JP6825734B2 - Fluorescent Thermoplastic Resin Filament - Google Patents

Description

The present invention relates to a phosphor-containing thermoplastic resin filament suitable for producing a wavelength conversion member containing a phosphor that converts the wavelength of light emitted from an LED to emit light of a different wavelength.

A general white LED is composed of a blue LED element and a phosphor that converts the light emitted from the element into a visible light component having a longer wavelength. In such a white LED, light having a wavelength longer than blue light generated by wavelength conversion of blue light, which is excitation light incident on the phosphor, and blue light not absorbed by the phosphor are combined. As a result, white light is generated. In a white LED, characteristics such as chromaticity, color temperature, and luminous efficiency of the emitted light largely depend on the type and density of the phosphor, and the characteristics of the emitted light are usually adjusted by the type and density of the phosphor. Will be done.

Special Table 2015-520494 Special Table 2015-515734 Special Table 2013-521614

In such an LED light emitting device, light emitting characteristics such as chromaticity, color temperature, and luminous efficiency of the emitted light also change depending on the shape and thickness of the wavelength conversion member. Since the phosphor used in such a wavelength conversion member is relatively expensive, it is required to reduce the amount used. However, the light emitting characteristics are improved depending on the shape and thickness of the wavelength conversion member. When trying to reduce the amount of phosphor used, in an LED package in which the phosphor is dispersed in a sealing material such as a resin that seals the LED element, the shape and thickness of the sealing material forming the wavelength conversion member are increased. There is a limit because it cannot be changed.

On the other hand, if the LED element or the remote phosphor type LED light emitting device using the wavelength conversion member formed as a member different from the LED package in which the LED element is sealed with the sealing material, the wavelength conversion member. It is possible to obtain higher emission characteristics with a smaller amount of phosphor by changing the shape and thickness of the wavelength conversion member and the arrangement of the wavelength conversion member with respect to the LED element or the LED element package. High degree of freedom of change.

However, in order to manufacture wavelength conversion members having various shapes and examine their optical characteristics, it is necessary to prepare a large number of molds in the manufacturing method using ordinary molds, which increases the cost. Further, the method for manufacturing the wavelength conversion member cannot obtain sufficient optical characteristics required for the wavelength conversion member unless the wavelength conversion member in which the phosphor is uniformly dispersed can be manufactured.

The present invention has been made in view of the above circumstances, and a wavelength conversion member capable of imparting higher emission characteristics, particularly higher luminous efficiency, with a smaller amount of phosphor, without using a mold. To provide a phosphor-containing thermoplastic resin filament that can be produced in a state where the dispersibility of the phosphor is high, that is, in a state where the phosphor is uniformly dispersed in the entire wavelength conversion member and the variation in the fluorescence concentration is suppressed. The purpose.

In order to solve the above problems, the present inventors convert the wavelength of the light emitted from the LED as a wavelength conversion member used in the remote phosphor type LED light emitting device, and generate light having a wavelength different from this wavelength. In studying the shape and thickness of the wavelength conversion member containing the luminescent phosphor, the arrangement of the wavelength conversion member with respect to the LED, etc., we repeated diligent studies on a method that can efficiently manufacture the wavelength conversion member without using a mold. As a result, a wavelength conversion member containing a phosphor that converts the wavelength of the light emitted from the LED and emits light having a wavelength different from the wavelength is contained in the thermoplastic resin in an amount of 30% by mass. It has been found that a wavelength conversion member can be manufactured with high dispersibility of the phosphor by manufacturing with a 3D printer by a melt lamination method using a phosphor-containing thermoplastic resin filament dispersed at the following concentration. ..

Then, the present inventors mixed the phosphor-containing thermoplastic resin filament with the particulate phosphor to obtain the phosphor-containing thermoplastic resin, and then the present inventors obtained the phosphor-containing thermoplastic resin.
(1) The phosphor-containing thermoplastic resin is extruded with the ratio (L / D) of the effective screw length L to the molten screw diameter D set to 30 or more and 60 or less, or (2) the phosphor-containing thermoplastic resin is extruded. Extruded from an orifice hole in a state of being melted at a temperature of 180 ° C. or higher and lower than 240 ° C., and while stretching at a linear velocity of 3 to 30 times the linear velocity of extrusion of the molten phosphor-containing thermoplastic resin. By taking-back extrusion molding, the dispersibility of the phosphor in the phosphor-containing thermoplastic resin filament is increased, and by extension, the obtained phosphor-containing thermoplastic resin filament is used and manufactured by a 3D printer by the melt lamination method. The present invention has been made by finding that the wavelength conversion member is also a wavelength conversion member having high dispersibility of the phosphor.

