JP5633114B2 - SnO-P2O5 glass used for phosphor composite material - Google Patents

Description

The present invention relates to SnO—P ₂ O ₅ glass used for a phosphor composite material suitable for a semiconductor light emitting device such as an LED (light emitting diode) or an LD (laser diode).

  In recent years, semiconductor light-emitting element devices such as white LEDs are expected to be applied to lighting applications as next-generation light sources that replace incandescent bulbs and fluorescent lamps. In general, a white LED is formed by coating a light emitting surface of an LED chip, which is a semiconductor light emitting element, with an organic binder resin containing phosphor powder. When excitation light from the LED chip passes through this coated mold part, all of the light is absorbed by the phosphor powder and converted to another wavelength, or part of the excitation light is absorbed by the phosphor powder. Then, the wavelength-converted light and the light transmitted without wavelength conversion are combined to emit desired white light. However, since the mold resin constituting the white LED has low heat resistance, there is a problem in that it is deteriorated by high-power short-wavelength excitation light in the blue to ultraviolet region and causes discoloration.

  Therefore, in order to solve the above problem, by firing and sintering a material composed of a non-lead glass powder having a high softening point of 500 ° C. or higher and a phosphor powder at a temperature higher than the softening point of the glass powder, A phosphor composite member in which phosphor powder is dispersed in a glass matrix has been proposed (for example, see Patent Document 1). Since the phosphor composite member is dispersed in a glass matrix that is an inorganic material, the phosphor composite member is chemically stable and has little deterioration. Moreover, even after long-term use, the glass matrix itself is not easily discolored by excitation light.

However, some phosphor powders used in semiconductor light emitting device devices such as white LEDs have low heat resistance, and the method described in Patent Document 1 cannot sufficiently secure the stability of the phosphor powder. There is a case. That is, when phosphor powder with low heat resistance is mixed with a lead-free glass powder having a softening point of 500 ° C. or higher and fired, the phosphor powder deteriorates due to heat during firing, and the phosphor composite member emits light. There is a problem that efficiency decreases. Thus, in order to solve the above problem, a method of dispersing phosphor powder in SnO—P ₂ O ₅ —B ₂ O ₃ glass having a low softening point has been proposed (see, for example, Patent Document 2).

JP 2003-258308 A JP 2008-19421 A

Depending on the type of phosphor powder, a lower firing temperature may be required, and the SnO—P ₂ O ₅ —B ₂ O ₃ glass described in Patent Document 2 cannot sufficiently handle various phosphor powders. There is a case. On the other hand, the SnO—P ₂ O ₅ —B ₂ O ₃ -based glass described in Patent Document 2 also has a problem that weather resistance tends to be lowered when the softening point is lowered.

Therefore, the object of the present invention is to have a low-temperature softening characteristic applicable to various phosphor powders, hardly react with the phosphor powder by firing, and has excellent weather resistance, and can be used over a long period of time. An object of the present invention is to provide SnO—P ₂ O ₅ glass used for a phosphor composite material with little deterioration.

The present inventors have found that the SnO—P ₂ O ₅ glass used in the phosphor composite material can solve the above problem when the SnO—P ₂ O ₅ glass has a specific composition. As proposed.

That is, the present invention provides a _SnO-P 2 _{O 5} based glass used for phosphor composite material, in _{mol%, SnO 72~90%, P 2} O 5 10~28%, Al 2 O 3 0~ _{10%, SiO 2 0~10%,} Li 2 O 0~10%, Na 2 O 0~10%, K 2 O 0~10%, Li 2 O + Na 2 O + K 2 O 0~10%, MgO 0~10 %, CaO 0-10%, SrO 0-10%, BaO 0-10%, MgO + CaO + SrO + BaO 0-10% in composition, molar ratio SnO / P ₂ O ₅ is 2.6-15, B ₂ The present invention relates to SnO—P ₂ O ₅ glass characterized by substantially not containing O ₃ and ZnO.

In general, SnO-P ₂ O ₅ glass, which is a low softening point glass, is said to have low weather resistance, but in the present invention, by containing SnO content as high as 72 mol% or more, low-temperature softening characteristics and It has become possible to produce a phosphor composite material having both weather resistance. Therefore, the phosphor composite material using the SnO—P ₂ O ₅ glass of the present invention can be sintered at low temperature, there is little reaction between the glass powder and the phosphor powder during firing, and the phosphor composite material. The phosphor composite member obtained by sintering is characterized by excellent weather resistance and little deterioration even when used over a long period of time.

