JP2010283045A - Phosphor dispersed member and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor dispersed member having a phosphor dispersed in a resin, the phosphor-dispersed member exhibiting weatherability, and to provide a method of manufacturing the same. <P>SOLUTION: The method of manufacturing the phosphor dispersed member includes: a phosphor-containing resin material forming step of forming the phosphor-dispersed member 1 by coating a phosphor-containing resin material, obtained by dispersing and curing the phosphor 3 in the resin 2 having transparency, with a glass film 4 of predetermined film thickness exhibiting weatherability, and dispersing and curing the phosphor in the resin; a sol forming step of forming glass sol for immersion containing a predetermined sol gel glass material; a glass film forming step of immersion of the phosphor-containing resin material in the glass sol for immersion and lifting it at a predetermined speed to stick a gelled glass film of predetermined film thickness; and a sintering step of sintering the phosphor-containing resin material coated with the gelled glass film to form the phosphor-dispersed member. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a phosphor dispersion member used for converting light of an LED light emitting element into light of another color and a method for manufacturing the same.

  DESCRIPTION OF RELATED ART Conventionally, the light emitting diode light source provided with the glass which disperse | distributed the fluorescent substance which converts the light-emitting element which light-emits with a predetermined color and the light emitted from a LED light-emitting element into the light of a desired color is known.

  For example, it is possible to create a light emitting diode light source that emits white light by mixing blue and yellow using an LED light emitting element that emits blue light and a phosphor that converts the blue light to yellow.

  At this time, in order to obtain white light emission with a uniform color tone, a phosphor dispersion member in which the phosphor is uniformly dispersed in a transparent resin (glass) is used, and light is emitted from the LED light emitting element in this glass body. It is important to uniformly mix blue and yellow emitted from the phosphor to uniformly emit white light, which is mixed color light, outside the glass body.

  In addition, glass powder of a predetermined particle size and phosphor powder are mixed and sintered to synthesize blue light emitted from a blue light source and yellow converted by the phosphor to obtain white light, and blue with strong energy There has already been proposed a luminescent color conversion member that improves reliability by using a stable glass that does not change color with respect to light and has a small temperature rise (see, for example, Patent Document 1).

  The luminescent color conversion member (phosphor dispersion member) can be prepared by mixing glass powder and phosphor powder, adding a resin binder, press-molding into a predetermined shape and firing. In addition, a phosphor dispersion member in which phosphors are mixed can be manufactured using a sol-gel method.

The sol-gel method is, for example, a method for producing glass using hydrolysis and polymerization reaction using a metal alkoxide, and glass synthesis is possible at a relatively low temperature. Various phosphor powders and rare earth ions can be mixed to obtain phosphor dispersion members of various colors. For example, ultrafine particle-dispersed glass in which semiconductor ultrafine particles having a luminous efficiency of 3% or more are dispersed in glass at a particle concentration of 10 ⁻⁹ mol / cm ³ or more has already been proposed (for example, see Patent Document 2).

  In addition, a light emitting device including a phosphor and hydrolyzing a metal alkoxide / resin complex to form a gel layer (for example, a metalloxane gel layer) having excellent weather resistance has been proposed (for example, (See Patent Document 3).

Japanese Patent No. 4158012 Japanese Patent Laid-Open No. 2002-21935 JP 2002-134790 A

  In general, since the resin allows moisture to pass therethrough, in the configuration using the phosphor dispersion member in which the phosphor is mixed with the resin, there is a problem that the moisture penetrates into the inside as time passes and the optical characteristics deteriorate. In addition, even in a configuration using a metal alkoxide that forms a gel layer with excellent weather resistance, a complex with a resin in which a phosphor is dispersed is hydrolytically polymerized, so that a resin exposed to the outside is interposed. Thus, there is a risk that water gradually permeates, and water resistance (weather resistance) is not sufficient.

  Furthermore, it is not preferable to limit the resin mixed with the phosphor to a resin having excellent weather resistance such as water resistance and light resistance. In order to obtain various light-emitting diode light sources, it is necessary depending on required specifications and applications. It is preferable that various resins can be used.

  Accordingly, an object of the present invention is to provide a phosphor dispersion member configured to exhibit weather resistance even if the phosphor dispersion member has a configuration in which a phosphor is mixed with a resin, and a method for manufacturing the same.