Therefore, the present invention provides the following phosphor-containing thermoplastic resin filaments.
Claim 1:
A raw material filament for producing a wavelength conversion member containing a phosphor that converts the wavelength of light emitted from an LED and emits light having a wavelength different from the wavelength by a 3D printer by a melt lamination method. The above-mentioned phosphor in the form is dispersed in the thermoplastic resin at a concentration of 30% by mass or less.
The phosphor is A ₂ (M _1-x , Mn _x ) F ₆ (in the formula, A is selected from Li, Na, K, Rb and Cs, and one or 2 containing at least Na and / or K. More than one kind of alkali metal, M is one kind or two or more kinds of tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn, and x is a positive number in the range of 0.001 to 0.3. Includes a manganese-activated compound fluoride phosphor represented by)
A phosphor-containing thermoplastic resin filament, wherein the thermoplastic resin is selected from an olefin resin, a cyclic polyolefin resin, an acrylic resin, a styrene resin, and an acrylicimide resin.
Claim 2:
The manganese-activated compound fluoride phosphor is manganese represented by K ₂ (Si _1-x , Mn _x ) F ₆ (x is a positive number in the range of 0.001 to 0.3 in the formula). The phosphor-containing thermoplastic resin filament according to claim 1, which is an activated potassium fluoride phosphor.
Claim 3:
The phosphor-containing thermoplastic resin filament according to claim 1 or 2, wherein the thermoplastic resin is selected from an acrylic resin, polystyrene, a styrene copolymer, polyethylene, polypropylene, and an ethylene-propylene copolymer.

According to the present invention, the wavelength conversion member used in the remote phosphor type LED light emitting device can be efficiently manufactured without using a mold, and the dispersibility of the phosphor of the obtained wavelength conversion member is also good. Is.

It is a figure which shows an example of the wavelength conversion member (No. 1) of this invention produced in Example 1, (A) is a perspective view, (B) is a sectional view. It is a figure which shows an example of the wavelength conversion member (No. 2) of this invention produced in Example 1, (A) is a perspective view, (B) is a sectional view. It is a figure which shows an example of the wavelength conversion member (No. 3) of this invention produced in Example 1, (A) is a perspective view, (B) is a sectional view. It is an exploded perspective view which shows an example of the remote phosphor type LED light emitting device of this invention manufactured using the wavelength conversion member (No. 1) in Example 1. FIG.

Hereinafter, the present invention will be described in more detail.
The wavelength conversion member of the present invention contains a phosphor that converts the wavelength of light emitted from an LED and emits light having a wavelength different from this wavelength. In the present invention, the LED may be intended for the case of only the LED element, that is, only the LED semiconductor chip, but usually, the LED element (LED semiconductor chip) is installed on the base material or the substrate, and the lead wire, An LED package sealed with a sealing material such as resin is used together with a wiring member such as a terminal. As the LED package, usually, a sealing material containing no phosphor that converts the wavelength of the light emitted from the LED element and emits light having a wavelength different from this wavelength is used, but the sealing material is used. A material containing a phosphor in the material may be used.

As the LED, visible light such as a red LED whose emission light is red light, a green LED whose emission light is green, a blue LED whose emission light is blue, a yellow LED whose emission light is yellow, and a white LED whose emission light is white is emitted. A diode or an ultraviolet LED that emits ultraviolet light can be used, but a blue LED, particularly a blue LED that emits blue light having a peak wavelength of 440 to 470 nm is preferable.

The type of phosphor can be appropriately selected according to the wavelength of the excitation light emitted by the LED and the color of the light emitted from the LED light emitting device. For example, when a blue light emitting diode is used, a phosphor used for forming an LED light emitting device that emits white light by using the blue light emitting diode is suitable. Examples of such a phosphor include a phosphor that is excited by blue light, which is excitation light, and emits light such as yellow, green, orange, and red. Specifically, Y ₃ Al ₅ O ₁₂ : Ce, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ , (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce , (Lu, Y) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, (Sr, Ca, Ba) ₂ SiO ₄ : Eu, β-SiAlON: Eu and other yellow phosphors Alternatively, a green phosphor or the like can be mentioned.

When a low color temperature of 5000 K or less is required, a red phosphor can be used together with a yellow phosphor or a green phosphor. Examples of the red phosphor include CaAlSiN: Eu ²⁺ and Sr-CaAlSiN ₃ : Eu ³⁺ . In particular, when a white LED light emitting device having excellent color rendering properties is used, a manganese-activated compound fluoride phosphor is used. Is preferably used.

