JP5854367B2 - Method for manufacturing phosphor composite member - Google Patents

Description

  The present invention relates to a method for producing a phosphor composite member suitable for emitting fluorescence by irradiating excitation light, for example, and obtaining white light by synthesizing transmitted excitation light and fluorescence.

  In recent years, white LEDs have attracted attention as a highly efficient and highly reliable white light source and have already been put into practical use. White LEDs have advantages such as long life, high efficiency, high stability, low power consumption, high response speed, and no environmental load substances compared to conventional light sources such as lighting devices. As a light source for liquid crystal backlights for TVs and TVs, it is rapidly spreading. In the future, in addition to this, it is expected that the application will be advanced to general lighting.

  By the way, the white LED disclosed in Patent Document 1 has a configuration in which a light emitting surface of an LED chip is coated with a mold in which an inorganic phosphor powder is dispersed in an organic binder resin. Therefore, the organic binder resin deteriorates and causes discoloration due to high-output short-wavelength light in the blue to ultraviolet region, heat generation of the inorganic phosphor powder, or heat of the LED chip. As a result, there is a problem in that the emission intensity is lowered and the color shift occurs and the life is shortened.

  For these problems, a phosphor composite member obtained by mixing and sintering inorganic phosphor powder and glass powder has been proposed (see, for example, Patent Document 2). Since the phosphor composite member is formed by dispersing the inorganic phosphor powder in an inorganic glass powder having high heat resistance, it is possible to suppress a decrease in emission intensity over time. However, in Patent Document 2, in order to obtain a phosphor composite member having a desired size, a cutting and polishing process is required. For example, in order to obtain a thin phosphor composite member, the inorganic phosphor powder and the glass powder are once sintered to produce a relatively thick member, and then the member is cut and polished to reduce the thickness. There is a need. Therefore, in this production method, the material yield of the inorganic phosphor powder and the glass powder is poor, and as a result, the production cost of the phosphor composite member tends to increase.

  Therefore, a phosphor composite member has been proposed in which a glass sintered body layer containing an inorganic phosphor powder is formed on the surface of an inorganic base material (see, for example, Patent Document 3 or 4). The phosphor composite member is formed by forming a sintered body layer containing an inorganic phosphor powder on an inorganic substrate by a paste method or a green sheet method. Therefore, a thin phosphor composite member can be produced without going through steps such as cutting and polishing.

JP 2000-208815 A JP 2003-258308 A JP 2007-48864 A JP 2008-169348 A

  In the method described in Patent Document 3 or 4, a light emitting color conversion member having a desired shape can be manufactured with a high yield, but there is a problem that the light emission intensity of the member is low. Moreover, since the manufacturing process of the paste and the green sheet is required, there is a problem that the manufacturing process is complicated.

  In view of such a situation, an object of the present invention is to provide a method for easily manufacturing a phosphor composite member having a higher emission intensity than the conventional one.

  The present invention includes a step of placing a mixed powder containing a glass powder and an inorganic phosphor powder on an inorganic base material, and press-molding the mixed powder while heating using a mold to form a surface on the surface of the inorganic base material. And a step of forming an inorganic powder sintered body layer.

  When the glass sintered body layer containing the inorganic phosphor powder is formed on the inorganic base material by the paste method or the green sheet method, the carbon component resulting from the organic resin or the organic solvent remains in the sintered body, This causes a decrease in emission intensity. On the other hand, according to the production method of the present invention, it is possible to directly press-fuse the mixed powder containing the glass powder and the inorganic phosphor powder to the surface of the inorganic base material without adding an organic resin or an organic solvent. Therefore, there is no problem of a decrease in light emission intensity caused by a carbon component caused by an organic resin, an organic solvent, or the like. Therefore, it is possible to obtain a light emission color conversion member having excellent light emission intensity.

  In addition, since it is not necessary to paste the raw material powder into a green sheet and the mixed powder can be used for press molding as it is, the manufacturing process can be simplified. It is also easy to form a very thin inorganic powder sintered body layer on the inorganic substrate surface.

  Secondly, in the method for producing a phosphor composite member of the present invention, the inorganic base material is preferably YAG ceramics, crystallized glass, glass, metal, or a metal / ceramic composite.

  Thirdly, in the method for producing a phosphor composite member of the present invention, the thickness of the inorganic powder sintered body layer is preferably 0.3 mm or less.

