifications can be made without departing from the scope of the present invention.
FIG. 1 is a diagram schematically showing a configuration of a light emitting device according to an embodiment of the present invention. The light emitting device 1 of the present embodiment includes a frame 2, a blue LED 3 that is a light source, and a phosphor-containing portion 4 that absorbs part of light emitted from the blue LED 3 and emits light having a wavelength different from that.
The frame 2 is a resin base for holding the blue LED 3 and the phosphor-containing portion 4. On the upper surface of the frame 2, a trapezoidal concave section (dent) 2A having an opening on the upper side in FIG. Thereby, since the frame 2 has a cup shape, the light emitted from the light emitting device 1 can have directivity, and the emitted light can be used effectively. Further, the inner surface of the concave portion 2A of the frame 2 is enhanced in the reflectance of light in the entire visible light region by metal plating such as silver, so that the light hitting the inner surface of the concave portion 2A of the frame 2 can also be emitted. Can be discharged in a predetermined direction.

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

The blue LED 3 is installed at the bottom of the recess 2A of the frame 2 as described above. Here, the frame 2 and the blue LED 3 are bonded by a silver paste (a mixture of silver particles in an adhesive) 5. Thus, the blue LED 3 is installed on the frame 2. Further, the silver paste 5 also plays a role of efficiently radiating heat generated in the blue LED 3 to the frame 2.

  Further, a gold wire 6 for supplying power to the blue LED 3 is attached to the frame 2. That is, the electrode (not shown) provided on the upper surface of the blue LED 3 is connected by wire bonding using the wire 6, and when the wire 6 is energized, power is supplied to the blue LED 3. It emits blue light. One or a plurality of wires 6 are attached in accordance with the structure of the blue LED 3.

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

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

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

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

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

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

[3] Use of light-emitting device The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used, but has high luminance and color rendering properties. Since it is expensive, it is particularly preferably used as a light source for an image display device or a lighting device. In addition, when using the light-emitting device of this invention as a light source of an image display apparatus, using with a color filter is preferable.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[1] Example 1
The LED chip “C460-MB290” (emission wavelength = 461 nm) manufactured by CREE was bonded to the bottom of the SMD LED package “TY-SMD1202B” (2.8 mm × 3.5 mm × 1.9 mm) manufactured by Toyo Denpasha.
To 100 parts by weight (main material: curing agent = 100: 10) of a mixture of addition-curable silicone resin (trade name: LPS-1400; main material) and curing agent (trade name: C-1400) manufactured by Shin-Etsu Chemical Co., Ltd. 6 parts by weight of orange phosphor Sr ₂ BaSiO ₅ : Eu (hereinafter abbreviated as SBS; D50 = 21 μm) is added, and the mixture is kneaded for 3 minutes with a stirrer manufactured by Shinky Corporation (Awatori Kentaro AR-100). It was a thing. This was filled to the uppermost surface of the package with the LED chip and cured in an atmosphere at 150 ° C. for 4 hours. After sufficiently cooling, a semiconductor light emitting device deterioration degree measurement test (II) was performed in a room maintained at 25 ° C. ± 1 ° C. The luminous flux was measured using color / illuminance measurement software manufactured by Ocean Optics and USB2000 series spectrometer (integral sphere specification). The results are shown in Table 1.

In addition, when the infrared absorption spectra of the main material and the curing agent used in Example 1 were measured by “NEXUS670” and “Nic-Plan” manufactured by ThermoElectron, no aromatic group was detected.
The orange phosphor SBS used in this example had a degradation degree of 60% as a result of the phosphor degradation test (I). Here, “BM5” manufactured by Topcon Corporation was used for measuring the luminance of the phosphor.

Immediately after production, strontium carbonate was detected as a result of X-ray diffraction by X-ray diffraction using CuKα rays before and after being left in air at a temperature of 60 ° C. and a relative humidity of 90% for 1 day.
[2] Example 2
The same procedure as in Example 1 was performed except that the silicone resin main material and the curing agent in Example 1 were “LPS-2410” and “C-2410” manufactured by Shin-Etsu Chemical Co., Ltd., respectively. The results are shown in Table 1.