The manganese-activated difluoride phosphor has a structure in which some of the constituent elements of the difluoride are replaced with manganese (Mn), which is an activating element. For example, A ₂ MF ₆ (in the formula, A is Li). , Na, K, Rb and Cs, and one or more alkali metals containing at least Na and / or K, M is one or one selected from Si, Ti, Zr, Hf, Ge and Sn. (It is two or more kinds of tetravalent elements)), and some of the constituent elements of the difluoride have a structure in which manganese (Mn), which is an activating element, is substituted. As such, A ₂ (M _1-x , Mn _x ) F ₆ (In the equation, A and M are the same as above, and x is a positive number in the range of 0.001 to 0.3. A manganese-activated difluoride phosphor represented by) is suitable. This manganese-activated difluoride phosphor has a structure in which a part of the site of the tetravalent element represented by M is substituted with manganese, that is, a structure in which the site is substituted as tetravalent manganese (Mn ⁴⁺ ). ^Therefore , it may be expressed as A ₂ MF ₆ : Mn ⁴⁺ . In the present invention, among such manganese-activated difluoride phosphors, K ₂ (Si _1-x , Mn _x ) F ₆ in which A is K and M is Si (x is the same as above in the formula). A manganese-activated potassium fluoride phosphor represented by (.) (Generally referred to as a KSF phosphor) is particularly preferable from the viewpoint of the excitation wavelength range and weather resistance.

The KSF phosphor is excited by blue light to emit fluorescence having an emission peak or a maximum emission peak in the wavelength range of 600 to 660 nm. On the other hand, the light absorption characteristics of the KSF phosphor are different from those of red phosphors such as CaAlSiN: Eu ²⁺ and Sr-CaAlSiN ₃ : Eu ³⁺ described above, and the absorption rate sharply decreases when the wavelength is longer than 460 nm. .. Therefore, when a blue-green LED that emits blue-green light having a peak wavelength of around 460 nm is used as an excitation source of the auxiliary excitation light, the absorption / attenuation of the auxiliary excitation light can be reduced, which is particularly effective. ..

It is usually preferable to use a phosphor in the form of particles (for example, an average particle size D50 (volume basis) of 1 μm or more, particularly 2 μm or more, 30 μm or less, particularly 18 μm or less). The wavelength conversion member can be composed of only a phosphor (for example, it can be obtained by molding and sintering a particulate phosphor), but the particulate phosphor can be obtained. Inorganic or organic transparent or translucent materials, specifically, those dispersed in an inorganic material such as glass or an organic polymer material such as resin, rubber or elastomer are preferable. It is preferable that the phosphor is uniformly dispersed in the transparent material or the translucent material that forms the base material of the wavelength conversion member.

As the transparent material or the translucent material, it is preferable to use a resin, particularly a hard resin, among the organic polymer materials. Examples of the resin include thermosetting resins such as silicone resin and epoxy resin, ultraviolet curable resins, olefin resins such as polyethylene and polypropylene, cyclic polyolefin resins, acrylic resins, polystyrenes, AS resins, and styrene resins such as ABS resins. Examples thereof include thermoplastic resins such as acrylicimide resins, polycarbonate resins, and ester-based resins such as PET resins, and thermoplastic resins, particularly hard thermoplastic resins, are preferable.

In particular, when a manganese-activated difluoride phosphor is used as the phosphor, a resin other than the ester-based resin is preferable among the thermoplastic resins exemplified above. When a manganese-activated compound fluoride phosphor and an ester-based resin are used, the resin may be dissolved or embrittled due to a hydrolysis reaction. On the other hand, in olefin resins such as polyethylene and polypropylene, cyclic polyolefin resins, acrylic resins, polystyrenes, AS resins, ABS resins and other styrene resins and acrylic imide resins, the manganese-activated difluoride phosphors , Especially effective kneading and high dispersibility can be obtained without causing the above problems.

The concentration of the phosphor in the wavelength conversion member includes the type of phosphor used, the particle size, the type of transparent material or translucent material, the color temperature and thickness of light emitted when the LED light emitting device is used, the LED element and the fluorescent member. The total amount of the phosphor is 2% by mass or more, particularly 3% by mass or more, and 30% by mass or less, particularly 20% by mass or less, particularly 15% by mass or less, although it depends on the arrangement with and other conditions. preferable.

For example, when Y ₃ Al ₅ O ₁₂ : Ce phosphor is dispersed in a resin to form a wavelength conversion member having a thickness of 0.5 to 5 mm and white light having a color temperature of 6000 K is to be obtained, Y ₃ Al ₅ O ₁₂ : The concentration of the Ce phosphor is approximately 2 to 8% by mass. More specifically, when a wavelength conversion member having a thickness of 2 mm is used and white light having a color temperature of 6000 K is to be obtained, the concentration of the Y ₃ Al ₅ O ₁₂ : Ce phosphor is approximately 4 to 6% by mass.