By the way, B ₂ O ₃ and ZnO have an effect of improving the weather resistance of the glass, but there is a problem that the softening point is also increased. Therefore, in the present invention, it is possible to achieve a lower softening point by substantially not containing B ₂ O ₃ and Zn ₂ O. _Further, B 2 _{O 3} and ZnO may serve to ultraviolet region, especially to lower the ultraviolet transmittance of the wavelength 330～380Nm. Since the SnO—P ₂ O ₅ glass of the present invention does not substantially contain B ₂ O ₃ and ZnO , it has excellent ultraviolet light transmission characteristics. Therefore, the phosphor composite material using the SnO—P ₂ O ₅ glass of the present invention is suitable for a semiconductor light emitting device using an ultraviolet excitation light source.

In the present invention, “SnO—P ₂ O ₅ -based glass” refers to a glass containing SnO and P ₂ O ₅ in a total amount of 50 mol% or more.

In the present invention, the term "not containing B ₂ O ₃ and ZnO substantially" is meant that no added B ₂ O ₃ and ZnO intentionally, does not exclude the level as impurities . Specifically, it means that the contents of B ₂ O ₃ and ZnO are each less than 0.1 mol%.

Second , the SnO—P ₂ O ₅ glass of the present invention preferably has an internal transmittance of 80% or more at a wavelength of 365 nm.

The phosphor composite material using the SnO—P ₂ O ₅ glass having the above configuration is particularly suitable for a semiconductor light emitting device using an ultraviolet excitation light source. In the present invention, “internal transmittance at a wavelength of 365 nm” refers to a measured value at a thickness of 1 mm.

Third , the SnO—P ₂ O ₅ glass of the present invention preferably has a softening point of 350 ° C. or lower.

According to this configuration, even in the case of using a phosphor powder having low heat resistance, firing almost no phosphor composite that phosphor powder is deteriorated by reacting with SnO-P ₂ O ₅ based glass powder during Material can be obtained.

Fourth, the present invention relates to a _SnO-P 2 _{O 5} based glass powder comprising _SnO-P 2 _{O 5} based glass according to the one.

By using SnO—P ₂ O ₅ glass in powder form, the phosphor powder can be sufficiently dispersed in the SnO—P ₂ O ₅ glass, and a phosphor composite member having desired characteristics can be easily obtained. It can be produced.

Fifth , the present invention relates to a phosphor composite material containing the SnO—P ₂ O ₅ glass powder and phosphor powder.

Sixth , the phosphor composite material of the present invention preferably has a phosphor powder content of 0.01 to 30% by mass.

Seventh , the present invention relates to a phosphor composite member made of a sintered body of the phosphor composite material described above.

Eighth , it is preferable that the phosphor composite member of the present invention converts excitation light having a wavelength of 300 to 500 nm into visible light having a wavelength of 380 to 780 nm different from the wavelength of the excitation light.

Ninth , the present invention relates to a semiconductor light-emitting element device using any of the phosphor composite members described above.

  In the present invention, “%” represents “mol%” unless otherwise specified.

In the SnO—P ₂ O ₅ glass of the present invention, SnO is a component that forms a glass skeleton and lowers the softening point. The SnO content is preferably 72 to 90%, 73 to 88%, and particularly preferably 75 to 85%. There exists a tendency for a weather resistance to fall that content of SnO is less than 72%. On the other hand, when the content of SnO exceeds 90%, devitrification bumps resulting from Sn are precipitated in the glass, and the transmittance of the glass tends to be lowered. As a result, the phosphor composite member having high luminous efficiency. Is difficult to obtain. Moreover, glass becomes unstable and 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 10 to 28%, 12 to 27%, particularly preferably 15 to 25%. When the content of P ₂ O ₅ is less than 10%, vitrification becomes difficult. On the other hand, when the content of P ₂ O ₅ exceeds 28%, the weather resistance tends to be remarkably lowered.

