JP2007039303A - Luminescent color-converting member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminescent color-converting member in which the deterioration of luminescence intensity of white LED and a tendency to shorten the life due to the degradation of a resin are suppressed and a white light (light bulb color) high in color rendering property and low in color temperature is obtained. <P>SOLUTION: The luminescent color-converting member has a crystallized glass base material and a glass sintered layer and is made by forming the glass sintered layers on one or both surfaces of the crystallized glass base material. The luminescent color-converting member has a property that the crystallized glass and the glass sintered layer emit fluorescence having wavelengths different from each other when being irradiated with stimulating light. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an emission color conversion member, and more particularly to an emission color conversion member that emits fluorescence by excitation light and emits white light by combining transmitted excitation light and fluorescence.

  Development of blue light emitting diodes (LEDs) brings together the three primary colors RGB (R: red, G: green, B: blue) LEDs, and white LEDs are obtained by using these LEDs side by side. Has been proposed. However, since the light emission outputs of the three color LEDs are different, it is difficult to obtain white light by matching the characteristics of the light emitting diodes of the respective colors. In addition, even if the three primary color light emitting diodes are assembled and arranged on the same plane, for example, when the light emitting diodes are viewed at close positions as in a liquid crystal backlight, a uniform white light source Can not be. Further, since the color deterioration rates of the light emitting diodes of the respective colors are different, there is a problem in long-term stability of white light.

In order to solve this problem, an LED element that combines a blue LED chip and a YAG phosphor that emits yellow light by blue light emitted from the blue LED chip has been developed (see, for example, Patent Document 1). In this system, white light can be obtained by combining the transmitted light from the blue LED and the yellow light emitted from the YAG phosphor. With this method, only one type of LED is required, so the cost is low and the long-term stability of white light is excellent. In addition, this white LED has advantages such as long life, high efficiency, high stability, low power consumption, high response speed, and no environmental load substances compared to the light source such as a conventional lighting device. Currently, this type of white LED is used in the liquid crystal backlight of most mobile phones and digital cameras. In the future, this white LED is expected to be applied to illumination as a next-generation light source to replace incandescent bulbs and fluorescent lamps.
JP 2000-208815 A

  However, since the white LED disclosed in Patent Document 1 is molded by mixing phosphor powder with a resin that seals the light emitting surface of the LED chip, high-power short-wavelength light in the blue to ultraviolet region The resin constituting the LED element deteriorates due to heat generation of the phosphor or heat of the LED chip, causing discoloration or deformation. As a result, there is a problem in that the emission intensity is lowered and the color shift occurs and the life is shortened.

  Moreover, since the obtained white light is blue and yellow combined light, white light having a high color temperature (daylight color) can be obtained, but white light having a low color temperature (bulb color) cannot be obtained. There is also a problem. Furthermore, since the combined light is composed of two colors, the color rendering properties are low and it is not suitable for lighting applications.

  The present invention has been made in view of the above circumstances, and can suppress a decrease in the emission intensity and shortening of the lifetime of the white LED due to the deterioration of the resin, has high color rendering properties, and has a color temperature from white light (daylight color). An object of the present invention is to provide a light emitting color conversion member capable of emitting white light corresponding to various color temperatures up to white light (bulb color) at a low temperature.

  The luminescent color conversion member of the present invention is a luminescent color conversion member having a crystallized glass substrate and a glass sintered layer, wherein the glass sintered layer is formed on one or both sides of the crystallized glass substrate, When irradiated with excitation light, the crystallized glass and the sintered glass layer have a property of emitting fluorescence having different wavelengths.

  The light emitting color conversion member of the present invention can suppress a decrease in light emission intensity and a shortened life, has a high color rendering property, and has a high color temperature from white light (daylight color) to low color temperature white light (bulb color). White light corresponding to various color temperatures can be emitted. Therefore, it is suitable as a member used as a light emitting device such as an illumination, a display, or a headlight of an automobile or the like.

  In order to suppress deterioration of the emission intensity and shortening of the lifetime caused by high output light, heat generation of the phosphor, or heat of the LED chip in the phosphor material, an organic material should not be included in the phosphor material. Just design. The luminescent color conversion member of the present invention is formed only from crystallized glass and an inorganic material of a glass sintered layer. For this reason, it is possible to suppress the deterioration of the emission intensity and the shortening of the lifetime caused by the high output light and the heat generation of the phosphor.

  Moreover, the luminescent color conversion member of the present invention is excited when the excitation light is irradiated, the crystallized glass and the glass sintered layer emit fluorescence having different wavelengths, and these lights are transmitted through the luminescent color conversion member. Since it is combined with light, it can emit white light corresponding to various color temperatures from white light (daylight color) having high color rendering properties and high color temperature to white light (bulb color) having a low color temperature.

  The excitation light is preferably a light beam having a wavelength of 300 to 500 nm. The reason is that if the excitation light is in the wavelength range of 300 to 500 nm, both the crystallized glass and the glass sintered layer can emit fluorescence, and the inorganic fluorescence that emits fluorescence when irradiated with light in this wavelength range. This is because there are many types of body powders and it is easy to obtain members.

In order to improve the color rendering of white light emitted from the phosphor material and adjust the color temperature, increase the type (color) of light used to synthesize white light, or adjust the type and intensity of light. In the phosphor material of the present invention, the amount of crystals in the crystallized glass, the thickness of the crystallized glass, the content of Eu ₂ O ₃ in the glass powder constituting the glass sintered layer, the glass sintered layer By adjusting the type and content of the phosphor inside, or the thickness of the sintered glass layer, the type and intensity of light emitted from these members can be adjusted.

  In particular, in the luminescent color conversion member of the present invention, when irradiated with excitation light, the crystallized glass and the glass sintered layer absorb light having a wavelength of 300 to 500 nm (preferably blue light), and from the crystallized glass, If those that emit fluorescence of light with a wavelength of 450 to 780 nm (preferably yellow light) and emit fluorescence of light with a wavelength of 500 to 780 nm (preferably red and / or green) from the glass sintered layer, these are used. White light (bulb color) having a low color temperature can be emitted by combining light emitted from the member and excitation light transmitted through the light emitting color conversion member.