Further, Y ₃ Al ₅ O _12: with Ce phosphor, the case of using a manganese-activated double fluoride phosphors, the concentration of manganese activated double fluoride phosphor, Y ₃ Al ₅ O _12: the Ce phosphor, generally 2 ~ 4 times. Specifically, for example, a Y ₃ Al ₅ O ₁₂ : Ce phosphor and a manganese-activated difluoride phosphor are dispersed in a resin to form a wavelength conversion member having a thickness of 0.5 to 5 mm and having a color temperature of 3500 K. When white light is to be obtained, the concentration of the Y ₃ Al ₅ O ₁₂ : Ce phosphor is approximately 2 to 5% by mass, and the concentration of the manganese-activated difluoride phosphor is approximately 6 to 13% by mass. More specifically, when a wavelength conversion member having a thickness of 2 mm is used and white light having a color temperature of 3500 K is to be obtained, the concentration of Y ₃ Al ₅ O ₁₂ : Ce phosphor is approximately 2 to 5% by mass and manganese activation. The concentration of the difluoride phosphor is approximately 5 to 10% by mass.

Since the wavelength conversion member used in the remote phosphor type LED light emitting device is manufactured as a member separate from the LED, the shape, dimensions, arrangement with respect to the LED, etc. are determined according to the optical characteristics required for the LED light emitting device. It is possible to adjust independently on the conversion member side. The wavelength conversion member of the present invention preferably has a thickness of 0.6 mm or more, particularly 1 mm or more, and 4 mm or less, particularly 2 mm or less. This is because if the thickness of the wavelength conversion member is thinner than 0.6 mm, the influence of the dimensional error becomes large, and the influence of the variation in the dispersion of the phosphor is large. Therefore, the optical characteristics of the entire wavelength conversion member are made uniform. This is because if the thickness of the wavelength conversion member exceeds 4 mm, the amount of the phosphor increases and the utilization efficiency of the phosphor may decrease. The thickness usually targets the effective thickness, that is, the thickness at the position where the excitation light from the LED is directly incident.

The Fused Deposition Modeling method (FDM method), which is a typical method of the 3D printing molding method, is applied to the manufacture of the wavelength conversion member. The FDM method is a molding method in which a thermoplastic resin filament as a raw material is fed to a melting nozzle that can move in three axes to extrude and laminate the hot-melted thermoplastic resin to obtain a resin molded product having a desired shape. Is. The FDM method is a molding method using a mold, which is advantageous for manufacturing a wavelength conversion member having a shape in which the manufacturing conditions are complicated due to restrictions on mold release and the like, and it is not necessary to prepare a mold. Suitable for small-lot, high-mix production of wavelength conversion members. The FDM method, which obtains a resin molded product having a desired shape by laminating and curing the heat-melted resin raw material while discharging it from a nozzle, has an inner surface as compared with an injection molding method using a general mold. Is advantageous for forming a wavelength conversion member having a three-dimensional shape, particularly a deeper three-dimensional shape inner surface.

In the FDM method, a fine linear filament in which predetermined phosphor particles are dispersed in a thermoplastic resin (hereinafter, referred to as a phosphor-containing thermoplastic resin filament) is used. The phosphor-containing thermoplastic resin filament can be produced, for example, by extrusion molding. The phosphor is kneaded into the thermoplastic resin at a predetermined concentration in the process of melt extrusion molding, but in order to uniformly disperse the phosphor in the thermoplastic resin filament containing the phosphor, a biaxial screw type extrusion is performed. The use of a molding machine is preferred. Further, in order to prevent iron and the like from being mixed into the phosphor-containing thermoplastic resin filament due to wear by dispersed phosphor particles, extrusion molding using an inner wall or a screw formed of a hard material such as cemented carbide or a non-ferrous material. It is also effective to use a machine.

When a phosphor-containing thermoplastic resin filament is produced by extrusion molding, first, a particulate phosphor is mixed with the thermoplastic resin to obtain a phosphor-containing thermoplastic resin. After that, a phosphor-containing thermoplastic resin filament is manufactured using an extrusion molding machine. At the time of extrusion molding, the ratio (L / D) of the effective screw length L to the molten screw diameter D of the phosphor-containing thermoplastic resin is 30. It is preferable that the size is 60 or more and extrusion molding is performed.