Note that lowering the softening point of the _SnO-P 2 _{O 5} based glass, yet in stabilizes, the value of SnO _/ P 2 _{O 5,} in a molar ratio, 2.6～15,2.9～10, In particular, the range of 3 to 7 is preferable. When the value of SnO / P ₂ O ₅ is less than 2.6, the weather resistance tends to be remarkably lowered. On the other hand, if the value of SnO / P ₂ O ₅ exceeds 15, devitrification bumps due to Sn are deposited in the glass and the transmittance of the glass tends to decrease, and as a result, fluorescence having high luminous efficiency. It becomes difficult to obtain a body composite member.

As described above, B ₂ O ₃ and ZnO have the effect of improving the weather resistance of the glass, but increase the softening point and lower the ultraviolet transmittance, particularly the ultraviolet transmittance in the wavelength range of 330 to 380 nm. There is. Therefore, the total content of B ₂ O ₃ and ZnO is preferably 5% or less, 3% or less, 1% or less, and particularly not substantially contained. When the total content of B ₂ O ₃ and ZnO exceeds 5%, it becomes difficult to obtain a low-temperature softening characteristic, particularly a softening point of 350 ° C. or lower, and further 320 ° C. or lower. Further, inferior in ultraviolet transmittance, the phosphor composite material using the SnO-P ₂ O ₅ based glass, it is difficult to use the semiconductor light-emitting element device using the ultraviolet excitation light source. However, when the objective is to secure the weather resistance of the glass to some extent, the total amount of B ₂ O ₃ and ZnO can be 0.1% or more, and further 1% or more can be contained.

_SnO-P 2 _{O 5} based glass of the present invention, in _{mol%, SnO 72~90%, P 2} O 5 10~28%, Al 2 O 3 0~10%, SiO 2 0~10%, Li 2 O 0-10%, Na ₂ O 0-10%, K ₂ O 0-10%, Li ₂ O + Na ₂ O + K ₂ O 0-10%, MgO 0-10%, CaO 0-10%, SrO 0-10 As an example, a composition containing 1%, BaO 0 to 10%, MgO + CaO + SrO + BaO 0 to 10%, and B ₂ O ₃ + ZnO 0 to 5% is given. The reason for limiting the glass composition in this way is as follows. Note that SnO, P ₂ O ₅ , B ₂ O ₃ , and ZnO are as described above, and will not be described below.

Al ₂ O ₃ is a component that stabilizes the glass. The content of Al ₂ O ₃ is 0 to 10%, 0 to 7%, 1 to 5%, particularly 1 to 2%. When the content of Al ₂ O ₃ exceeds 10%, the softening point of the glass rises and the phosphor composite material becomes difficult to be sintered at a low temperature, and the phosphor powder tends to deteriorate.

SiO ₂ is a component that stabilizes the glass in the same manner as Al ₂ O ₃ . The content of SiO ₂ is 0 to 10%, 0 to 7%, 0.1 to 5%, particularly 0.1 to 2%. When the content of SiO ₂ exceeds 10%, the softening point of the glass rises, and it becomes difficult to sinter the phosphor composite material at low temperature, and the phosphor powder tends to deteriorate. Moreover, it becomes easy to phase-separate glass.

The total amount of Al ₂ O ₃ and SiO ₂ is preferably 0 to 10%, 0 to 5%, particularly preferably 0.1 to 2%. If the total amount of Al ₂ O ₃ and SiO ₂ exceeds 10%, the softening point of the glass is increased, making it difficult to sinter the phosphor composite material at low temperature, and the phosphor powder tends to deteriorate.

Li ₂ O is a component that significantly lowers the softening point of glass. The content of Li ₂ O is preferably 0 to 10%, 0 to 7%, particularly preferably 1 to 5%. When the content of Li ₂ O exceeds 10%, the glass becomes extremely unstable and becomes difficult to vitrify.

Na ₂ O is a component that lowers the softening point of glass. The content of Na ₂ O is preferably 0 to 10%, 0 to 7%, particularly preferably 0.1 to 5%. When the content of Na 2 _O exceeds 10%, the vitrification hardly occurs glass becomes unstable.

K ₂ O is a component that slightly lowers the softening point of glass. The content of K ₂ O is preferably 0 to 10%, 0 to 7%, particularly preferably 1 to 5%. When the content of K ₂ O increases, the glass tends to become unstable and is difficult to vitrify.

The total amount of Li ₂ O, Na ₂ O and K ₂ O is preferably 0 to 10%, 0 to 7%, particularly 1 to 5%. When the total amount of these components exceeds 10%, the glass becomes unstable and it is difficult to vitrify.