  In the present invention, blue light is light having a central wavelength at a wavelength of 430 to 480 nm, green light is light having a central wavelength at a wavelength of 500 to 535 nm, and yellow light is light having a wavelength of 535 to 590 nm. The light having a central wavelength and the red light mean light having a central wavelength at a wavelength of 610 to 780 nm.

  In the luminescent color conversion member of the present invention, the crystallized glass substrate and the glass sintered layer are preferably in close contact by fusing and integrating the glass sintered layer onto the crystallized glass substrate. By adopting a structure in which no space is provided between the crystallized glass and the glass sintered layer, it is possible to suppress a decrease in light emission intensity and to improve mechanical strength. Further, it is not necessary to use a resin such as an adhesive that causes discoloration.

  In order to prevent the glass sintered layer from peeling from the crystallized glass substrate, α1−α2 ≦ ± 1 ppm / when the thermal expansion coefficient of the crystallized glass is α1 and the thermal expansion coefficient of the glass sintered layer is α2. It is preferable to make it into ° C. When it is out of this range, it becomes easy to peel off. Preferably, α1−α2 ≦ ± 0.8 ppm / ° C.

As the crystallized glass constituting the luminescent color conversion member of the present invention, it is preferable to use a glass obtained by precipitating a crystal containing Ce ³⁺ in a garnet crystal. The reason for this is that Ce ³⁺ in the garnet crystal becomes the emission center, absorbs blue excitation light, and easily emits yellow fluorescence.

Further, by precipitating a garnet crystal containing Ce ³⁺ from the glass, the garnet crystal is easily dispersed without entraining bubbles in the matrix glass of the crystallized glass. For this reason, fluorescence and transmitted excitation light are scattered in all directions, and the light easily spreads at a wide angle. Moreover, since there are few bubbles which block light, it becomes easy to permeate | transmit fluorescence and transmitted excitation light, and luminous efficiency becomes high.

The garnet crystal is generally a crystal represented by A ₃ B ₂ C ₃ O ₁₂ (A = Mg, Mn, Fe, Ca, Y, Gd, etc .: B = Al, Cr, Fe, Ga, Sc, etc .: C = Al, Si, Ga, Ge, etc.) As the above-mentioned garnet crystal, particularly a YAG crystal (Y ₃ Al ₅ O ₁₂ crystal) or a YAG crystal solid solution, a desired yellow fluorescence can be obtained. It is preferable because it emits light. As the YAG crystal solid solution, a part of Y is at least one element selected from the group consisting of Gd, Sc, Ca and Mg, and / or a part of Al is a group consisting of Ga, Si, Ge and Sc. YAG crystal solid solution substituted with at least one element selected from

  The crystallized glass is preferably plate-shaped. The reason is that when the crystallized glass is plate-like, it becomes easy to form a glass sintered layer on the crystallized glass substrate. As a method for forming crystallized glass into a plate shape, the crystalline glass is formed into a plate shape by roll forming, slot down forming, overflow forming, down draw forming, redraw forming, etc., and subjected to heat treatment to precipitate crystals. Can be obtained.

  The crystallized glass preferably has a thickness of 0.1 to 2.0 mm. The reason is that if the wall thickness is too thin, the amount of crystals in the crystallized glass decreases, and the crystallized glass cannot emit yellow fluorescence. As a result, it is difficult to obtain an emission color conversion member that emits white light. On the other hand, when the wall thickness is too thick, it becomes difficult to transmit blue excitation light, and as a result, it is difficult to obtain an emission color conversion member that emits white light.

Further, the preferred composition range of the crystallized glass, in _{mol%, SiO 2 + B 2 O} 3 10~60%, Al 2 O 3 + GeO 2 + Ga 2 O 3 15~50%, Y 2 O 3 + Gd 2 O 3 _{5~30%, Li 2 O 0~25%} , TiO 2 + ZrO 2 0~15%, CaO + 0~5% MgO, a Ce ₂ O ₃ 0.01~5%.

  The reason for determining the composition range of the crystallized glass is as follows.

SiO ₂ and B ₂ O ₃ are glass network-forming oxides, and are both components that suppress devitrification during the production of the mother glass, and these components are preferably 10 to 60 mol% in total. If the total amount is less than 10 mol%, it will not vitrify, and if it exceeds 60 mol%, the desired crystals will not easily precipitate. A preferable range of the total amount of these components is 30 to 47 mol%. When the total amount of these components is less than 40.5 mol%, a small amount of devitrification occurs during glass molding. This devitrification disappears by heat treatment for crystallization, and a dense garnet crystal is precipitated. There is no particular problem. The content of each _component, SiO 2 10 to 50 mol%, preferably B ₂ O ₃ 0 to 40 mol%.

Al ₂ O ₃ , Ga ₂ O _3, and GeO ₂ are constituents of the garnet crystal and components that improve chemical durability, and these components are preferably 15 to 50 mol% in total. . If the total amount is less than 15 mol%, garnet crystals are difficult to precipitate and the chemical durability is lowered. Moreover, when more than 50 mol%, it becomes difficult to vitrify and garnet crystals are hardly precipitated, which is not preferable. The preferable range of the total amount of these components is 20 to 40 mol%. The content of each component, Al ₂ O ₃ 15 to 45 mol%, Ga ₂ O ₃ 0 to 15 mol%, is preferably GeO ₂ 0 to 15 mol%.

Y ₂ O ₃ and Gd ₂ O ₃ are components of garnet crystals and are components that improve the uniform dispersibility of Ce and suppress concentration quenching. These components are combined in an amount of 5 to 30 mol%. Preferably there is. If the total amount is less than 5 mol%, garnet crystals are difficult to precipitate, and if it exceeds 30 mol%, vitrification is difficult, which is not preferable. A preferable range of the total amount of these components is 10 to 25 mol%. The content of each component, Y ₂ O ₃ 5 to 30 mol%, preferably Gd ₂ O ₃ 0 to 20 mol%.

Li ₂ O is a component that adjusts the viscosity of the glass as a network modification oxide without coarsening the crystal size and without reducing the amount of precipitated crystals, and its content is 0 to 25 mol%. preferable. Li content of ₂ O is hardly vitrified large amount of devitrification occurs during glass molding and more than 25 mol% is not preferable not devitrification disappears be subjected to heat treatment for crystallization. In particular, when the content of Li ₂ O is more than 2 mol%, it is preferable because garnet crystals are likely to precipitate. A preferable range of Li ₂ O is 2 to 20 mol%, and a more preferable range is 2.5 to 10 mol%.