As a method of melting the thermoplastic resin while uniformly dispersing the phosphor particles in the thermoplastic resin without uneven distribution, kneading and melting by an extrusion molding machine is effective, but the dispersibility of the phosphor particles is the melt screw diameter. It is affected by the ratio of effective screw length L to D (L / D). The higher the L / D, the better the dispersibility of the phosphor particles in the thermoplastic resin, but if the L / D is too high, the productivity decreases. When a thermoplastic resin in which a phosphor is dispersed is extruded, good dispersibility can be obtained by setting the L / D to 30 or more, particularly 40 or more. On the other hand, in the case of phosphor particles, if the L / D is too high, the phosphor particles strongly rub against the inner wall and the screw of the extruder, causing the device to wear, and the phosphor-containing thermoplastic resin filament becomes the inner wall and the screw. 60 or less, particularly preferably 50 or less, because the components of the material of the above may be mixed.

Further, during extrusion molding, it is preferable to extrude the phosphor-containing thermoplastic resin from the orifice hole in a state of being melted at a temperature of 180 ° C. or higher, particularly 200 ° C. or higher, and lower than 240 ° C., particularly 235 ° C. or lower. By setting the temperature of the photobody-containing thermoplastic resin in the above range, the diameter of the phosphor-containing thermoplastic resin filament, which is a wire rod, becomes stable. This temperature is usually the device operating temperature, that is, a temperature about 10 to 40 ° C. lower than the average temperature of the melting region of the barrel.

Further, during extrusion molding, the linear velocity of extrusion of the molten phosphor-containing thermoplastic resin (the linear velocity of ejection of the phosphor-containing thermoplastic resin filament), that is, three times or more the linear velocity at the orifice portion. In particular, it is also preferable to take over while stretching at a linear velocity of 5 times or more, 30 times or less, particularly 10 times or less. By setting the ratio of the linear velocity of the extrusion of the phosphor-containing thermoplastic resin to the linear velocity of the take-up of the phosphor-containing thermoplastic resin filament within the above range, the dispersion of the phosphor is partially incomplete immediately after ejection. Even if there is a uniform portion, the portion is expanded by sufficient stretching and averaged to homogenize the dispersion of the phosphor, and the concentration of the phosphor in the phosphor-containing thermoplastic resin filament varies. It can be suppressed. If the ratio between the linear velocity of extrusion of the phosphor-containing thermoplastic resin and the linear velocity of take-up of the phosphor-containing thermoplastic resin filament is too high, the relatively thin portion is subjected to rapid stretching and becomes thinner and thicker. Non-uniformity of the resin and breakage of the filament may occur.

When the wavelength conversion member is manufactured by the FDM method, the above-mentioned thermoplastic resin can be used, but in addition to the good dispersibility of the phosphor in the thermoplastic resin at the time of molding, it is rapidly melted by a predetermined heating. It is necessary to consider rapid curing after lamination, welding characteristics between layers during lamination, adhesion to the reference pedestal, durability against compressive stress accumulated inside the wavelength conversion member due to melting and curing, and the like. From this point of view, in the production of wavelength conversion members by the FDM method, styrene copolymers such as acrylic resin, polystyrene, AS resin and ABS resin, polyethylene such as high-density polyethylene, polypropylene, ethylene-propylene copolymer and the like The thermoplastic resin of is particularly suitable.

The particle size of the phosphor dispersed in the phosphor-containing thermoplastic resin filament is set according to the type of the phosphor used, the particle shape thereof, and the resin material as the base material, and is usually set to an average particle size D50 (volume basis). Is 1 μm or more, particularly 2 μm or more, and 30 μm or less, particularly 18 μm or less is preferably used. The concentration of the phosphor dispersed in the phosphor-containing thermoplastic resin filament is set according to the type of the phosphor to be used and the emission chromaticity targeted by the wavelength conversion member after molding, and the total amount of the phosphor is 2. It is preferably 3% by mass or more, particularly 3% by mass or more, and 30% by mass or less, particularly 20% by mass or less, particularly 15% by mass or less. If the phosphor concentration is too high, the melting nozzle is more likely to be clogged, and the stiffness at the time of melting is lost, which may cause sagging during molding. The diameter of the phosphor-containing thermoplastic resin filament is usually φ1.75 mm or φ3 mm in a 3D printer to which the FDM method currently used is applied.