  In order to achieve the above object, the present invention provides a phosphor-dispersed member in which a predetermined phosphor is dispersed, and a phosphor-containing resin body obtained by dispersing and curing a phosphor in a light-transmitting resin. It is characterized by being covered with a glass film having a predetermined film thickness that exhibits the weather resistance.

  If it is said structure, since resin which disperse | distributed fluorescent substance is coat | covered with the glass film of the predetermined | prescribed film thickness which exhibits predetermined | prescribed weather resistance, predetermined | prescribed water resistance and light resistance are exhibited, and resin A phosphor-dispersed member having improved weather resistance without being deteriorated by external light or moisture can be obtained.

  According to the present invention, in the phosphor dispersion member having the above-described configuration, the glass film is formed by using a sol-gel method, and the formed film thickness exhibits predetermined weather resistance and does not cause cracking or peeling. It is characterized by its thickness. According to this configuration, a glass film that is thick enough to exhibit the predetermined weather resistance and thin enough not to cause cracking or peeling can be easily formed by the sol-gel method, and exhibits the expected weather resistance and quality. A stable phosphor dispersion member can be easily obtained.

  In the phosphor dispersion member having the above-described configuration, the present invention is characterized in that the glass film has a thickness of 10 to 300 nm. According to this configuration, it is possible to prevent both the deterioration of weather resistance that is likely to occur when the film thickness is thin, and the cracking and peeling of the glass film that is likely to occur when the film thickness is thick, and is excellent in predetermined weather resistance and further damaged. It is possible to obtain a phosphor dispersion member that is difficult to perform.

  According to the present invention, in the phosphor dispersion member configured as described above, the resin is a heat-resistant resin made of an epoxy resin, a silicon resin, or a hybrid resin thereof. According to this configuration, the phosphor dispersion member further has heat resistance in addition to predetermined weather resistance.

  The present invention also relates to a method for producing a phosphor dispersion member in which a predetermined phosphor is dispersed, the phosphor-containing resin body preparation step for dispersing and curing the phosphor in a resin, and an immersion including a predetermined sol-gel glass material A sol creating step of creating a glass sol for glass, a glass film creating step of dipping the phosphor-containing resin body in the dipping glass sol and pulling it up at a predetermined speed to attach a gel glass film of a predetermined film thickness, And sintering the phosphor-containing resin body coated with the glass film to prepare a phosphor dispersion member.

  With the above configuration, a phosphor-containing resin body in which an arbitrary phosphor is uniformly dispersed can be manufactured, and this resin body is formed by a sol-gel method using a predetermined sol-gel glass material with a glass film having a predetermined thickness. Since it coat | covers, it becomes a manufacturing method which can manufacture easily the fluorescent substance dispersion member excellent in predetermined weather resistance.

  Further, the present invention provides the method for producing a phosphor dispersion member having the above-described structure, wherein the film thickness is a predetermined thickness that exhibits weather resistance and does not cause cracking or peeling, and the sintering temperature is such as discoloration or deformation of the resin. The temperature is within a predetermined range that does not adversely affect the temperature. According to this configuration, since a glass film that exhibits a predetermined weather resistance function is formed without deteriorating the resin in the sintering step, a high-quality and long-life phosphor dispersion member can be manufactured.

  Moreover, the present invention is characterized in that, in the method for producing a phosphor dispersion member having the above-described configuration, the film thickness is 10 to 300 nm. According to this configuration, the phosphor dispersion member is excellent in weather resistance and strength by preventing both deterioration of weather resistance that tends to occur when the film thickness becomes thin and cracking and peeling of the glass film that tends to occur when the film thickness becomes thick. Can be manufactured.

Moreover, the present invention is characterized in that, in the method for producing a phosphor dispersion member having the above-described configuration, the sintering temperature in the sol-gel method is 130 to 250 ° C. According to this configuration, it is possible to prevent both the sintering failure of the glass film that is likely to occur at low temperatures and the discoloration and deformation of the resin that are likely to occur at high temperatures, and to satisfactorily manufacture a phosphor dispersion member having excellent weather resistance.

  According to the present invention, in the method for manufacturing a phosphor dispersion member having the above-described configuration, the resin is a heat-resistant resin made of an epoxy resin, a silicon resin, or a hybrid resin thereof. According to this configuration, it is possible to manufacture a phosphor dispersion member having heat resistance in addition to predetermined weather resistance.