ZrO ₂ and TiO ₂ can be contained in a total amount of up to 15 mol%, but garnet crystals are precipitated even if ZrO ₂ and TiO ₂ are not contained. Rather, the smaller the amount of ZrO ₂ and TiO ₂ , the higher the luminous efficiency, which is preferable. Thus, for example, it is preferred that it is less than 3 mol%, more preferably essentially free of content. Moreover, when these are more than 15 mol% in total amount, since it becomes difficult to precipitate a desired crystal | crystallization, it is unpreferable.

CaO and MgO partially dissolve in the precipitated YAG crystal, and adjust the crystal amount and the crystal particle system, and also have a function of adjusting the wavelength of fluorescence emitted from Ce ^{3+ in} the crystal. The total amount of these components is preferably 0 to 5 mol%. When the total amount is more than 5 mol%, it is difficult to vitrify, which is not preferable. The preferable range of the total amount of these components is 0.1 to 4.5 mol%. Moreover, it is preferable that content of each component is CaO 0-4 mol% and MgO 0-4 mol%.

Ce ₂ O ₃ is a component that becomes a light emission center, and the content of Ce ₂ O ₃ is 0.01 to 5 mol%. When the content of Ce ₂ O ₃ is less than 0.01 mol%, it is difficult to serve as a luminescent center component, and the fluorescence intensity is not sufficient. On the other hand, if it exceeds 5 mol%, the light emission efficiency is lowered by concentration quenching, which is not preferable. The preferred range of ce ₂ O ₃ is 0.01 to 2 mol%.

In addition to the above-described components, Na ₂ O, K ₂ O, Sc ₂ O _{3 and the} like can be added up to 10 mol%, respectively.

  Moreover, in order to obtain the above crystallized glass, a glass raw material is prepared and melted so as to be in the glass composition range described above to produce a plate-like crystalline glass, and then the obtained plate-like glass is obtained. The crystalline glass can be obtained by heat treatment at 1150 to 1600 ° C. (preferably 1200 to 1500 ° C.) for 0.5 to 20 hours and then polishing to a desired thickness.

As the sintered glass layer constituting the light emitting color conversion member of the present invention, (1) the Eu ₂ O ₃ made by firing a glass powder containing a glass component, (2) a glass powder and an inorganic phosphor It is preferable to use any one obtained by firing a mixture containing powder. Since such a glass sintered layer has a structure in which Eu ions or inorganic phosphors are dispersed in glass, it is chemically stable and can suppress discoloration even when exposed to high output light for a long period of time. This is because it can.

In the case of using a sintered glass layer obtained by firing glass powder containing Eu ₂ O ₃ as a glass component, the glass powder includes SiO ₂ —B ₂ O ₃ —RO (RO is MgO, CaO, SrO). , BaO) glass, SiO ₂ —B ₂ O ₃ glass, SiO ₂ —B ₂ O ₃ —R ₂ O (R ₂ O represents Li ₂ O, Na ₂ O, K ₂ O) glass. SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ glass and SiO ₂ —B ₂ O ₃ —ZnO glass can be used. Among them, it is preferable to use SiO ₂ —B ₂ O ₃ —RO-based glass that is hard to devitrify even when melted and that can easily obtain sufficient light emission intensity even when Eu ₂ O _{3 serving} as a component of the emission center is added. .

The composition range of the SiO ₂ —B ₂ O ₃ —RO-based glass is SiO ₂ 30 to 70%, B ₂ O ₃ 1 to 15%, MgO 0 to 10%, CaO 0 to 25%, SrO 0 in terms of mole percentage. ~10%, BaO 5~40%, RO 10~45%, Al 2 O 3 0~20%, 0~10% ZnO, is preferably Eu ₂ O ₃ 0.1~5%. The reason for determining the above range is as follows.

SiO ₂ is a component that forms a network of glass. When the content is less than 30 mol%, chemical durability tends to deteriorate. On the other hand, if it exceeds 70 mol%, the meltability tends to deteriorate. A more preferred range of SiO ₂ is 45 to 65%.

B ₂ O ₃ is a component that significantly improves the meltability by lowering the melting temperature of the glass. When the content is less than 1 mol%, it is difficult to obtain the effect. On the other hand, when it exceeds 15 mol%, chemical durability tends to deteriorate. A more preferable range of B ₂ O ₃ is 2 to 10%.

  MgO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of MgO is 0 to 5%.

  CaO is a component that improves the meltability by lowering the melting temperature of the glass. When the content is more than 25 mol%, chemical durability tends to deteriorate. A more preferable range of CaO is 3 to 20%.

  SrO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of SrO is 0 to 5%.

  BaO is a component that improves the meltability by lowering the melting temperature of the glass. When the content is less than 5 mol%, the effect of improving the meltability tends to decrease. On the other hand, when it exceeds 40 mol%, chemical durability tends to deteriorate. A more preferable range of BaO is 10 to 35%.

  In order to improve the meltability of the glass without deteriorating the chemical durability, it is preferable that the total amount of RO of MgO, CaO, SrO and BaO is 10 to 45 mol%. If the RO content is less than 10 mol%, it is difficult to obtain the effect of improving the meltability. On the other hand, when it exceeds 45 mol%, chemical durability tends to deteriorate. A more preferable range of RO is 11 to 40%.

Al ₂ O ₃ is a component that improves chemical durability. When the content exceeds 20 mol%, the meltability of the glass tends to deteriorate. A more preferable range of Al ₂ O ₃ is 2 to 15%.

  ZnO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of ZnO is 1 to 7%.

Eu ₂ O ₃ is a component that becomes a light emission center in the glass sintered layer. If the content is less than 0.1%, it will be difficult to fulfill the role as a light emission center component, and sufficient light emission intensity cannot be obtained. On the other hand, if it exceeds 5 mol%, the light emission efficiency decreases due to concentration quenching, which is not preferable. The preferred range of Eu ₂ O ₃ is 0.5-2%.

In addition to the above components, various components can be added as long as the gist of the present invention is not impaired. For example, an alkali metal oxide, P ₂ O ₅ , La ₂ O ₃ or the like may be added.