  By thinning the inorganic powder sintered body layer, light scattering loss in the inorganic powder sintered body layer can be reduced, and as a result, the emission intensity of the phosphor composite member can be improved.

  Fourthly, in the method for producing a phosphor composite member of the present invention, the surface roughness (Ra) of the inorganic powder sintered body layer is preferably 0.5 μm or less.

  According to the said structure, the light scattering loss in the inorganic powder sintered layer surface can be reduced, and excitation light and fluorescence become easy to permeate | transmit. As a result, the emission intensity of the phosphor composite member can be improved.

  Fifth, in the method for producing the phosphor composite member of the present invention, it is preferable that the average particle diameter (D50) of the glass powder is 100 μm or less.

  According to the said structure, the dispersion state of the inorganic fluorescent substance powder in a fluorescent substance composite member becomes a favorable thing, and it becomes possible to suppress the dispersion | variation in luminescent color.

  Sixth, in the method for producing a phosphor composite member of the present invention, the ratio of the inorganic phosphor powder in the inorganic powder sintered body layer is preferably 0.01 to 90% by mass.

  Seventhly, in the method for producing a phosphor composite member of the present invention, the inorganic powder sintered body layer preferably contains 0 to 30% by mass of an inorganic filler.

  By adding an inorganic filler in the inorganic powder sintered body layer, it is possible to reduce the difference in expansion coefficient from the inorganic base material and suppress the occurrence of peeling and cracking.

Eighth, in the method for producing the phosphor composite member of the present invention, the glass powder is SiO ₂ —B ₂ O ₃ —RO glass powder (R is one or more selected from Mg, Ca, Sr and Ba), SiO ₂ —TiO ₂ —Nb ₂ O ₅ —R ′ ₂ O glass powder (R ′ is one or more selected from Li, Na, K), SnO—P ₂ O ₅ glass powder, or ZnO—B ₂ O _{A 3-} SiO ₂ glass powder is preferred.

Ninthly, in the method for producing the phosphor composite member of the present invention, SnO-P ₂ O ₅ glass powder is a mol% as a glass composition, SnO 35-80%, P ₂ O ₅ 5-40%, B preferably contains ₂ O _{3 0~30%.}

  Tenth, in the method for producing the phosphor composite member of the present invention, the inorganic phosphor powder is an oxide, nitride, oxynitride, sulfide, oxysulfide, oxyfluoride, halide, aluminate or A halophosphate is preferred.

  Eleventh, in the method for producing a phosphor composite member of the present invention, the temperature at the time of press molding is preferably 900 ° C. or lower.

  According to this configuration, it is possible to suppress the deactivation of the inorganic phosphor powder and the denaturation of the glass powder due to heat.

  12thly, as for the manufacturing method of the fluorescent substance composite member of this invention, it is preferable that the atmosphere at the time of press molding is air, vacuum, nitrogen, or argon.

  Thirteenthly, in the method for manufacturing a phosphor composite member of the present invention, the phosphor composite member preferably has a plate shape, a hemispherical shape, or a hemispherical dome shape.

  14thly, the manufacturing method of the fluorescent substance composite member of this invention is related with the fluorescent substance composite member produced by one of the said manufacturing methods.

It is a schematic diagram which shows the manufacturing method of the fluorescent substance composite member of this invention.

  In FIG. 1, the schematic diagram of the manufacturing method of the fluorescent substance composite member of this invention is shown.

  First, in FIG. 1A, the inorganic base material 2 is allowed to stand on the lower mold 3b, and a predetermined amount of the mixed powder 1 containing the inorganic phosphor powder and the glass powder is placed on the inorganic base material 2. To do.

  Next, in FIG.1 (b), the mixed powder 1 is heated using the upper metal mold | die 3a, pressing, and the mixed powder 1 is sintered. Thereby, as shown in FIG.1 (c), the fluorescent substance composite member 5 by which the inorganic powder sintered compact layer 4 was formed on the inorganic base material 2 is obtained. Here, the heating method is not particularly limited, and pressing may be performed using a mold heated to a predetermined temperature, or pressing may be performed in an atmosphere set at a predetermined temperature (for example, in an electric furnace).