In addition, when the infrared absorption spectrum of the said main material and hardening | curing agent which were used in Example 2 was measured by the method similar to Example 1, neither aromatic group was detected.
[3] Example 3
The silicone resin main material and the curing agent in Example 1 were “LPS” manufactured by Shin-Etsu Chemical Co., Ltd.
-3400 "and" C-3400 ". The results are shown in Table 1.
In addition, when the infrared absorption spectrum of the said main material and hardening | curing agent which were used in Example 3 was measured by the method similar to Example 1, neither aromatic group was detected.

[4] Example 4
Example phosphor orange phosphor _SBS in 2 _(D 50 = 21μm) 6.3 parts by weight of a green phosphor _{(Ba 0.75 Sr 0.25) 2 SiO} 4: .D 50 be abbreviated as Eu (hereinafter BSS = 15 μm) The same procedure as in Example 2 except that 6.3 parts by weight and 0.5 parts by weight of RY200S manufactured by Nippon Aerosil Co., Ltd. were added as fillers. The results are shown in Table 1.
The green phosphor BSS used in this example was found to have a degradation level of 0% as a result of the phosphor degradation test (I). Here, “BM5” manufactured by Topcon Corporation was used for measuring the luminance of the phosphor.
In addition, as a result of X-ray diffraction performed by X-ray diffraction using CuKα rays immediately before and after being left in an air at a temperature of 60 ° C. and a relative humidity of 90% for 1 day, the detection of carbonate was not recognized.

[5] Comparative Example 1
In place of the silicone resin main material and the curing agent of Example 1, 100 parts by weight and 90 parts by weight of an epoxy resin (trade name: 828EL) and a curing agent (trade name: YLH-1230) manufactured by Japan Epoxy Resin Co., respectively. A phosphor-containing composition was prepared in the same manner as in Example 1 except that 6 parts by weight of the orange phosphor SBS (D ₅₀ = 21 μm) was added to 100 parts by weight of the mixture. This was filled up to the top surface of the package with the LED chip and cured by heating at 100 ° C. for 3 hours and then at 140 ° C. for 3 hours. After sufficiently cooling, the semiconductor light emitting device deterioration degree measurement test (II) was conducted in the same manner as in Example 1 in a room maintained at 25 ° C. ± 1 ° C. The results are shown in Table 1.

[6] Comparative example 2
The epoxy resin main material and the curing agent of Comparative Example 2 were epoxy resin (trade name: YL-7301) and curing agent (trade name: YLH-1230) manufactured by Japan Epoxy Resin Co., Ltd. in a ratio of 100 parts by weight to 80 parts by weight, respectively. A phosphor-containing composition was produced in the same manner as in Comparative Example 1 except that 6 parts by weight of the orange phosphor SBS (D ₅₀ = 21 μm) was added to 100 parts by weight of the mixture, and the degradation of the semiconductor light emitting device was measured. Test (II) was conducted. The results are shown in Table 1.

[7] Comparative Example 3
The same procedure as in Example 1 was performed except that the silicone resin main material and the curing agent in Example 1 were “LPS-3500” and “C-3500” manufactured by Shin-Etsu Chemical Co., Ltd. The results are shown in Table 1.
In addition, when the infrared absorption spectrum of the main material and hardening | curing agent which were used in the comparative example 3 was measured by the method similar to Example 1, the aromatic group was confirmed.

[8] Comparative example 4
The silicone resin main material and curing agent in Example 1 were “LPS-5500” and “C-5500” manufactured by Shin-Etsu Chemical Co., Ltd., and the same procedure as in Example 1 was performed except that the blending ratio of both was 100: 10. The results are shown in Table 1.
In addition, when the infrared absorption spectrum of the main material and hardening | curing agent which were used in Comparative Example 4 was measured by the method similar to Example 1, the aromatic group was confirmed.

[9] Comparative Example 5
The silicone resin main material and curing agent in Example 4 were “LPS-5500” and “C-5500” manufactured by Shin-Etsu Chemical Co., Ltd., and the same procedure as in Example 4 was performed except that the blending ratio of both was 100: 10. The results are shown in Table 1.