  Moreover, it is desirable to use a glass powder having an average particle size of 1 to 100 μm. If the average particle size of the glass powder is reduced, the cost is likely to increase. On the other hand, when the average particle size increases, it becomes difficult to efficiently irradiate the Eu ions in the glass sintered layer with excitation light.

When using a glass sintered layer obtained by firing a mixture containing glass powder and inorganic phosphor powder, the inorganic phosphor powder contained in the glass sintered layer is generally available in the market. Can be used, and there are oxides, nitrides, oxynitrides, sulfides, oxysulfides, halides, halophosphates, and the like. Among the above inorganic phosphors, it is particularly preferable to use 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 red and / or green. Specifically, as phosphors emitting red fluorescence when irradiated with blue light, CaS: Eu ²⁺ , ZnS: Mn ²⁺ , Te ²⁺ , Mg ₂ TiO ₄ : Mn ⁴⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , SrS: Eu ²⁺ , Na _1.23 K _0.42 Eu _0.12 TiSi ₄ O ₁₁ , Na _1.23 K _0.42 Eu _0.12 TiSi ₅ O ₁₃ : Eu ³⁺ , CdS: In, Te, CaAlSiN ₃ : Eu ²⁺ , CaSiN ₃ ^{: Eu 2+, (Ca, Sr} ) 2 Si 5 N 8: can be used _{^{Eu 2+, Eu 2 W 2 O}} 7. Further, as phosphors that emit green fluorescence when irradiated with blue light, SrAl ₂ O ₄ : Eu ²⁺ , SrGa ₂ S ₄ : Eu ²⁺ , SrBaSiO ₄ : Eu ²⁺ , CdS: In, CaS: Ce ³⁺ Y ₃ (Al, Gd) ₅ O ₁₂ : Ce ²⁺ , Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce ³⁺ , SrSiO _N : Eu ²⁺ can be used. Some of these phosphors react with glass by heating at the time of sintering and cause abnormal reactions such as foaming and discoloration, and the degree becomes more remarkable as the sintering temperature is higher. However, even such inorganic phosphors can be used by optimizing the firing temperature and glass composition.

The glass powder used when producing the glass sintered layer has a role as a medium for stably holding the inorganic phosphor. Further, since the color tone of the sintered body varies depending on the composition system of the glass powder and the reactivity with the inorganic phosphor varies, it is necessary to select the composition of the glass powder in consideration of various conditions. It is also important to determine the amount of inorganic phosphor added suitable for the glass composition and the thickness of the member. The glass powder is not particularly limited as long as it does not easily react with the inorganic phosphor. For example, SiO ₂ —B ₂ O ₃ —RO (RO represents MgO, CaO, SrO, BaO). system glass, SiO ₂ -B ₂ O ₃ based _{glass, SiO 2 -B 2 O 3 -R} 2 O (R 2 O represents _{Li 2 O, Na 2 O,} K 2 O) -based glass, SiO ₂ -B ₂ O ₃ —Al ₂ O ₃ glass and SiO ₂ —B ₂ O ₃ —ZnO glass can be used. Among these, it is preferable to use SiO ₂ —B ₂ O ₃ —RO-based glass that hardly reacts with the inorganic phosphor during firing.

The composition range of the SiO ₂ —B ₂ O ₃ —RO-based glass is SiO ₂ 30 to 70%, B ₂ O ₃ 1 to 15%, MgO 0 to 10%, CaO 0 to 25%, SrO 0 in terms of mole percentage. ~10%, BaO 5~40%, RO 10~45%, Al 2 O 3 0~20%, is preferably 0% ZnO. The reason for determining the above range is as follows.

SiO ₂ is a component that forms a network of glass. When the content is less than 30 mol%, chemical durability tends to deteriorate. On the other hand, if it exceeds 70 mol%, the sintering temperature becomes high, and the phosphor tends to deteriorate. A more preferable range of SiO ₂ is 45 to 65%.

B ₂ O ₃ is a component that significantly improves the meltability by lowering the melting temperature of the glass. When the content is less than 1 mol%, it is difficult to obtain the effect. On the other hand, when it exceeds 15 mol%, chemical durability tends to deteriorate. A more preferable range of B ₂ O ₃ is 2 to 10%.

  MgO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of MgO is 0 to 5%.

  CaO is a component that improves the meltability by lowering the melting temperature of the glass. When the content is more than 25 mol%, chemical durability tends to deteriorate. A more preferable range of CaO is 3 to 20%.

  SrO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of SrO is 0 to 5%.

  BaO is a component that improves the meltability by lowering the melting temperature of the glass and suppresses the reaction with the phosphor. When the content is less than 5 mol%, the reaction suppression effect with the phosphor tends to be reduced. On the other hand, when it exceeds 40 mol%, chemical durability tends to deteriorate. A more preferable range of BaO is 10 to 35%.

  In order to improve the meltability of the glass without deteriorating the chemical durability, it is preferable that the total amount of RO of MgO, CaO, SrO and BaO is 10 to 45 mol%. If the RO content is less than 10 mol%, it is difficult to obtain the effect of improving the meltability. On the other hand, when it exceeds 45 mol%, chemical durability tends to deteriorate. A more preferable range of RO is 11 to 40%.

Al ₂ O ₃ is a component that improves chemical durability. When the content exceeds 20 mol%, the meltability of the glass tends to deteriorate. A more preferable range of Al ₂ O ₃ is 2 to 15%.

  ZnO is a component that improves the meltability by lowering the melting temperature of the glass. When the content exceeds 10 mol%, chemical durability tends to deteriorate. A more preferable range of ZnO is 1 to 7%.

In addition to the above components, various components can be added as long as the gist of the present invention is not impaired. For example, an alkali metal oxide, P ₂ O ₅ , La ₂ O ₃ or the like may be added.

  Moreover, it is desirable to use a glass powder having an average particle size of 1 to 100 μm. If the average particle size of the glass powder is reduced, the cost is likely to increase. On the other hand, when the average particle size becomes large, it becomes difficult to efficiently irradiate the phosphor in the glass sintered layer with excitation light.