Thus, Li ₂ O, Na ₂ O and K ₂ O have the effect of lowering the softening point of the glass, so that the firing temperature of the phosphor composite material can be lowered, resulting in deterioration of the phosphor powder. Is suppressed, and a phosphor composite member having excellent luminous efficiency can be manufactured.

  MgO is a component that stabilizes glass and facilitates vitrification. The content of MgO is preferably 0 to 10%, 0 to 7%, particularly preferably 1 to 5%. If the content of MgO exceeds 10%, the glass tends to devitrify and the transmittance tends to decrease, and as a result, it becomes difficult to obtain a phosphor composite member having high luminous efficiency.

  CaO is a component that stabilizes glass and facilitates vitrification. The content of CaO is preferably 0 to 10%, 0 to 7%, particularly preferably 0.1 to 5%. If the content of CaO exceeds 10%, the glass tends to devitrify and the transmittance tends to decrease, and as a result, it becomes difficult to obtain a phosphor composite member having high luminous efficiency.

  SrO is a component that stabilizes glass and facilitates vitrification. The SrO content is preferably 0 to 10%, 0 to 7%, particularly preferably 0.1 to 5%. If the SrO content exceeds 10%, the glass tends to devitrify and the transmittance tends to decrease, and as a result, it becomes difficult to obtain a phosphor composite member having high luminous efficiency.

  BaO is a component that stabilizes glass and facilitates vitrification. The content of BaO is preferably 0 to 10%, 0 to 5%, 0 to 3%, particularly preferably 0.1 to 1%. If the content of BaO exceeds 5%, the glass tends to devitrify significantly and the transmittance tends to decrease, and as a result, it becomes difficult to obtain a phosphor composite member having high luminous efficiency.

  The total amount of MgO, CaO, SrO and BaO is preferably 0 to 10%, 0 to 7%, particularly 1 to 5%. If the total amount of these components exceeds 10%, the glass tends to devitrify and the transmittance tends to decrease, and as a result, it becomes difficult to obtain a phosphor composite member having high luminous efficiency.

  When SnO is contained in a large amount or when an alkali oxide is added, the glass has a low softening point, but the glass tends to be unstable. On the other hand, since MgO, CaO, SrO and BaO have an effect of stabilizing the glass, the addition of these components makes it possible to reduce the softening point while maintaining the stability of the glass.

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, in order to improve the weather resistance, Ta ₂ O ₅ , Nb ₂ O ₅ , Gd ₂ O ₃ , and La ₂ O ₃ may be added up to 10% in total.

The SnO—P ₂ O ₅ glass of the present invention preferably has an internal transmittance of 80% or more, particularly 82% or more at a wavelength of 365 nm. When the internal transmittance at a wavelength of 365 nm is less than 80%, it becomes difficult to use the phosphor composite material using the SnO—P ₂ O ₅ glass in a semiconductor light emitting device using an ultraviolet excitation light source. .

The softening point of the SnO—P ₂ O ₅ glass of the present invention is preferably 350 ° C. or lower, particularly preferably 320 ° C. or lower. When the softening point of SnO—P ₂ O ₅ glass exceeds 350 ° C., when a phosphor powder having low heat resistance is used, the phosphor powder tends to deteriorate during firing, and the luminous efficiency of the phosphor composite member is high. It tends to decrease.

The SnO—P ₂ O ₅ glass of the present invention is preferably used in a powder form. It is preferable that the average particle diameter _{D 50} of the _SnO-P 2 _{O 5} based glass powder is 0.1 to 300, in particular 0.7～250Myuemu. When _SnO-P 2 _{O 5} based glass powder having an average particle diameter _{D 50} of greater than 300 [mu] m, tend to low-temperature sintering it becomes difficult. On the other hand, when the average particle diameter D ₅₀ is smaller than 0.1 [mu] m, and foaming during firing, the porosity of the phosphor composite member is increased, the emission efficiency tends to decrease.