  According to the present invention, a phosphor-dispersed member in which a phosphor-containing resin body obtained by dispersing and curing a phosphor in a light-transmitting resin is coated with a glass film having a predetermined film thickness that exhibits predetermined weather resistance. Therefore, a phosphor dispersion member that exhibits predetermined weather resistance such as water resistance and light resistance can be obtained. Further, according to the present invention, a phosphor-containing resin body creation step for dispersing and curing a phosphor in a resin, a sol creation step for creating a dipping glass sol containing a predetermined sol-gel glass material, and the phosphor-containing resin body A glass film creating step of dipping the glass sol for dipping and pulling it up at a predetermined speed to adhere a gel glass film of a predetermined film thickness, and sintering the phosphor-containing resin body coated with the gel glass film And a sintering process for producing a phosphor dispersion member, so that a phosphor-containing resin body in which an arbitrary phosphor is uniformly dispersed can be produced, and this resin body Is coated with a glass film having a predetermined thickness by using a predetermined sol-gel glass material by a sol-gel method, whereby a phosphor dispersion member having excellent predetermined weather resistance such as water resistance and light resistance can be manufactured.

It is a schematic explanatory drawing of the fluorescent substance dispersion member which concerns on this invention.

  Embodiments of the present invention will be described below with reference to the drawings.

  First, the phosphor dispersion member according to the present embodiment will be described with reference to FIG. The phosphor dispersion member 1 according to this embodiment is a glass film having a predetermined film thickness that exhibits predetermined weather resistance on a phosphor-containing resin body 10 in which a phosphor 3 is dispersed and cured in a translucent resin 2. 4 is formed. That is, the phosphor-containing resin body 10 is covered with the glass film 4 having weather resistance.

  Further, in the phosphor dispersion member 1, the primary light R1 emitted from the LED light emitting element 5 is converted into the secondary light R2 by the phosphor 3 added therein, and the primary light R1 and the secondary light R2 are mixed. The generated third light R3 is generated and emitted.

  Since the resin 2 in which the phosphor 3 is dispersed is covered with a glass film 4 having a predetermined film thickness that exhibits a predetermined weather resistance, the resin 2 exhibits a predetermined water resistance and a predetermined light resistance. Therefore, the phosphor dispersion member 1 having this configuration is a phosphor dispersion member that exhibits a predetermined weather resistance regardless of the characteristics of the resin 2 being used.

  Moreover, since it heats up by the heat_generation | fever of the LED light emitting element 5, or primary light R1 which this LED light emitting element 5 light-emits, it is preferable that the resin 2 is resin which has heat resistance.

  Here, an epoxy resin or silicon resin having heat resistance, or a hybrid resin thereof is used.

  The method of forming the glass film 4 on the phosphor-dispersed resin body 10 in which the phosphor 3 is dispersed and cured is immersed in a sol body having a predetermined viscosity and slowly pulled up to form a coating film having a predetermined thickness. Thereafter, a sol-gel method that can be manufactured by sintering at a relatively low temperature is preferable. Therefore, in this embodiment, it is set as the manufacturing method of the fluorescent substance dispersion member 1 which forms the glass film 4 using a sol-gel method.

  Further, in the normal sol-gel method, firing is performed until the bubbles generated in the sintering process are completely extinguished. If the bubbles have an appropriate size and an appropriate density, the LED light emitting element 5 emits light. The primary light R1 and the secondary light R2 emitted from the phosphor 3 are appropriately scattered to emit the third light with a uniform color, so that the firing temperature and firing time to leave appropriate bubbles are adjusted. May be.

  For example, when the temperature of the dried gel body is raised to a predetermined temperature and all the bubbles can be extinguished if this state is maintained for 3 hours, the baking time is set to 1 hour, so that the predetermined size is predetermined. Bubbles having a density of 5 mm can be left.

  Next, an example in which the phosphor dispersion member 1 is actually manufactured will be described. The phosphor dispersion member manufacturing method employed here includes a phosphor-containing resin body creation step of dispersing and curing a phosphor in a resin, a sol creation step of creating a dipping glass sol containing a predetermined sol-gel glass material, A glass film forming step in which a phosphor-containing resin body is immersed in the dipping glass sol and pulled up at a predetermined speed to adhere a gel-like glass film having a predetermined thickness; and a phosphor-containing resin coated with the gel-like glass film And a sintering step of producing a phosphor dispersion member by sintering the body.