  The luminous efficiency of the sintered glass layer varies depending on the type and content of phosphor particles dispersed in the glass and the thickness of the sintered glass layer. The phosphor content and the thickness of the sintered glass layer may be adjusted to optimize the energy conversion efficiency. However, if the phosphor is too much, it becomes difficult to sinter and the porosity increases. There arises a problem that it becomes difficult to efficiently irradiate the phosphor with the excitation light. On the other hand, if the amount is too small, it becomes difficult to emit light sufficiently. Therefore, the mixing ratio of the glass powder and the inorganic phosphor powder is 70 to 99.99% (preferably 80 to 99.95%, more preferably 85 to 99.92%) of the glass powder in terms of mass ratio, inorganic. It is preferable to adjust the phosphor powder to a range of 0.01 to 30% (preferably 0.5 to 20%, more preferably 0.08 to 15%).

  Moreover, in order to obtain said glass sintered layer, the mixture which added the organic solvent and binder resin to said glass powder or glass powder and inorganic fluorescent substance powder is made into forms, such as a paste and a green sheet, for example It can be obtained by firing.

  A method for obtaining a glass sintered layer using a paste will be described.

  A paste uses a binder, a plasticizer, a solvent, etc. with the glass powder mentioned above or glass powder and inorganic fluorescent substance powder.

  As a ratio of the glass powder which occupies for the whole paste, or a glass powder and an inorganic fluorescent substance powder, about 30-90 mass% is common.

  A binder is a component which increases the film | membrane intensity | strength after drying and provides a softness | flexibility, and the content is about 0.1-20 mass% in general. As the binder, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose, nitrocellulose and the like can be used, and these are used alone or in combination.

  The plasticizer is a component that controls the drying speed and imparts flexibility to the dry film, and the content thereof is generally about 0 to 10% by mass. As the plasticizer, dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, dibutyl phthalate and the like can be used, and these are used alone or in combination.

  The solvent is a material for pasting the material, and its content is generally about 10 to 50% by mass. As the solvent, terpineol, isoamyl acetate, toluene, methyl ethyl ketone, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate and the like can be used alone or in combination.

  The paste can be prepared by preparing glass powder, inorganic phosphor powder, binder, plasticizer, solvent and the like and kneading them at a predetermined ratio.

  In order to directly form a sintered glass layer on a substrate using such a paste, the paste is applied on the substrate using a screen printing method, a batch coating method, or the like, and a coating layer having a predetermined film thickness is formed. After forming, a predetermined glass sintered layer can be obtained by drying and firing at 700 to 1000 ° C.

  Next, a method for obtaining a sintered glass layer using a green sheet will be described.

  The green sheet uses a binder, a plasticizer, a solvent and the like together with the glass powder or the glass powder and the inorganic phosphor powder.

  As for the ratio of the glass powder which occupies in a green sheet, or glass powder and inorganic fluorescent substance powder, about 50-80 mass% is common.

  As the binder, plasticizer, and solvent, the same binder, plasticizer, and solvent as those used in the preparation of the paste can be used, and the mixing ratio of the binder is 0.1 to 30 mass. The mixing ratio of the plasticizer is generally about 0 to 10% by mass, and the mixing ratio of the solvent is generally about 1 to 40% by mass.

  As a general method for producing a green sheet, the above glass powder, inorganic phosphor powder, binder, plasticizer, etc. are prepared, and a solvent is added to these to form a slurry. A sheet is formed on a film of terephthalate (PET) or the like. Subsequently, after forming the sheet, it is possible to obtain a green sheet by removing the organic solvent by drying.

  In order to directly form a glass sintered layer on a substrate using the green sheet obtained as described above, the green sheet is laminated on the substrate and thermocompression-bonded to form a coating layer. A sintered glass layer can be obtained by firing in the same manner as in the case of the paste.

  In addition, although the example which uses a paste or a green sheet was given as a manufacturing method of a glass sintered layer, the glass sintered layer used for the luminescent color conversion member of this invention is not limited to this, Generally ceramics are used. Various methods used for manufacturing can be applied.

  The glass sintered layer preferably has a thickness of 0.1 to 1.0 mm. If the wall thickness is too thin, the glass sintered layer cannot emit red and / or green fluorescence, and as a result, it is difficult to obtain a luminescent color conversion member that emits white light. On the other hand, if the wall thickness is too thick, it is difficult to transmit blue excitation light or yellow fluorescence emitted from crystallized glass, and as a result, it is difficult to obtain an emission color conversion member that emits white light.

  Next, a preferred method for producing the luminescent color conversion member of the present invention will be described.

  First, a crystallized glass produced using the above-described method and a paste or green sheet for obtaining a glass sintered layer are prepared. Next, a paste is applied to the crystallized glass surface using a screen printing method, a batch coating method, or the like, or a green sheet is laminated, and a glass layer is formed on the crystallized glass surface. Thereafter, the crystallized glass on which the glass layer is formed is fired. By doing in this way, the luminescent color conversion member of this invention can be obtained.

  In addition, the luminescent color conversion member of the present invention is obtained by cutting and polishing the luminescent color conversion member obtained by firing the crystallized glass on which the glass layer has been formed, and having any shape, for example, a disc shape, a column shape, or a rod shape. You may process into the shape of these.

  In addition, as a temperature which bakes the crystallized glass in which the glass layer was formed, it is preferable to bake at 700-1000 degreeC. The reason is that at a temperature lower than 700 ° C., the glass sintered layer is easily peeled off from the crystallized glass, or a dense glass sintered layer is difficult to obtain. It becomes difficult to obtain a luminescent color conversion member that emits the light. On the other hand, at a temperature higher than 1000 ° C., it is difficult to obtain a luminescent color conversion member that emits desired light due to a change in crystal structure in the crystallized glass or a reaction between the glass in the glass sintered layer and the inorganic phosphor.

  Hereinafter, based on an Example, the luminescent color conversion member of this invention is demonstrated in detail.

Example 1 is a luminescent color conversion member produced by applying a glass powder containing Eu ₂ O ₃ as a glass component to a crystallized glass surface in the form of a paste and baking it.

  The luminescent color conversion member was produced as follows.

  First, a crystallized glass and a paste for obtaining a glass sintered layer were prepared. Next, the paste was applied on the surface of the crystallized glass by a batch coating method to form a glass layer (thickness 50 μm). Next, the crystallized glass coated with the glass layer was degreased at 300 ° C. for 1 hour and baked at 850 ° C. for 20 minutes to produce a light emitting color conversion member.

  The thickness of the sintered glass layer measured for the luminescent color conversion member thus obtained was 40 μm. Further, when light emitted from a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side and emitted from the glass sintered layer side was measured using a chromaticity meter, x = 0.400 in CIE coordinates, Since y = 0.380, a light bulb-colored white light with a high color rendering property was obtained.