The phosphor composite material of the present invention contains the SnO—P ₂ O ₅ glass powder and phosphor powder of the present invention. The phosphor powder is not particularly limited as long as it has an emission peak in the visible range. In the present invention, the visible range refers to a wavelength range of 380 to 780 nm. Such phosphor powders include oxides, nitrides, oxynitrides, chlorides, acid chlorides, sulfides, oxysulfides, halides, chalcogenides, aluminates, halophosphates, YAG compounds. And inorganic phosphor powders. Phosphor powders such as nitrides, oxynitrides, chlorides, acid chlorides, sulfides, oxysulfides, halides, chalcogenides, aluminates, and halophosphates are made from glass by the heat during firing. The reaction tends to cause an abnormal reaction such as foaming or discoloration, and the degree becomes more remarkable as the firing temperature is higher. Since the SnO—P ₂ O ₅ glass powder used in the present invention has a sufficiently low softening point, these phosphor powders can be used.

The phosphor composite material of the present invention may be composed only of SnO—P ₂ O ₅ glass powder and phosphor powder. An inorganic powder such as a softening point glass or a crystal powder such as alumina or silica may be contained for the purpose of improving the strength of the phosphor composite member or adjusting the hue, orientation, and scattering properties. The content of these inorganic powders is preferably 0.01 to 50% by mass and more preferably 0.05 to 20% by mass in the total amount in the phosphor composite material.

  The phosphor composite member of the present invention comprises a sintered body of the phosphor composite material of the present invention. The shape of the phosphor composite member is not particularly limited, but a polygon such as a rectangle or a circular plate shape is common. Other examples include a spherical shape, a hemispherical shape, a meniscus lens shape, a conical shape, and a film shape. These shapes may be produced by polishing or cutting, but can be easily produced by repress molding a sintered product of the phosphor composite material using a mold having a desired shape.

  The luminous efficiency of the phosphor composite member varies depending on the type and content of the phosphor powder dispersed in the glass, the thickness of the phosphor composite member, etc., so these parameters are adjusted as appropriate to optimize the luminous efficiency. do it.

  However, if the content of the phosphor powder is too large, it becomes difficult to sinter, the porosity becomes large, and it becomes difficult to efficiently irradiate the phosphor powder with the excitation light, or the mechanical strength of the phosphor composite member. This causes problems such as being easily lowered. On the other hand, when the content of the phosphor powder is too small, it becomes difficult to obtain sufficient emission intensity. Therefore, the content of the phosphor powder in the phosphor composite material is preferably 0.01 to 30% by mass, 0.05 to 20% by mass, and particularly preferably 0.08 to 15% by mass.

  Moreover, the thickness of the phosphor composite member is preferably 0.05 to 2 mm, 0.08 to 1 mm, 0.1 to 0.5 mm, and particularly preferably 0.1 to 0.2 mm. When the thickness of the phosphor composite member is less than 0.05 mm, the mechanical strength is inferior and manufacturing and processing are difficult. On the other hand, when the thickness of the phosphor composite member exceeds 2 mm, the excitation light is hardly transmitted and the light flux value tends to decrease.

  The phosphor composite material may be fired in the air. However, in order to obtain a denser sintered body or to suppress the reaction between the glass powder and the phosphor powder, the atmosphere is reduced or in a vacuum atmosphere, or nitrogen or argon. It is preferable to bake in an inert gas atmosphere.

  The firing temperature is preferably in the range of 250 to 350 ° C. When the firing temperature is less than 250 ° C., the porosity of the phosphor composite member, which is a sintered body, increases, and the light transmittance may decrease. On the other hand, when the firing temperature exceeds 350 ° C., the phosphor powder deteriorates, or the glass powder and the phosphor powder react with each other, so that the light emission efficiency tends to be lowered.

  The form of the phosphor composite material used for firing is not particularly limited, and may be, for example, a pressure-molded body having a desired shape, or a paste or a green sheet.

  A method for pressure-molding the phosphor composite material of the present invention to form a phosphor composite member is performed, for example, as follows. First, a resin binder is added to the phosphor composite material in an amount of 0 to 5% by mass, and pressure molding is performed with a mold to prepare a preform. Subsequently, the preform is subjected to binder removal at a temperature of 250 ° C. or lower, and then baked in the above temperature range to obtain a phosphor composite member.

  As the resin binder, it is preferable to use a resin whose decomposition end temperature is 250 ° C. or lower. Examples of such a resin binder include nitrocellulose, polyisobutyl acrylate, polyethyl carbonate, and the like. These can be used alone or in admixture of two or more.