If the phosphor-containing thermoplastic resin filament contains a large amount of water during molding of the wavelength conversion member, it melts and generates water vapor in the melting head when laminating, which becomes fine bubbles during laminating. The haze of the wavelength conversion member may be excessively increased, which may cause fluctuations in optical characteristics, and the density may decrease. In particular, when a phosphor-containing thermoplastic resin filament is produced by extrusion molding, the phosphor-containing thermoplastic resin filament comes into contact with water via a cooling water tank, so that the inside of the phosphor-containing thermoplastic resin filament is formed. Water may be taken in. Therefore, it is preferable to use the phosphor-containing thermoplastic resin filament after reducing the water content thereof. For example, the phosphor-containing thermoplastic resin filament is heated at, for example, 70 ° C. or higher, particularly 80 ° C. or higher, preferably 100 ° C. or lower, in a gas atmosphere such as an atmospheric atmosphere, a vacuum atmosphere, or the like, for example, for 6 hours or longer. As a result, the amount of water can be reduced. The upper limit of the heating time is usually 24 hours or less. A heating furnace such as a vacuum furnace can be used for this heating.

In the FDM method, a wavelength conversion member may be formed by an FDM device (FDM3D printer) using a phosphor-containing thermoplastic resin filament. The inner diameter of the melting nozzle is preferably φ0.2 mm or more and φ0.6 mm or less. This is because if the inner diameter of the nozzle is less than φ0.2 mm, the molten nozzle is likely to be blocked by the phosphor, while if the inner diameter exceeds φ0.6 mm, the dimensional accuracy of the wavelength conversion member is lowered, so the size is adjusted after molding. This is because it may be necessary to process. The temperature of the melting nozzle during molding is preferably 190 ° C. or higher, particularly 220 ° C. or higher, and 280 ° C. or lower, particularly 260 ° C. or lower. This is because if the temperature of the melting nozzle is less than the above range, the melting of the thermoplastic resin may be insufficient, while if it exceeds the above range, the stiffness at the time of melting is lost and the curing after laminating is delayed. This is because there is a risk of sagging during stacking.

The LED light emitting device of the present invention includes an LED, a substrate on which the LED is installed, and a wavelength conversion member, and the wavelength conversion member is arranged so as to be separated from the LED via a gas layer or a vacuum layer. It is a phosphor type LED light emitting device. In the LED light emitting device of the present invention, by using the wavelength conversion member of the present invention, the inner surface of the wavelength conversion member is a part of the front side of the irradiation direction of the light emitted from the LED and a part of the side side of the irradiation direction. Surrounding the whole, the wavelength conversion member, together with the substrate, is configured to include the LED and form a space through which the light emitted from the LED passes. As the LED light emitting device, an LED light emitting device that emits white light is particularly preferable, but an LED light emitting device that emits visible light such as red light, green light, blue light, and yellow light may also be used.

Hereinafter, the present invention will be specifically described with reference to Experimental Examples and Examples, but the present invention is not limited to the following Examples.

[Experimental Example 1]
YAG: Ce and KSF are kneaded into an acrylic resin (Delpet 60N (manufactured by Asahi Kasei Co., Ltd.)) as phosphors, and the YAG: Ce phosphor concentration is 2.8% by mass and the KSF phosphor concentration is 8. Pellets of 4% by mass phosphor-containing thermoplastic resin were obtained. Next, the pellets were put into a twin-screw extruder TEM-18 (manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at an average barrel heating temperature of 240 ° C., and then lowered to 220 ° C. to φ4. Extrude from a 5 mm orifice hole at a linear speed of 1.1 m / min, immerse the discharged thermoplastic resin in cold water, and then use a constant speed take-up machine IMC-19A5R (manufactured by Imoto Seisakusho Co., Ltd.) to increase the draw ratio. It was taken up at a linear velocity of 6.5 m / min, which is 6 times higher, and linearized to an average of φ1.75 mm, and further heated in a vacuum furnace at 70 ° C. for 12 hours to obtain a phosphor-containing thermoplastic resin filament. .. The ratio (L / D) of the effective screw length L to the molten screw diameter D in this extrusion molding was 42.

The obtained phosphor-containing thermoplastic resin filament had a uniform diameter of each part, and the number of minute deformed parts (fish eyes) due to poor melting was about 1 in 150 m.

[Experimental Example 2]
YAG: Ce was kneaded into polypropylene (Noblen Z144 (manufactured by Asahi Kasei Corporation)) as a phosphor to obtain pellets of a phosphor-containing thermoplastic resin having a YAG: Ce phosphor concentration of 6% by mass. Next, the pellets were put into a twin-screw extruder TEM-18 (manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at an average barrel heating temperature of 220 ° C., and then lowered to 180 ° C. to φ4. Extrude from a 5 mm orifice hole at a linear speed of 0.6 m / min, immerse the discharged thermoplastic resin in cold water, and then use a constant speed take-up machine IMC-19A5R (manufactured by Imoto Seisakusho Co., Ltd.) to increase the draw ratio. It was taken up at a linear velocity of 12 m / min, which is 20 times higher, and linearized with an average of φ1.75 mm, and further heated in a vacuum furnace at 80 ° C. for 8 hours to obtain a phosphor-containing thermoplastic resin filament. The ratio (L / D) of the effective screw length L to the molten screw diameter D in this extrusion molding was 42.