  The crystallized glass was prepared as follows.

First, in mol%, SiO ₂ 34%, Al ₂ O ₃ 33%, Y ₂ O ₃ 15%, GeO ₂ 6%, Gd ₂ O ₃ 8%, Li ₂ O 3%, CaO + MgO + Sc ₂ O ₃ 0.5% The glass raw material prepared to have a composition containing 0.5% Ce ₂ O ₃ is placed in a platinum crucible, melted at 1650 ° C. for 3 hours, and then the glass melt is poured into a carbon plate to obtain crystallinity. Glass was obtained. Next, the obtained crystalline glass was heat-treated at 1400 ° C. for 9 hours, and both surfaces were polished so that the thickness became 0.5 mm, thereby obtaining crystallized glass.

  The crystallized glass thus obtained was identified as precipitated crystals using an X-ray powder diffractometer, and it was confirmed that YAG crystals were precipitated. Moreover, when the light emitted from the blue light emitting diode having a peak at a wavelength of 465 nm is irradiated from the rear of the crystallized glass and the light emitted from the front is measured using a fluorescence spectrophotometer, a blue spectrum having a center near the wavelength of 465 nm, A yellow spectrum having a center near a wavelength of 560 nm was observed.

  Moreover, about the paste for obtaining a glass sintered layer, it produced as follows.

A composition containing 58.75% SiO ₂ , 5% B ₂ O ₃ , 10% CaO, 15% BaO, 5% Al ₂ O _3, 5% ZnO, and 1.25% Eu ₂ O _{3 in a} mole percentage. The glass raw material prepared in 1 was put in a platinum crucible and melted at 1400 ° C. for 2 hours to obtain a uniform glass. Next, this was pulverized with alumina balls and classified to obtain glass powder having an average particle size of 2.5 μm. Next, 6% by mass of ethyl cellulose as a binder and 90% by mass of terpineol as a solvent were added to the prepared glass powder 100 and mixed to prepare a paste.

  For the glass sintered layer (thickness 40 μm) produced using the paste, the light emitted from the blue light emitting diode having a peak at a wavelength of 465 nm is irradiated from the rear of the glass sintered layer, and the light emitted from the front is used with a fluorescence spectrophotometer. As a result, a blue spectrum having a center near a wavelength of 465 nm and a red spectrum having a center near a wavelength of 610 nm were observed. The glass sintered layer was formed by applying the paste prepared by the above method onto the porous mullite ceramic substrate by a batch coating method to form a glass layer (thickness 50 μm), degreased at 300 ° C. for 1 hour, and 850 ° C. After baking for 20 minutes, cooling was performed to remove the mullite substrate.

Example 2 is a luminescent color conversion member produced by applying a mixture containing glass powder and inorganic phosphor powder (SrS: Eu ²⁺ ) in the form of a paste to the crystallized glass surface and baking it.

  In the same manner as in Example 1, a paste was applied to the surface of crystallized glass and baked to produce a light emitting color conversion member.

  The thickness of the sintered glass layer measured for the luminescent color conversion member thus obtained was 40 μm. Further, when the light emitted from the glass sintered layer side by irradiating light of a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side was measured using a chromaticity meter, x = 0.390 in CIE coordinates, Since y = 0.390, white light of a light bulb color having high color rendering properties was obtained.

As for crystallized glass, SiO ₂ 34%, Al ₂ O ₃ 35%, Y ₂ O ₃ 12%, GeO ₂ 6%, Gd ₂ O ₃ 9%, Li ₂ O 3%, CaO + MgO + Sc _{2 in} mol%. O ₃ 0.5%, with those having a composition of Ce ₂ O ₃ 0.5%, was prepared in the same manner as in example 1, the wall thickness was used as a 0.5 mm. When the crystallized glass was identified as a precipitated crystal, a YAG crystal was precipitated, and the light emitted from the blue light emitting diode having a peak at a wavelength of 465 nm was irradiated from the rear of the crystallized glass. When measured using a fluorescence spectrophotometer, the same spectrum as in Example 1 was observed.

  About the paste for obtaining a glass sintered layer, it produced as follows.

As for the glass powder, a glass having a composition of 60% SiO ₂ , 5% B ₂ O ₃ , 10% CaO, 15% BaO, 5% Al ₂ O _3, 5% ZnO is used in Example 1. And having an average particle diameter of 2.5 μm was used. Next, SrS: Eu ²⁺ (average particle size: 8 μm) was added to the prepared glass powder as an inorganic phosphor powder at a mass ratio of 95: 5, and mixed to prepare a mixed powder. Next, 6% by mass of ethyl cellulose as a binder and 90% by mass of terpineol as a solvent were added to the prepared mixed powder 100 and mixed to prepare a paste. The paste prepared by the above method was applied on a porous mullite ceramic substrate to form a glass layer (thickness: 50 μm), fired to produce only a glass sintered layer, and the obtained glass sintered The layer (thickness 40 μm) was irradiated with light from a blue light emitting diode having a peak at a wavelength of 465 nm from the rear of the sintered glass layer, and the light emitted from the front was measured using a fluorescence spectrophotometer. A blue spectrum having a wavelength and a red spectrum having a center near a wavelength of 620 nm were observed.

Example 3 is a luminescent color conversion member produced by applying a mixture containing glass powder and inorganic phosphor powder (CaS: Eu ²⁺ ) in the form of a paste to the crystallized glass surface and baking it.

  In the same manner as in Examples 1 and 2, a paste was applied to the surface of crystallized glass and baked to produce a luminescent color conversion member.

  With respect to the luminescent color conversion member thus obtained, the light emitted from the glass sintered layer side by irradiating light from a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side was measured using a chromaticity meter. However, x = 0.390 and y = 0.390 in CIE coordinates, and a light bulb color white light with high color rendering properties was obtained.

  In addition, about the crystallized glass, the same thing as what was produced in Example 2 was used.