First, as a sol preparation step, 25 grams of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), 37.6 grams of ethanol (C ₂ H ₆ O), 23.5 grams of water (H ₂ 0), 0.3 grams of hydrochloric acid (HCl) was weighed and mixed, and allowed to stand for 30 minutes to prepare an immersion glass sol having a viscosity increased to 0.03 poise by hydrolysis and polymerization reaction.

  Next, as a phosphor-containing resin body creation step, a silica hybrid epoxy resin (Composeran E103: manufactured by Arakawa Chemical Industries, Ltd.) is prepared by dispersing and curing 3 grams of a predetermined phosphor.

  The phosphor uses, for example, an oxide as a raw material of Y, Gd, Ce, Sm, Al, La, and Ga, or a compound that easily becomes an oxide at a high temperature, and mixes them sufficiently in a stoichiometric ratio. And get raw materials. Alternatively, a coprecipitated oxide obtained by firing a solution obtained by coprecipitation of a solution obtained by dissolving a rare earth element of Y, Gd, Ce, or Sm in an acid with a stoichiometric ratio with oxalic acid, and aluminum oxide or gallium oxide. Mix to obtain a mixed raw material. An appropriate amount of fluoride such as ammonium fluoride is mixed with this as a flux and packed in a crucible and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a fired product. Next, the fired product is ball milled in water, washed, separated, dried, and finally passed through a sieve to obtain a desired phosphor.

In particular, when obtaining a cerium-doped YAG phosphor that is excited by blue light and emits yellow light, appropriate amounts of Y ₂ O ₃ , Gd ₂ O ₃ , CeO ₂ , and Al ₂ O ₃ are prepared as raw materials. Then, a raw material mixture in which these are sufficiently mixed is filled in an aluminum crucible, and an appropriate amount of fluoride such as ammonium fluoride is mixed therein as a flux, and 1350 to 1450 in a reducing atmosphere while flowing hydrogen-containing nitrogen gas. Firing is performed for 2 to 5 hours in a temperature range of ° C to obtain a fired product. The obtained baked product is pulverized, washed, separated, and dried to obtain a desired phosphor. Further, the composition of the obtained phosphor was examined to confirm that it was a desired phosphor, and the emission wavelength in the excitation light of 465 nm was examined. As a result, it was confirmed that the peak wavelength was approximately 570 nm. That is, a phosphor that emits yellow light when irradiated with blue light can be obtained.

  Therefore, a phosphor-containing resin body was prepared using 3 grams of the cerium-added YAG phosphor. Then, as a glass film preparation step, the phosphor-containing resin body made of the silica hybrid epoxy resin is immersed in the above-described immersion sol and pulled up at a speed of 1.8 mm / s to adhere a glass film having a predetermined thickness (coating) ) To form a gel.

  Finally, as a sintering step, the phosphor-containing resin body coated with the gel glass film was sintered at 150 ° C. for 60 minutes. Thereby, a phosphor dispersion member coated with a glass film having a film thickness of 100 nm was produced.

  Next, the results of a weather resistance test at constant temperature and humidity using a phosphor dispersion member coated with a glass film having a thickness of 100 nm will be described.

  A weather resistance test was carried out using a small environmental tester (SH-641: manufactured by Espec Corp.) under conditions of a temperature of 60 ° C. and a humidity of 90% for 1000 hours, but no cloudiness was generated on the surface. However, those not covered with the glass film were cloudy in the weather resistance test under the same conditions.

  The film thickness of the glass film covering the phosphor-containing resin body is preferably about 10 to 300 nm. When the film thickness is thinner than 10 nm, the moisture resistance and weather resistance are insufficient, and the surface may be clouded in the weather resistance test. Further, when the film thickness exceeds 300 nm, the glass film may be cracked or peeled off. The film thickness can be adjusted by the viscosity of the dipping glass sol and the speed of dipping and lifting, and can also be adjusted by repeatedly dipping and then dipping.

  The temperature at which the glass film immersed and coated is sintered is preferably about 130 to 250 ° C. At a sintering temperature lower than 130 ° C., the glass film cannot be completely sintered. Further, at a sintering temperature higher than 250 ° C., discoloration or deformation may occur depending on the resin.

  As described above, a glass film exhibiting weather resistance is formed on a resin body containing a phosphor by the sol-gel method, the film thickness of the glass film is set to a predetermined thickness, and the sintering temperature adversely affects the resin. By setting the temperature within a predetermined range, a high-quality phosphor dispersion member having excellent weather resistance can be obtained regardless of the characteristics of the resin.