As glass powder used in the present invention, SiO ₂ —B ₂ O ₃ —RO glass powder (R is one or more selected from Mg, Ca, Sr and Ba), SiO ₂ —TiO ₂ —Nb ₂ O. _5- R ′ ₂ O glass powder (R ′ is one or more selected from Li, Na, K), SnO—P ₂ O ₅ glass powder, or ZnO—B ₂ O ₃ —SiO ₂ glass powder. It is done. Especially, it is preferable to use SnO—P ₂ O ₅ glass powder having a relatively low softening point because the press molding temperature is lowered and the deactivation of the inorganic phosphor powder can be suppressed.

The _SnO-P 2 _{O 5} based glass powder, in mol% as a glass _{composition, SnO 35~80%, P 2 O} 5 5~40%, those containing 2 O 3 0 to 30% _B is preferred. The reason for limiting the glass composition in this way will be described below.

  SnO is a component that forms a glass skeleton and lowers the softening point. The SnO content is preferably 35 to 80%, 40 to 70%, 50 to 70%, particularly 55 to 65%. When there is too little content of SnO, it exists in the tendency for the softening point of glass to rise, and there exists a tendency for a weather resistance to deteriorate. On the other hand, when the content of SnO is too large, devitrification bumps resulting from Sn are deposited in the glass and the transmittance tends to decrease, and as a result, the emission intensity of the phosphor composite member 5 tends to decrease. . Moreover, it becomes difficult to vitrify.

P ₂ O ₅ is a component that forms a glass skeleton. The content of P ₂ O ₅ is preferably 5 to 40%, 10 to 30%, particularly preferably 15 to 24%. When the content of P ₂ O ₅ is too small, it is difficult to vitrify. On the other hand, when the content of P ₂ O ₅ is too large, or the softening point rises, there is a tendency that weather resistance is significantly lowered.

B ₂ O ₃ is a component that improves the weather resistance and suppresses the reaction between the glass powder and the inorganic phosphor powder. It is also a component that stabilizes the glass. The content of B ₂ O ₃ is preferably 0 to 30%, 1 to 25%, 2 to 20%, particularly 4 to 18%. If the B ₂ O ₃ content is too large, the weather resistance tends to lower. Also, the softening point tends to increase.

The SiO ₂ -B ₂ O ₃ -RO based glass powder, in mass% as a glass _{composition, SiO 2 30~70%, B 2} O 3 1~15%, 0~10% MgO, CaO 0~25%, SrO 0~10%, BaO 8~40%, MgO + CaO + SrO + BaO 10~45%, Al 2 O 3 0~20%, those preferably contain 0% ZnO.

The SiO ₂ —TiO ₂ —Nb ₂ O ₅ —R ′ ₂ O-based glass powder is, by mass percentage, SiO ₂ 20-50%, Li ₂ O 0-10%, Na ₂ O 0-15%, K _{2. O 0~20%, Li 2 O +} Na 2 O + K 2 O 1~30%, B 2 O 3 1~20%, 0~10% MgO, CaO 0~20%, SrO 0~20%, BaO 0~15% Al ₂ O ₃ 0-20%, ZnO 0-15%, TiO ₂ 0.01-20%, Nb ₂ O ₅ 0.01-20%, La ₂ O ₃ 0-15%, TiO ₂ + Nb ₂ O ₅ + _La 2 _O 3 which contains 1 to 30% is preferred.

The _{ZnO-B 2} O 3 -SiO ₂ based glass powder, in mass% as a glass _{composition, 5~60% ZnO, B 2 O} 3 5~50%, those containing SiO 2 2 to 30% preferred.

  The average particle diameter (D50) of the glass powder is preferably 100 μm or less, particularly preferably 50 μm or less. When the average particle diameter of the glass powder is too large, the dispersed state of the inorganic phosphor powder in the phosphor composite member 5 is inferior, and the emission color tends to vary. The lower limit is not particularly limited, but if the average particle size of the glass powder is too small, the production cost is likely to increase, so that it is preferably 0.1 μm or more, particularly 1 μm or more.

  In the present specification, “average particle diameter (D50)” refers to a value measured by a laser diffraction method.

  In order to suppress light scattering loss at the interface between the inorganic base material 2 and the inorganic powder sintered body layer 4, it is preferable that the refractive index difference between the two is small. For example, when YAG ceramics is used as the inorganic base material 2, the refractive index (nd) of the glass powder is preferably 1.5 or more, 1.7 or more, particularly 1.8 or more.