Moreover, about the paste for obtaining a glass sintered layer, CaS: Eu <^2+> (average particle diameter: 8 micrometers) is used as the inorganic fluorescent substance powder to the glass powder produced in Example 2, and 95: 5 by mass ratio. The paste was used at a ratio of It should be noted that the types and amounts of the binder and the solvent were the same as those in Example 2. In addition, a glass layer (thickness: 50 μm) is formed on a porous mullite ceramic substrate by using the paste prepared by the above method, fired to produce only a glass sintered layer, and the obtained glass sintered layer For (thickness 40 μm), the light emitted from the blue light emitting diode having a peak at a wavelength of 465 nm was irradiated from the rear of the sintered glass layer, and the light emitted from the front was measured using a fluorescence spectrophotometer. A blue spectrum and a red spectrum centered around a wavelength of 650 nm were observed.

Example 4 is a luminescent color conversion member produced by laminating and firing a glass powder containing Eu ₂ O ₃ as a glass component on a crystallized glass surface in the form of a green sheet.

  The luminescent color conversion member was produced as follows.

  First, a green sheet for obtaining crystallized glass and a sintered glass layer was prepared. Next, after a green sheet (thickness 50 μm) is laminated on the surface of the crystallized glass and integrated by thermocompression bonding to produce a laminate, degreased at 400 ° C. for 1 hour and fired at 900 ° C. for 20 minutes The luminescent color conversion member was produced by cooling.

  The thickness of the sintered glass layer measured for the luminescent color conversion member thus obtained was 40 μm. Further, when the light emitted from the glass sintered layer side by irradiating light of a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side was measured using a chromaticity meter, x = 0.390 in CIE coordinates, Since y = 0.400, white light of a light bulb color having high color rendering properties was obtained.

  About the crystallized glass, the same one as produced in Example 2 was used.

  About the green sheet for obtaining a glass sintered layer, it produced as follows.

  To the glass powder 100 produced in Example 1, 12% by mass of polyvinyl butyral resin as a binder, 3% by mass of dibutyl phthalate as a plasticizer, and 40% by mass of toluene as a solvent are added and mixed to obtain a slurry. Produced. Subsequently, the slurry was formed into a sheet on a PET film by the doctor blade method and dried to obtain a green sheet having a thickness of 50 μm.

  The glass sintered layer (thickness 40 μm) produced using the green sheet is irradiated with blue light emitting diode light having a peak at a wavelength of 465 nm from the rear of the glass sintered layer, and the light emitted from the front is measured with a fluorescence spectrophotometer As a result, the same spectrum as in Example 1 was observed. The glass sintered layer was prepared by laminating the green sheet produced by the above method on a porous mullite ceramic substrate and integrating it by thermocompression bonding, then degreased at 400 ° C. for 1 hour, and at 900 ° C. After baking for 20 minutes, it was cooled and the mullite substrate was removed.

Example 5 is a luminescent color produced by laminating and firing a mixture containing glass powder and inorganic phosphor powder (SrS: Eu ²⁺ and SrBaSiO ₄ : Eu ²⁺ ) in the form of a green sheet on the surface of crystallized glass. It is a conversion member.

  In the same manner as in Example 4, a green sheet (thickness 50 μm) was laminated on the surface of crystallized glass, integrated by thermocompression bonding to produce a laminate, degreased for 1 hour at 400 ° C., and 20 at 900 ° C. After the partial firing, it was cooled to produce a light emitting color conversion member.

  The thickness of the sintered glass layer measured for the luminescent color conversion member thus obtained was 40 μm. When light emitted from a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side and emitted from the glass sintered layer side was measured using a chromaticity meter, x = 0.430 in CIE coordinates and CIE coordinates. Y = 0.380, and light bulb-colored white light having high color rendering properties was obtained.

  In addition, about the crystallized glass, the same thing as what was produced in Example 2 was used.

  About the green sheet for obtaining a glass sintered layer, it produced as follows.

SrS: Eu ²⁺ (average particle size: 8 μm) and SrBaSiO ₄ : Eu ²⁺ (average particle size: 8 μm) were added as inorganic phosphor powder to the glass powder prepared in Example 2 at a mass ratio of 94: 3. : The one added at a ratio of 3 was used. In addition, about the kind of binder, a plasticizer, and a solvent, and quantity, it carried out similarly to Example 4, and produced it. Subsequently, the slurry was formed into a sheet on a PET film by the doctor blade method and dried to obtain a green sheet having a thickness of 50 μm. Moreover, it laminates | stacks on a porous mullite ceramic board | substrate using the said green sheet, thermocompression-bonded, it bakes and produces only a glass sintered layer, About glass sintering layer (thickness 40 micrometers) obtained, glass sintering A blue light emitting diode light having a peak at a wavelength of 465 nm was irradiated from the back of the layer, and the light emitted from the front was measured using a fluorescence spectrophotometer. As a result, a blue spectrum having a center near a wavelength of 465 nm and a center near a wavelength of 525 nm A green spectrum having a red color and a red spectrum having a center near a wavelength of 620 nm were observed. The sintered glass layer was obtained by degreasing at 400 ° C. for 1 hour, firing at 900 ° C. for 20 minutes, cooling, and removing the mullite substrate.

Example 6 is a luminescent color produced by laminating and firing a mixture containing glass powder and inorganic phosphor powder (CaS: Eu ²⁺ and SrBaSiO ₄ : Eu ²⁺ ) in the form of a green sheet on the surface of crystallized glass. It is a conversion member.

  In the same manner as in Example 4, a green sheet (thickness: 50 μm) was laminated on the surface of crystallized glass and integrated by thermocompression bonding to prepare a laminate, and then degreased at 400 ° C. for 1 hour, at 900 ° C. After baking for 20 minutes, it cooled and produced the luminescent color conversion member.

  The thickness of the sintered glass layer measured for the luminescent color conversion member thus obtained was 40 μm. When light emitted from a blue light emitting diode having a peak at a wavelength of 465 nm from the crystallized glass side and emitted from the glass sintered layer side was measured using a chromaticity meter, x = 0.430 in CIE coordinates and CIE coordinates. Y = 0.380, and light bulb-colored white light having high color rendering properties was obtained.

  In addition, about the crystallized glass, the same thing as what was produced in Example 2 was used.

  About the green sheet for obtaining a glass sintered layer, it produced as follows.