The obtained phosphor-containing thermoplastic resin filament had a uniform diameter of each part, and the number of minute deformed parts (fish eyes) due to poor melting was about 1 in 300 m.

[Experimental Example 3]
YAG: Ce was kneaded into an acrylic resin (Delpet 60N (manufactured by Asahi Kasei Corporation)) as a phosphor to obtain pellets of a phosphor-containing thermoplastic resin having a YAG: Ce phosphor concentration of 7% by mass. Next, the pellets were put into a twin-screw extruder TEM-18 (manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at an average barrel heating temperature of 250 ° C., and then lowered to 235 ° C. to φ4. Extrude from a 5 mm orifice hole at a linear speed of 1.2 m / min, immerse the discharged thermoplastic resin in cold water, and then use a constant speed take-up machine IMC-19A5R (manufactured by Imoto Seisakusho Co., Ltd.) to increase the draw ratio. It was taken up at a linear velocity of 18 m / min, which is 15 times higher, and a phosphor-containing thermoplastic resin filament was obtained in a linear shape having an average diameter of 1.75 mm. The ratio (L / D) of the effective screw length L to the molten screw diameter D in this extrusion molding was 38.

The obtained phosphor-containing thermoplastic resin filament had a uniform diameter of each part, and the number of minute deformed parts (fish eyes) due to poor melting was about 1 in 200 m.

[Experimental Example 4]
The pellets of the phosphor-containing thermoplastic resin obtained by the same method as in Experimental Example 3 were put into a twin-screw extruder TEM-18 (manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at an average barrel heating temperature of 240 ° C. After that, while maintaining the temperature, it is extruded from an orifice hole of φ4.5 mm at a linear speed of 0.5 m / min, and the discharged phosphor-containing resin is submerged in cold water, and then the constant speed take-up machine IMC-19A5R ((( (Manufactured by Imoto Seisakusho Co., Ltd.) took over at a linear velocity of 1.3 m / min, which increases the draw ratio by 2.6 times, and obtained a phosphor-containing thermoplastic resin filament as a linear shape having an average of φ1.75 mm. The ratio (L / D) of the effective screw length L to the molten screw diameter D in this extrusion molding was 38.

In the obtained phosphor-containing thermoplastic resin filament, the diameter of each part varied greatly from 1.5 to 1.9 mm, and it was not possible to obtain a continuous filament of 10 m or more with a constant diameter.

[Experimental Example 5]
Pellets of phosphor-containing thermoplastic resin obtained in the same manner as in Experimental Example 1 were put into a twin-screw extruder TEM-18 (manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at an average barrel heating temperature of 240 ° C. After that, the temperature is lowered to 220 ° C., the resin is extruded from an orifice hole of φ1.8 mm at a linear velocity of 28 m / min, the discharged thermoplastic resin is submerged in cold water, and then the constant speed take-up machine IMC-19A5R (((() (Manufactured by Imoto Seisakusho Co., Ltd.) took over at a linear velocity of 30 m / min, which increases the stretching ratio by 1.1 times, to make a linear shape with an average of φ1.75 mm, and further heat it in a vacuum furnace at 70 ° C. for 12 hours. , A phosphor-containing thermoplastic resin filament was obtained. The ratio (L / D) of the effective screw length L to the molten screw diameter D in this extrusion molding was 29.

In the obtained phosphor-containing thermoplastic resin filament, the diameter of each part varied widely, and a continuous molded product of 10 m or more could not be obtained. In addition, the number of minute deformed parts (fish eyes) caused by poor melting was about 1 in 15 m.

[Example 1]
Using the filament obtained in Experimental Example 1, a 3D printer Ninjabot series NJB-300W (manufactured by Sanho Kogyo Co., Ltd.) of the FDM method was applied with a molding nozzle of φ0.25 mm, as shown in FIGS. Three types of ring cap-shaped wavelength conversion members were produced. For molding, slicing software manufactured by Simply 3D was used.

1A and 1B are views showing an example of a wavelength conversion member of the present invention, in which FIG. 1A is a perspective view and FIG. 1B is a sectional view. The inner surface of the wavelength conversion member (No. 1) shown in FIG. 1 is only a circular ring-shaped plane (top surface), an inner peripheral surface (side surface) which is a truncated cone peripheral surface, and an outer surface (side surface) which is a circumferential surface. It is a multifaceted discontinuous surface in which the top surface and the side surface are joined via a tangent line. Table 1 shows the sizes of the parts a to f shown in the figure. The inner circumference of the inner surface was φ29 mm, and the height from the LED to the upper end was 8.3 mm.