  The softening point of the glass powder is preferably 500 ° C. or lower, 450 ° C. or lower, and particularly preferably 400 ° C. or lower. If the softening point is too high, the sintering temperature becomes high and the inorganic phosphor powder tends to deteriorate.

  Inorganic phosphor powders include oxides, nitrides, oxynitrides, sulfides, oxysulfides, oxyfluorides, halides, aluminates or halophosphates. Of these, those having an excitation band at a wavelength of 300 to 500 nm and having an emission peak at a wavelength of 500 to 780 nm, particularly those emitting light in red, yellow or green are preferably used.

As inorganic phosphor powders that emit red fluorescence when irradiated with blue excitation light, CaS: Eu ²⁺ , SrS: Eu ²⁺ , CaAlSiN ₃ : Eu ²⁺ , CaSiN ₃ : Eu ²⁺ , (Ca, Sr) ₂ Si ₅ N ₈ : Eu ^{2+ and the} like can be mentioned.

As inorganic phosphor powder that emits yellow fluorescence when irradiated with blue excitation light, (Sr, Ba, Ca) ₂ SiO ₄ : Eu ²⁺ , (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce ³⁺ , CaGa ₂ S ₄ : Eu ²⁺ , La ₃ Si ₆ N ₁₁ : Ce ^{3+ and the} like.

As inorganic phosphor powders that emit green fluorescence when irradiated with blue excitation light, SrAl ₂ O ₄ : Eu ²⁺ , SrGa ₂ S ₄ : Eu ²⁺ , SrBaSiO ₄ : Eu ²⁺ , Ba ₃ Si ₆ O ₁₂ N ₂ : Eu ²⁺ Si ₂ Al ₄ O ₄ N ₄ : Eu ²⁺ , Sr ₃ Si ₁₃ Al ₃ O ₂ N ₂₁ : Eu ²⁺ , Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce ³⁺ , CaSc ₂ O ₄ : Ce ³⁺ .

  The content of the inorganic phosphor powder in the inorganic powder sintered body layer 4 is preferably 0.01 to 90% by mass, 0.05 to 30% by mass, and particularly preferably 0.08 to 15%. When there is too much content of inorganic fluorescent substance powder, there exists a tendency for content of glass powder to decrease relatively and for porosity to become large. As a result, the strength of the inorganic powder sintered body layer 4 decreases and the light scattering loss increases. On the other hand, when there is too little content of inorganic fluorescent substance powder, it becomes difficult to obtain sufficient light emission intensity.

In order to adjust the expansion coefficient of the inorganic powder sintered body layer 4, an inorganic filler powder may be added to the mixed powder 1 (inorganic powder sintered body layer 4). In particular, when a glass powder having a large thermal expansion coefficient, such as SnO—P ₂ O ₅ glass powder, is used, the difference in thermal expansion coefficient between the inorganic base material 2 and the inorganic powder sintered body layer 4 is increased. Since the surface of the powder sintered body layer 4 is easily cracked or peeled off, it is effective to add an inorganic filler powder having low expansion characteristics.

Examples of the inorganic filler powder include zirconium phosphate, zirconium phosphate tungstate, zirconium tungstate, NZP type crystals and solid solutions thereof having low expansion characteristics, and these may be used alone or in combination. it can. Here, the “NZP type crystal” includes, for example, a crystal having a basic structure of NbZr (PO ₄ ) ₃ or [AB ₂ (MO ₄ ) ₃ ].
A: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc. B: Zr, Ti, Sn, Nb, Al, Sc, Y etc. M: P, Si, W, Mo etc.

In addition, it is preferable to use the inorganic filler powder containing a Zr component. Inorganic filler powder containing Zr component, compatibility with _SnO-P 2 _{O 5} based glass is satisfactory, i.e. low reactivity with the _SnO-P 2 _{O 5} based glass, a glass powder was devitrification during press molding This is because it has difficult properties.

  The content of the inorganic filler powder in the inorganic powder sintered body layer 4 is preferably 0 to 30% by mass, 1.5 to 25% by mass, and particularly preferably 2 to 20% by mass. When there is too much content of an inorganic filler powder, content of glass powder will decrease relatively and it will become easy to reduce mechanical strength. In addition, light scattering loss at the interface between the glass matrix and the inorganic filler powder increases, and the light emission intensity tends to decrease.