[10] Reference example 1
The same procedure as in Comparative Example 1 was performed except that Y ₃ Al ₅ O ₁₂ : Ce (hereinafter abbreviated as YAG; D ₅₀ = 6 μm) was used instead of the phosphor SBS used in Comparative Example 1. The results are shown in Table 1.
In addition, as a result of the phosphor deterioration degree test (I), the deterioration degree of the phosphor YAG used in this example was 0%. Here, “BM5” manufactured by Topcon Corporation was used for measuring the luminance of the phosphor.
In addition, as a result of X-ray diffraction performed by X-ray diffraction using CuKα rays immediately before and after being left in an air at a temperature of 60 ° C. and a relative humidity of 90% for 1 day, the detection of carbonate was not recognized.

[11] Reference example 2
Reference Example 1 except that the epoxy resin main material and the curing agent used in Reference Example 1 were replaced by Shin-Etsu Chemical's silicone resin (trade name: LPS-5500) and Shin-Etsu Chemical's curing agent "C-5500". As well as. The results are shown in Table 1.

It is typical sectional drawing which shows one Example of the light-emitting device of this invention. It is typical sectional drawing which shows an example of the surface emitting illumination apparatus using the light-emitting device of this invention. It is a typical perspective view which shows other embodiment of the light-emitting device of this invention. Sr ₂ BaSiO _5; is a graph showing an X-ray diffraction immediately after preparation of Eu (SBS). Sr ₂ BaSiO _5; Eu of (SBS)) the temperature 60 ° C., is a graph showing an X-ray diffraction after leaving for one day in a relative humidity of 90%. It is a figure showing an example of the infrared absorption spectrum of the silicone resin preferable to be used for this invention, and a preferable silicone resin.

Explanation of symbols

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

Claims (7)

A phosphor-containing composition comprising (A) a phosphor and (B) a silicone compound,
The phosphor (A) has a degradation degree of 1% or more according to the following phosphor degradation degree measurement test (I), and M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ as a base crystal. Contains at least one of the group consisting of Si ₅ N ₈ and MSi ₂ N ₂ O ₂ (where M represents one or more selected from the group consisting of Ca, Sr, and Ba), and as an activator Containing at least one of Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb,
(B) the silicone compound, a phosphor-containing composition characterized by having no free aromatic group.
Phosphor degradation test (I)
a) The brightness of the phosphor powder is measured, and the measured value is defined as x.
b) The phosphor powder whose luminance was measured in a) is left in air at a temperature of 60 ° C. and a relative humidity of 90% for one day.
c) The luminance of the phosphor powder obtained in b) is measured by the same method as in a), and the measured value obtained is y.
d) The phosphor deterioration degree (%) = (1−y / x) × 100 is obtained. Wherein (A) phosphor, an alkaline earth metal, and the temperature 60 ° C., Ru phosphor der to produce the alkaline earth metal carbonate when allowed to stand for 1 day in a 90% relative humidity of the air < The phosphor-containing composition according to claim 1, wherein: The phosphor (A) is (Sr _1-a Ba _a ) ₃ SiO ₅ : Eu (a satisfies 0 ≦ a ≦ 1
. )
The phosphor-containing composition according to claim 1 or 2, wherein: The light-emitting device formed using the fluorescent substance containing composition of any one of Claims 1-3. A light-emitting device formed using the semiconductor light-emitting element and the phosphor-containing composition according to any one of claims 1 to 3,
A light emitting device having a deterioration degree of 5% or less according to the following semiconductor light emitting device deterioration degree test (II).
Semiconductor light emitting device degradation measurement test (II)
e) A semiconductor light emitting device is fabricated by sealing the semiconductor light emitting element with the phosphor-containing composition.
f) For the semiconductor light emitting device fabricated in e), let φ _{1 be} the total luminous flux of the semiconductor light emitting device when the rated current of the semiconductor light emitting element is applied.
g) The semiconductor light emitting device whose luminous flux has been measured in f) is left in an unpowered state for 3 days in air at a temperature of 60 ° C. and a relative humidity of 90%.
The total flux of when the rated current for the semiconductor light-emitting device obtained in h) g) and phi _2.
i) Deterioration degree (%) = (1−φ ₂ / φ ₁ ) × 100 is obtained. An illumination device formed using the light-emitting device according to claim 4. An image display device formed using the light emitting device according to claim 4.

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