2A and 2B are views showing an example of a wavelength conversion member of the present invention, in which FIG. 2A is a perspective view and FIG. 2B is a sectional view. The inner surface of the wavelength conversion member (No. 2) shown in FIG. 2 is a dodecagonal ring-shaped plane (top surface), an inner peripheral surface (side surface) which is a peripheral surface of a dodecagonal pyramid, and an outer surface (side surface) which is a peripheral surface of a dodecagonal prism. It is composed of only side surfaces), and is a multifaceted discontinuous surface in which the top surface and the side surface are joined via a tangent line. Table 1 shows the sizes of the parts a to f shown in the figure. The outer peripheral size of the inner surface was set to a maximum outer diameter of 46 mm and a height from the LED to the upper end of 5 mm.

3A and 3B are views showing an example of a wavelength conversion member of the present invention, in which FIG. 3A is a perspective view and FIG. 3B is a sectional view. The inner surface of the wavelength conversion member (No. 3) shown in FIG. 3 is composed of only a circular ring-shaped plane (top surface), an inner peripheral surface (side surface) which is a cylindrical peripheral surface, and an outer surface (side surface). The side surface is a multi-faceted discontinuous surface that is joined via a tangent line. Table 1 shows the sizes of the parts a to f shown in the figure. The outer peripheral size of the inner surface was φ46 mm, and the height from the LED to the upper end was 6.3 mm.

FIG. 4 is an exploded perspective view showing an example of the remote phosphor type LED light emitting device of the present invention manufactured by using the wavelength conversion member (No. 1). As shown in FIG. 4, 12 LEDs 22 (PK2N blue (manufactured by ProLight Opti Technology, peak wavelength 453 nm), peak wavelength 453 nm) are connected in series on a white-painted aluminum substrate 21 at equal intervals on a φ38 mm circumference. In this case, the remote phosphor type LED light emitting device 10 is provided by arranging the wavelength conversion member 1 so that the LED array is located between the inner and outer peripheral surfaces on the bottom side of the wavelength conversion member 1. The height from the surface of the aluminum substrate to the upper end of the LED is 1.7 mm. Then, a voltage of 3 V and a current of 200 mA are applied to the LED with a stabilized power supply to measure the optical characteristics of the LED light emitting device. It was evaluated by the system HM-9100B (manufactured by Otsuka Electronics Co., Ltd.), and the color variation was visually evaluated. The results are shown in Table 1. The color temperature of the light emitted by the three types of LED light emitting devices is 4500. The average color performance evaluation number Ra was in the range of 91 to 93 at ~ 5000K.

From the evaluation results of the optical characteristics, the remote phosphor having high light emission characteristics with high luminous efficiency and small variation in chromaticity and color temperature by the wavelength conversion member manufactured by using the phosphor-containing thermoplastic resin filament of the present invention. It can be seen that the type LED light emitting device was obtained.

1 Wavelength conversion member 10 Remote phosphor type LED light emitting device 21 Substrate 22 LED

Claims (3)

A raw material filament for producing a wavelength conversion member containing a phosphor that converts the wavelength of light emitted from an LED and emits light having a wavelength different from the wavelength by a 3D printer by a melt lamination method. The above-mentioned phosphor in the form is dispersed in the thermoplastic resin at a concentration of 30% by mass or less.
The phosphor is A ₂ (M _1-x , Mn _x ) F ₆ (in the formula, A is selected from Li, Na, K, Rb and Cs, and one or 2 containing at least Na and / or K. More than one kind of alkali metal, M is one kind or two or more kinds of tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn, and x is a positive number in the range of 0.001 to 0.3. Includes a manganese-activated compound fluoride phosphor represented by)
A phosphor-containing thermoplastic resin filament, wherein the thermoplastic resin is selected from an olefin resin, a cyclic polyolefin resin, an acrylic resin, a styrene resin, and an acrylicimide resin. The manganese-activated compound fluoride phosphor is manganese represented by K ₂ (Si _1-x , Mn _x ) F ₆ (x is a positive number in the range of 0.001 to 0.3 in the formula). The phosphor-containing thermoplastic resin filament according to claim 1, which is an activated potassium fluoride phosphor. The phosphor-containing thermoplastic resin filament according to claim 1 or 2, wherein the thermoplastic resin is selected from an acrylic resin, polystyrene, a styrene copolymer, polyethylene, polypropylene, and an ethylene-propylene copolymer.

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