The thermal expansion coefficient of the inorganic filler powder is preferably 50 × 10 ⁻⁷ / ° C. or less, particularly preferably 30 × 10 ⁻⁷ / ° C. or less in the temperature range of 30 to 380 ° C. If the thermal expansion coefficient of the inorganic filler powder is too large, it is difficult to obtain the effect of reducing the thermal expansion coefficient of the inorganic powder sintered body layer 4. In addition, although it does not specifically limit about the minimum of the thermal expansion coefficient of inorganic filler powder, Actually, it is more than -100x10 < ^-7 > / degreeC.

  The average particle size (D50) of the inorganic filler powder is preferably 0.1 to 50 μm, particularly 3 to 20 μm. If the average particle size of the inorganic filler powder is too small, the effect of reducing the thermal expansion coefficient of the inorganic powder sintered body layer 4 tends to be inferior. Alternatively, it may be dissolved in the glass powder at the time of press molding and may not serve as a filler. If the average particle size of the inorganic filler powder is too large, cracks are likely to occur at the boundary between the glass powder and the inorganic filler powder.

  In order to prevent peeling of the inorganic powder sintered body layer 4 from the inorganic base material 2, the thermal expansion coefficient of the inorganic base material 2 is α1, and the thermal expansion coefficient of the inorganic powder sintered body layer 4 is α2. -5 ppm / ° C. ≦ α 1 −α 2 ≦ 5 ppm / ° C., particularly preferably −1 ppm / ° C. ≦ α 1 −α 2 ≦ 1 ppm / ° C. When α1-α2 is out of the above range, the inorganic powder sintered body layer 4 is easily peeled off from the inorganic substrate 2.

  Examples of the inorganic substrate 2 include YAG ceramics, crystallized glass, glass, metal, or a composite of metal and ceramic. The YAG ceramics can be used regardless of whether they are transparent or translucent.

  Here, by using a material that transmits excitation light or fluorescence as the inorganic base material 2, for example, white light can be obtained by a combination of transmitted light of excitation light and fluorescence emitted from the inorganic phosphor powder. Is possible.

  In addition, by using a metal or a composite of metal and ceramics as the inorganic substrate 2, a reflective phosphor composite member can be obtained. Examples of the metal include Al, Cu, and Ag. Examples of the composite of metal and ceramic include a composite (sintered body) of Al and SiC or AlN. A reflective layer (not shown) such as Ag or Al may be provided on the interface between the inorganic base material 2 and the inorganic powder sintered body 4 as necessary. Metals and composites of metals and ceramics are excellent in thermal conductivity, so it is possible to efficiently dissipate heat generated from phosphors when exposed to high-intensity excitation light such as blue LD. Temperature quenching of the phosphor powder can be reduced.

  Although the thickness of the inorganic base material 2 is not specifically limited, For example, it is preferable that it is 0.1-10.0 mm. If the thickness of the inorganic substrate 2 is too small, the mechanical strength tends to be insufficient. On the other hand, when the thickness of the inorganic base material 2 is too large, the excitation light is difficult to transmit, and the light emission efficiency tends to decrease, or the weight of the phosphor composite member 5 tends to be unreasonably large.

  The press temperature is preferably 900 ° C. or lower, 700 ° C. or lower, particularly 500 ° C. or lower, from the viewpoint of preventing the deactivation of the inorganic phosphor powder and the glass denaturation. On the other hand, since the glass powder needs to be sufficiently softened and fixed to the surface of the inorganic substrate 2, the lower limit is preferably 200 ° C. or higher, particularly 250 ° C. or higher.

Press pressure, depending on the thickness of the inorganic powder sintered body layer 4 for the purpose, 1N / mm ² or more, particularly suitably adjusted 3N / mm ² or more. On the other hand, although an upper limit is not specifically limited, In order to prevent the damage of the inorganic base material 2, it is preferable to set it as 100 N / mm < ² > or less, especially 50 N / mm < ² > or less.

  The pressing time is not particularly limited, but is appropriately adjusted for 0.1 to 30 minutes, 0.5 to 10 minutes, particularly 1 to 5 minutes so that the inorganic powder sintered body layer 4 is sufficiently fixed to the surface of the inorganic base material 2. do it.