  When the phosphor composite material of the present invention is used in the form of a paste, it is preferable to add and knead a predetermined amount of a binder or a solvent to the phosphor composite material to form a paste. The proportion of the phosphor composite material in the entire paste is generally 30 to 90% by mass.

  The binder is a component that enhances the strength of the film-like phosphor composite member and imparts flexibility when the paste is dried to obtain the film-like phosphor composite member. As for content of binder, about 0.1-20 mass% is common. Specific examples of the binder include polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose, nitrocellulose and the like. These can be used alone or in admixture of two or more.

  The solvent is used to paste the phosphor composite material. As for content of a solvent, about 10-50 mass% is common. Specific examples of the solvent include terpineol, isoamyl acetate, toluene, methyl ethyl ketone, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate and the like. These can be used alone or in admixture of two or more.

  Using the paste, a film-like phosphor composite member can be formed on a base material made of an inorganic material. Specifically, a base material of an inorganic material having a thermal expansion coefficient comparable to that of the phosphor composite member is prepared, and a paste is applied on the base material using a screen printing method, a batch coating method, or the like. A thick coating layer is formed. Thereafter, the film-like phosphor composite member can be formed by drying and baking at the above temperature.

  When the phosphor composite material of the present invention is used in the form of a green sheet, a binder, a plasticizer, a solvent, etc. are added to the phosphor composite material to form a green sheet. The proportion of the phosphor composite material in the green sheet is generally about 50 to 80% by mass.

  As the binder and the solvent, those similar to those used for the preparation of the paste can be used. The mixing ratio of the binder is generally about 0.1 to 30% by mass, and the mixing ratio of the solvent is generally about 1 to 40% by mass.

  The plasticizer is a component that controls the drying speed when forming a green sheet and imparts flexibility to the green sheet. As for content of a plasticizer, about 0-10 mass% is common. Examples of the plasticizer include dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, and dibutyl phthalate. These can be used alone or in admixture of two or more.

  As a general method for producing a green sheet, a binder, a plasticizer, and a solvent are added to the phosphor composite material of the present invention to form a slurry, and the slurry is polyethylene terephthalate (PET) by a doctor blade method. It is formed into a sheet on a film such as. Thereafter, by drying the obtained sheet-like molded product, organic substances such as a solvent can be removed to obtain a green sheet.

  The green sheet obtained as described above is placed on a base material of an inorganic material, thermocompression bonded, and then fired at the above temperature, whereby a phosphor composite member can be obtained. Note that only one green sheet may be used, or two or more green sheets may be laminated and used.

  By using the phosphor powder, the phosphor composite member of the present invention can convert excitation light having any wavelength of 300 to 500 nm into visible light having a wavelength of 380 to 780 nm different from the wavelength of the excitation light, for example. Can be converted to

  The semiconductor light-emitting element used as the excitation light source of the semiconductor light-emitting element device of the present invention is an LED or LD of light having a wavelength of 300 to 500 nm, for example, ultraviolet light having a wavelength of 330 to 380 nm or blue light having a wavelength of 430 to 480 nm. preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

Tables 1 and 2, Examples of the present invention (Sample Nos. 1 to 9) and Comparative Examples (Sample No. 10)
To 13) respectively.

  Each sample in the table was prepared as follows.

First, the raw materials were prepared so as to have the glass compositions shown in Tables 1 and 2, and mixed uniformly. Next, the prepared raw material was put into an alumina crucible and melted at 900 ° C. for 2 hours in an N ₂ atmosphere, and then the glass melt was formed into a film using a roller molding machine. Subsequently, after the obtained film-like glass was pulverized with a sieve, it was classified with a 325 mesh sieve to obtain SnO—P ₂ O ₅ glass powder (average particle diameter D ₅₀ = 15 μm).

The softening point of SnO—P ₂ O ₅ glass was measured using a macro differential thermal analyzer, and the value of the fourth inflection point was taken as the softening point.

The internal transmittance of SnO—P ₂ O ₅ glass was measured by measuring the internal transmittance at a wavelength of 365 nm using a sample obtained by molding a molten glass and optically polishing it so as to have a thickness of 1 mm.