To the glass powder produced in Example 2, CaS: Eu ²⁺ (average particle size: 8 μm) and SrBaSiO ₄ : Eu ²⁺ (average particle size: 8 μm) were used as the inorganic phosphor powder in a mass ratio of 94: 3. : The one added at a ratio of 3 was used. In addition, about the kind of binder, a plasticizer, and a solvent, and quantity, it carried out similarly to Example 4, and produced it. Subsequently, the slurry was formed into a sheet on a PET film by the doctor blade method and dried to obtain a green sheet having a thickness of 50 μm. Moreover, it laminates | stacks on a porous mullite ceramic board | substrate using the said green sheet, thermocompression-bonded, it bakes and produces only a glass sintered layer, About glass sintering layer (thickness 40 micrometers) obtained, glass sintering A blue light emitting diode light having a peak at a wavelength of 465 nm was irradiated from the back of the layer, and the light emitted from the front was measured using a fluorescence spectrophotometer. As a result, a blue spectrum having a center near a wavelength of 465 nm and a center near a wavelength of 525 nm A green spectrum having a red color and a red spectrum having a center near a wavelength of 620 nm were observed. The sintered glass layer was obtained by degreasing at 400 ° C. for 1 hour, firing at 900 ° C. for 20 minutes, cooling, and removing the mullite substrate.

  The luminescent color conversion member of the present invention is not limited to LED applications, and can also be used for a device that emits high-power excitation light such as a laser diode.

It is explanatory drawing which shows the luminescent color conversion member which consists of crystallized glass and a glass sintered layer.

Explanation of symbols

1 Glass sintered layer 2 Crystallized glass

Claims (22)

  A luminescent color conversion member having a crystallized glass substrate and a glass sintered layer, wherein the glass sintered layer is formed on one or both sides of the crystallized glass substrate, and when the excitation light is irradiated, A luminescent color conversion member, wherein the crystallized glass and the glass sintered layer have a property of emitting fluorescence having different wavelengths.   2. The luminescent color conversion member according to claim 1, which is excited by light having a wavelength of 300 to 500 nm.   The luminescent color conversion member according to claim 1 or 2, wherein the crystallized glass substrate has a property of absorbing part or all of the excitation light and emitting fluorescence of light having a wavelength of 450 to 780 nm.   The luminescent color conversion member according to any one of claims 1 to 3, wherein the crystallized glass substrate has a property of absorbing part or all of blue light and emitting yellow fluorescence.   The luminescent color conversion member according to claim 1 or 2, wherein the glass sintered layer has a property of absorbing part or all of excitation light and emitting fluorescence of light having a wavelength of 500 to 780 nm.   6. The luminescent color conversion according to claim 1, wherein the sintered glass layer has a property of absorbing part or all of blue light and emitting red and / or green fluorescence. Element.   Crystallized glass substrate and glass sintered layer absorb part or all of blue light, crystallized glass substrate emits yellow fluorescence, and glass sintered layer emits red and / or green fluorescence. It has the property that when blue light is irradiated, the blue light transmitted through the luminescent color conversion member and the fluorescence emitted from the crystallized glass base material and the glass sintered layer are synthesized to emit white light. The luminescent color conversion member according to any one of claims 1 to 6.   The crystallized glass substrate and the glass sintered layer are in close contact with each other by fusing a glass sintered layer to the surface of the crystallized glass substrate. The luminescent color conversion member as described.   The thermal expansion coefficient of the crystallized glass is α1, and the thermal expansion coefficient of the glass sintered layer is α2, α1−α2 ≦ ± 1 ppm / ° C. Luminescent color conversion member. The luminescent color conversion member according to any one of claims 1 to 4 and 7 to 9, wherein the crystallized glass substrate is formed by depositing a crystal containing Ce ³⁺ in a garnet crystal.   The luminescent color conversion member according to claim 10, wherein the garnet crystal is a YAG crystal or a YAG crystal solid solution.   The luminescent color conversion member according to any one of claims 1 to 4 and 7 to 11, wherein the crystallized glass substrate is plate-shaped and has a thickness of 0.1 to 2.0 mm. . The crystallized glass substrate has a molar percentage of SiO ₂ + B ₂ O ₃ 10-60%, Al ₂ O ₃ + GeO ₂ + Ga ₂ O ₃ 15-50%, Y ₂ O ₃ + Gd ₂ O ₃ 5-30%, _{li 2 O 0~25%, TiO 2} + ZrO 2 0~15%, CaO + 0~5% MgO, claims 1-4 and 7, characterized in that it consists of glass containing Ce ₂ O ₃ 0.01~5% The luminescent color conversion member according to any one of -12. The luminescent color conversion member according to any one of claims 1, 2, and 5 to 9, wherein the glass sintered layer is obtained by firing glass powder containing Eu ₂ O ₃ as a glass component. Glass powder, in mole _{percent, SiO 2 30~70%, B 2} O 3 1~15%, 0~10% MgO, CaO 0~25%, SrO 0~10%, BaO 5~40%, RO 10 _{~45%, Al 2 O 3 0~20} %, 0~10% ZnO, emitting color conversion member according to claim 14, characterized in that it contains Eu ₂ O ₃ 0.1~5%.   The luminescent color conversion member according to any one of claims 1, 2, and 5 to 9, wherein the glass sintered layer is formed by firing a mixture containing glass powder and inorganic phosphor powder. Glass powder, in mole _{percent, SiO 2 30~70%, B 2} O 3 1~15%, 0~10% MgO, CaO 0~25%, SrO 0~10%, BaO 5~40%, RO 10 The luminescent color conversion member according to claim 16, comprising: ˜45%, Al ₂ O ₃ 0-20%, ZnO 0-10%.   The luminescent color conversion member according to claim 16, wherein the inorganic phosphor powder has an excitation band at a wavelength of 300 to 500 nm and an emission peak at a wavelength of 500 to 780 nm.   The luminescent color conversion member according to claim 16 or 18, wherein the inorganic phosphor powder has a property of emitting red and / or green light.   The luminescent color conversion member according to claim 16, wherein the mixture is in a range of 70 to 99.99% glass powder and 0.01 to 30% inorganic phosphor powder in terms of mass ratio.   The glass sintered layer is formed by firing a paste or a green sheet containing glass powder, an organic solvent and a binder resin, according to any one of claims 1, 2, 5 to 9, 14 and 16. Luminescent color conversion member.   The luminescent color conversion member according to any one of claims 1, 2, 5 to 9, 14, 16, and 21, wherein the glass sintered layer has a thickness of 0.01 to 1.0 mm.