  The atmosphere at the time of press molding includes air, vacuum, nitrogen or argon. Among them, in order to suppress the deactivation of the inorganic phosphor powder, the modification of the glass powder, and the deterioration due to the oxidation of the press mold, the inert gas such as nitrogen and argon, especially nitrogen in consideration of running cost. Is preferred.

  The thickness of the inorganic powder sintered body layer 4 is preferably 0.3 mm or less, 0.25 mm or less, particularly preferably 0.2 mm or less. When the thickness of the inorganic powder sintered body layer 4 is too large, the excitation light is hardly transmitted, and it becomes difficult to obtain light having a desired color. On the other hand, if the thickness of the inorganic powder sintered body layer 4 is too small, the mechanical durability tends to be insufficient. Therefore, the lower limit is 0.01 mm or more, 0.03 mm or more, particularly 0.05 mm or more. Is preferred.

  The surface roughness (Ra) of the inorganic powder sintered body layer 4 is preferably 0.5 μm or less, 0.2 μm or less, and particularly preferably 0.1 μm or less. When the surface roughness of the inorganic powder sintered body layer 4 is too large, the light scattering loss increases, and the transmittance of excitation light and fluorescence tends to decrease and the emission intensity tends to decrease.

  The shape of the phosphor composite member 5 is not particularly limited, and examples thereof include a plate shape, a hemispherical shape, and a hemispherical dome shape.

  Hereinafter, the phosphor composite member of the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

Example 1
(1) Production of ceramic base material First, using a raw material having a high purity and a particle size of 2 μm or less, Y ₂ O in mol% so as to have a stoichiometric composition of YAG (Y ₃ Al ₅ O ₁₂ ). ₃ 37.4625%, Al ₂ O ₃ 62.5%, Ce ₂ O ₃ 0.0375% were weighed, and 0.6% by mass of tetraethoxysilane was added thereto as a sintering aid. Next, using a ball mill, the prepared raw materials were stirred and mixed in ethanol for 17 hours, and then dried under reduced pressure to obtain a powder. Subsequently, the obtained powder was press-molded at a pressure of 200 MPa to produce a press-molded body having a diameter of 10 mm and a thickness of 3 mm, and this was fired at 1750 ° C. in a vacuum atmosphere for 10 hours to obtain a sintered body. Obtained. Thereafter, the sintered body was polished on both sides so as to have a thickness of 0.12 mm to obtain a ceramic substrate.

  About the ceramic base material obtained in this way, when the deposited crystal was identified using an X-ray powder diffractometer, it was confirmed that the YAG crystal was precipitated in a single phase.

  Further, when the emission spectrum of the obtained YAG ceramic substrate was measured, yellow fluorescence having a center near a wavelength of 550 nm and blue excitation light having a center near a wavelength of 465 nm (excitation light transmitted through the ceramic substrate) A peak due to was observed.

(2) Production of phosphor composite member Glass powder, inorganic phosphor powder and inorganic filler powder listed in Table 1 were mixed at a predetermined ratio to obtain a mixed powder.

  The glass powder was produced as follows. First, glass raw materials prepared so as to have the composition shown in Table 1 were put into an alumina crucible and melted in an electric furnace at 950 ° C. in a nitrogen atmosphere for 1 hour. Thereafter, the glass melt was formed into a film and pulverized with a rough machine to obtain glass powder. The average particle diameter (D50) of the obtained powder was 32 μm.

  The YAG ceramic substrate obtained in (1) was allowed to stand on a hot plate, and a predetermined amount of the mixed powder was placed thereon. Next, a metal mold is pressed against the mixed powder, and press-molded for 3 minutes in a nitrogen atmosphere at the press pressure and press temperature shown in Table 1, so that an inorganic powder sintered body layer is formed on the surface of the YAG ceramic substrate. To obtain a phosphor composite member.

(3) Measurement of total luminous flux and chromaticity The emission spectrum of the obtained phosphor composite member was measured as follows. Inside the calibrated integrating sphere, the phosphor composite member is excited by a blue LED that is lit at a current of 200 mA, and the emitted light is taken into a small spectroscope (USB-4000 manufactured by Ocean Optics) through an optical fiber. (Energy distribution curve) was obtained. Total luminous flux and chromaticity were calculated from the obtained emission spectrum. The results are shown in Table 1.