Next, 1% by mass of SrBaSiO ₄ : Eu ²⁺ powder (phosphor powder having a heat resistance of about 500 ° C.) is added to and mixed with 99% by mass of the obtained SnO—P ₂ O ₅ glass powder. A phosphor composite material was obtained. Next, the phosphor composite material was pressure-molded using a mold to prepare a preform of 15 mm × 15 mm × 5 mm. The preform was fired at a firing temperature shown in Tables 1 and 2 under a reduced pressure of 100 Pa (1 atm = 1.014 × 10 ⁵ Pa), and then a sample of a phosphor composite member of 10 mm × 10 mm × 1 mm was obtained. It was. About the obtained sample, luminous efficiency and weather resistance were evaluated. The results are shown in Tables 1 and 2.

  The luminous efficiency of the phosphor composite member was calculated as follows. A sample was placed on a blue LED (wavelength 450 nm) or an ultraviolet LED (wavelength 365 nm), and an energy distribution spectrum of light emitted from the upper surface of the sample was measured in an integrating sphere. The total luminous flux was calculated by multiplying the obtained spectrum by the standard relative luminous sensitivity, and the luminous efficiency was calculated by dividing the total luminous flux by the power of the light source.

  The weather resistance was evaluated using a pressure cooker tester. That is, the sample was held for 24 hours under test conditions of 2 atm, humidity 95%, and temperature 121 ° C., and then the luminous efficiency and surface condition of the sample were evaluated. The luminous efficiency after the test was determined in the same manner as described above. In addition, the surface condition of the sample after the test was observed by visual and microscopic observation of the surface of each sample, and “O” indicates that no white turbidity was observed due to elution of microcracks and glass components, and microcracks and / or white turbidity. The thing where was recognized as "x".

As is apparent from Tables 1 and 2, sample No. 1 to 9 have a glass softening point of 350
The temperature was as low as below ℃, and low temperature sintering was possible. The luminous efficiency was as high as 20 lm / W or more for the blue LED and 5 lm / W for the ultraviolet LED. Further, after the weather resistance test, no reduction in luminous efficiency or surface turbidity was observed, and the weather resistance was excellent. The internal transmittance at a wavelength of 365 nm was as high as 80% or more.

In contrast, sample no. Nos. 10 to 12 contain a large amount of B ₂ O ₃ and ZnO in the glass, and therefore the internal transmittance at a wavelength of 365 nm was as low as 10% or less, and the luminous efficiency of ultraviolet LEDs was as low as 0.6 lm / W or less. Sample No. No. 13 has a low content of SnO, so the luminous efficiency of the blue LED after the weather resistance test was 6 lm / W, and the luminous efficiency of the ultraviolet LED was as low as 1.5 lm / W. Further, the surface of the sintered body after the test was clouded when visually observed, and microcracks and elution of glass components were observed when observed with a microscope, and it was confirmed that the weather resistance was low.

Claims (9)

A _SnO-P 2 _{O 5} based glass used for phosphor composite material, in _{mol%, SnO 72~90%, P 2} O 5 10~28%, Al 2 O 3 0~10%, SiO 2 0 _{~10%, Li 2 O 0~10%} , Na 2 O 0~10%, K 2 O 0~10%, Li 2 O + Na 2 O + K 2 O 0~10%, 0~10% MgO, CaO 0~10 %, SrO 0-10%, BaO 0-10%, MgO + CaO + SrO + BaO 0-10% , the molar ratio SnO / P ₂ O ₅ is 2.6-15, and B ₂ O ₃ and ZnO are substantially SnO—P ₂ O ₅ -based glass, characterized by not containing it. _2. The SnO—P ₂ O ₅ based glass according to claim 1, wherein the internal transmittance at a wavelength of 365 nm is 80% or more. _SnO-P 2 _{O 5} based glass according to claim 1 or 2 softening point, characterized in that at 350 ° C. or less. Claim 1~ _SnO-P 2 _{O 5} based glass powder comprising _SnO-P 2 _{O 5} based glass according to any one of 3. A phosphor composite material containing the SnO—P ₂ O ₅ glass powder and phosphor powder according to claim 4 .   The phosphor composite material according to claim 5, wherein the content of the phosphor powder is 0.01 to 30% by mass. Phosphor composite member formed of a sintered body of the phosphor composite material according to claim 5 or 6. 8. The phosphor composite member according to claim 7 , wherein excitation light having a wavelength of 300 to 500 nm is converted into visible light having a wavelength of 380 to 780 nm different from the wavelength of the excitation light. The semiconductor light-emitting element device using a phosphor composite member according to claim 7 or 8.