  In this example, silica glass prepared from tetramethoxysilane is used, but the present invention is also effective for glasses other than the silica glass used here, and various glasses can be used. it can. In that case, it is natural to adjust to an appropriate sintering temperature according to the glass to be used. Moreover, the kind of fluorescent substance is not limited to an Example, Various fluorescent substance can be used.

  As described above, according to the phosphor dispersion member according to the present invention, the phosphor-containing resin body obtained by dispersing and curing the phosphor in the translucent resin has a predetermined film thickness that exhibits a predetermined weather resistance. Since the phosphor dispersion member is formed with a glass film, it becomes a phosphor dispersion member coated with a glass film having a predetermined thickness, and exhibits a predetermined weather resistance such as water resistance and light resistance, and has excellent strength. A body dispersion member can be obtained.

  Further, by using a resin having heat resistance as the resin, a phosphor dispersion member having heat resistance in addition to predetermined weather resistance can be obtained.

  Furthermore, according to the method for manufacturing a phosphor dispersion member according to the present invention, a phosphor dispersion member in which a phosphor-containing resin body obtained by dispersing and curing a phosphor in a resin is coated with a glass film using a sol-gel method. Since it is a manufacturing method, while being able to manufacture the fluorescent substance containing resin body which disperse | distributed arbitrary fluorescent substance uniformly, the fluorescent substance dispersion | distribution member excellent in the weather resistance and intensity | strength can be manufactured.

  In addition, the glass film has a predetermined thickness (for example, 10 to 300 nm) that exhibits predetermined weather resistance and does not cause cracking or peeling, and the sintering temperature is a temperature within a predetermined range that does not adversely affect the resin ( For example, by setting the temperature to 130 to 250 ° C., it is possible to manufacture a phosphor dispersion member that is excellent in predetermined weather resistance and that can sustain stable light emission without deteriorating the resin.

  The phosphor dispersion member and the manufacturing method thereof according to the present invention are suitable for a light emitting diode light source that emits third light having a desired color by mixing primary light emitted from an LED light emitting element and secondary light emitted from a phosphor. Applicable phosphor dispersion member and manufacturing method thereof.

DESCRIPTION OF SYMBOLS 1 Phosphor dispersion | distribution member 2 Resin 3 Phosphor 4 Glass film 5 LED light emitting element 10 Phosphor containing resin body R1 Primary light R2 Secondary light R3 Third light

Claims (9)

A phosphor dispersion member in which a predetermined phosphor is dispersed,
A phosphor-dispersed member, wherein a phosphor-containing resin body obtained by dispersing and curing a phosphor in a light-transmitting resin is coated with a glass film having a predetermined film thickness that exhibits predetermined weather resistance.   The glass film is formed using a sol-gel method, and the formed film thickness is set to a predetermined thickness that exhibits weather resistance and does not cause cracking or peeling. Phosphor dispersion member.   The phosphor dispersion member according to claim 2, wherein the glass film has a thickness of 10 to 300 nm.   The phosphor dispersion member according to any one of claims 1 to 3, wherein the resin is a heat-resistant resin made of an epoxy resin, a silicon resin, or a hybrid resin thereof. A method of manufacturing a phosphor dispersion member in which a predetermined phosphor is dispersed,
A phosphor-containing resin body creation step for dispersing and curing the phosphor in a resin, a sol creation step for creating a dipping glass sol containing a predetermined sol-gel glass material, and dipping the phosphor-containing resin body in the dipping glass sol A glass film forming step of attaching a gel-like glass film having a predetermined film thickness by pulling up at a predetermined speed and a phosphor-dispersing member are prepared by sintering a phosphor-containing resin body coated with the gel-like glass film And a sintering step. A method for manufacturing a phosphor dispersion member.   The film thickness is a predetermined thickness that exhibits weather resistance and does not cause cracking or peeling, and the sintering temperature is a temperature in a predetermined range that does not adversely affect the resin such as discoloration or deformation. Item 6. A method for producing a phosphor dispersion member according to Item 5.   The method for producing a phosphor dispersion member according to claim 6, wherein the film thickness is 10 to 300 nm.   The method for producing a phosphor dispersion member according to claim 6 or 7, wherein the sintering temperature is 130 to 250 ° C.   The method for producing a phosphor dispersion member according to claim 5, wherein the resin is a heat-resistant resin made of an epoxy resin, a silicon resin, or a hybrid resin thereof.

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