(Comparative Example 1)
(1) Preparation of inorganic powder sintered body layer paste A glass powder, an inorganic phosphor powder and an inorganic filler powder described in Table 1 were mixed at a predetermined ratio to prepare a mixed powder. Next, 50 parts by mass of 2,4-diethyl-1,5-pentanediol (MARS manufactured by Nippon Fragrance Chemicals Co., Ltd.) is added and mixed as a solvent to 100 parts by mass of the obtained mixed powder. A paste was obtained.

(2) Production of phosphor composite member On the surface of the YAG ceramic substrate obtained in Example 1, the paste for inorganic powder sintered body layer obtained in (1) above is about 300 μm thick by the dispense method. It was applied as follows. Next, the solvent was removed by heat treatment on a hot plate at about 250 ° C. Then, it baked for 10 minutes at 430 degreeC in nitrogen atmosphere, and also hot-pressed by the pressure of 1 N / mm < ² >, and surface shape was adjusted, and the fluorescent substance composite member was obtained.

  The total luminous flux and chromaticity of the phosphor composite member thus obtained were measured by the same method as in Example 1. The results are shown in Table 1. As is clear from Table 1, the phosphor composite member obtained in Comparative Example 1 was inferior to Example 1 in total luminous flux value.

(Comparative Example 2)
(1) Production of Green Sheet for Inorganic Powder Sintered Body Layer Glass powder and inorganic phosphor powder described in Table 1 were mixed at a predetermined ratio to produce a mixed powder. Next, 12 parts by mass of polyvinyl butyral resin as a binder, 3 parts by mass of dibutyl phthalate as a plasticizer, and 40 parts by mass of toluene as a solvent are added to 100 parts by mass of the mixed powder, and mixed to prepare a slurry. did. Subsequently, the slurry was formed into a sheet on a PET film by a doctor blade method and dried to obtain a green sheet having a thickness of 250 μm.

(2) Production of phosphor composite member The green sheet produced in (1) above is laminated on the surface of the YAG ceramic substrate obtained in Example 1, and is integrated by thermocompression bonding to produce a laminate. Degreased for 1 hour at ° C. Next, after baking at 400 degreeC for 20 minutes, it cooled and the fluorescent substance composite member was obtained.

  The total luminous flux and chromaticity of the phosphor composite member thus obtained were measured by the same method as in Example 1. The results are shown in Table 1. As is clear from Table 1, as in Comparative Example 1, the phosphor composite member obtained in Comparative Example 2 was inferior to Example 1 in total luminous flux value.

(Example 2)
Glass powder, inorganic phosphor powder and inorganic filler powder listed in Table 1 were mixed at a predetermined ratio to obtain a mixed powder.

The glass powder was produced as follows. First, a glass raw material prepared so as to have a composition containing 72% SnO and 28% P ₂ O ₅ in mol% was put into an alumina crucible and melted in an electric furnace at 950 ° C. in a nitrogen atmosphere for 1 hour. Thereafter, the glass melt was formed into a film and pulverized with a rough machine to obtain glass powder. The average particle size (D50) of the obtained powder was 36 μm.

  The YAG ceramic base material obtained in Example 1 was allowed to stand on a hot plate, and a predetermined amount of the mixed powder was placed thereon. Next, a metal mold is pressed against the mixed powder, and press-molded for 3 minutes in a nitrogen atmosphere at the press pressure and press temperature shown in Table 1, so that an inorganic powder sintered body layer is formed on the surface of the YAG ceramic substrate. To obtain a phosphor composite member.

  The total luminous flux and chromaticity of the phosphor composite member thus obtained were measured in the same manner as in Example 1. The results are shown in Table 1.

(Examples 3 to 6)
Glass powder, inorganic phosphor powder, and inorganic filler powder listed in Table 2 were mixed at a predetermined ratio to obtain a mixed powder.

  A cover glass substrate (manufactured by Matsunami Glass Co., Ltd.) having a thickness of 0.15 mm was allowed to stand on the hot plate, and a predetermined amount of the mixed powder was placed thereon. Next, a metal mold is pressed against the mixed powder, and press molding is performed for 3 minutes in a nitrogen atmosphere at the press pressure and press temperature shown in Table 2, thereby forming an inorganic powder sintered body layer on the surface of the cover glass substrate. To obtain a phosphor composite member.

  The total luminous flux and chromaticity of the phosphor composite member thus obtained were measured in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 3)
The glass powder and inorganic phosphor powder shown in Table 3 were mixed at a predetermined ratio to obtain a mixed powder.

  By placing a predetermined amount of the mixed powder directly on the hot plate, pressing a mold against the mixed powder, and press-molding in a nitrogen atmosphere for 3 minutes at the press pressure and press temperature described in Table 3, An inorganic powder sintered body layer was formed.

  The inorganic powder sintered body layer was very brittle and was damaged when removed from the hot plate, so that the total luminous flux and chromaticity could not be measured.

  The phosphor composite member of the present invention is suitable as a member for an LED device used in lighting, a light emitting device such as a display, and a headlamp such as an automobile. Further, the phosphor composite member of the present invention is not limited to the LED application, and can also be used as a wavelength conversion member in an LED device that emits high-power excitation light such as a laser diode.

DESCRIPTION OF SYMBOLS 1 Mixed powder 2 Inorganic base material 3a Upper die 3b Lower die 4 Inorganic powder sintered body layer 5 Phosphor composite member P Pressure direction

Claims (14)

A step of placing a mixed powder containing glass powder and an inorganic phosphor powder on an inorganic base material (excluding a surface where a light emitting element is mounted) , and a mixed powder while heating using a mold A method for producing a phosphor composite member, comprising the step of press molding and forming an inorganic powder sintered body layer on the surface of an inorganic base material. 2. The method for producing a phosphor composite member according to claim 1, wherein an inorganic powder sintered layer is formed on the entire surface of at least one of the plate-like inorganic base materials. The method for producing a phosphor composite member according to claim 1 or 2 , wherein the inorganic base material is YAG ceramic, crystallized glass, glass, metal, or a composite of metal and ceramic. The method for producing a phosphor composite member according to any one of claims 1 to 3, wherein the inorganic powder sintered body layer has a thickness of 0.3 mm or less. The method for producing a phosphor composite member according to any one of claims 1 to 4 , wherein the inorganic powder sintered body layer has a surface roughness (Ra) of 0.5 µm or less. The average particle diameter (D50) of glass powder is 100 micrometers or less, The manufacturing method of the fluorescent substance composite member in any one of Claims 1-5 characterized by the above-mentioned. The method for producing a phosphor composite member according to any one of claims 1 to 6 , wherein a ratio of the inorganic phosphor powder in the inorganic powder sintered body layer is 0.01 to 90% by mass. The method for producing a phosphor composite member according to any one of claims 1 to 7 , wherein the inorganic powder sintered body layer contains 0 to 30% by mass of an inorganic filler. Glass powder is SiO ₂ —B ₂ O ₃ —RO glass powder (R is one or more selected from Mg, Ca, Sr and Ba), SiO ₂ —TiO ₂ —Nb ₂ O ₅ —R ′ ₂ O system The glass powder (R ′ is at least one selected from Li, Na, and K), SnO—P ₂ O ₅ glass powder, or ZnO—B ₂ O ₃ —SiO ₂ glass powder. The manufacturing method of the fluorescent substance composite member in any one of 1-8 . _SnO-P 2 _{O 5} based glass powder, in mol% as a glass composition, SnO 35 to _80%, characterized in that it contains _{P 2 O 5 5~40%, B} 2 O 3 0~30% claims Item 10. A method for producing a phosphor composite member according to Item 9 . Inorganic phosphor powder, oxides, nitrides, oxynitrides, sulfides, oxysulfides, oxyfluorides, halides, claim 1-10, characterized in that the aluminate or halophosphate chloride The manufacturing method of the fluorescent substance composite member in any one of. The method for producing a phosphor composite member according to any one of claims 1 to 11 , wherein the temperature during press molding is 900 ° C or lower. The method for producing a phosphor composite member according to any one of claims 1 to 12 , wherein an atmosphere during press molding is air, vacuum, nitrogen, or argon. The shape of the phosphor composite member, a plate shape, a hemispherical shape, the manufacturing method of the phosphor composite member according to claim 1 to 13, characterized in that a hemispherical dome.