TW201347242A - Wavelength conversion unit and semiconductor light-emitting device using the wavelength conversion unit - Google Patents

Abstract

The problem to be solved of this invention is to provide a wavelength conversion unit which can reduce manufacturing cost by cutting the amount of phosphors without lowering luminous efficiency of the semiconductor light-emitting device when the unit is provided on the semiconductor light-emitting device, and to provide the semiconductor light-emitting device using the wavelength conversion unit. The problem is solved by the wavelength conversion unit that converts at least a part of incident light into emitting light whose wavelength is different from the incident light and emits the emitting light, the wavelength conversion unit comprising phosphors which absorb at least a part of the incident light and emit the emitting light whose wavelength is different from the incident light, a light scattering element which scatters the incident light and the emitting light, and a base which holds the light scattering element, in which the wavelength conversion unit satisfies the following formula; 0.01 ≤ |(refraction index of the light scattering element)-(refraction index of the base)| * (thickness of the wavelength conversion unit [mm]) * (volume fraction of the light scattering element[vol%]) ≤ 1.0.

Description

Wavelength conversion member and semiconductor light emitting device using same

The present invention relates to a wavelength conversion member that converts at least a part of wavelength of incident light to emit emitted light having a wavelength different from the incident light, and a semiconductor light-emitting device using the wavelength conversion member and the semiconductor light-emitting element.

As a light source of a light-emitting device, an incandescent light bulb or a fluorescent lamp has been widely used. In recent years, in addition to these, the semiconductor light-emitting device using a semiconductor light-emitting device such as a light-emitting diode (LED) or an organic light-emitting diode (OLED) as a light source has been developed and used. Since various light-emitting colors can be obtained by the semiconductor light-emitting elements, the industry has also developed and started to use a plurality of semiconductor light-emitting elements having different combined light-emitting colors, and combining the respective light-emitting colors to obtain a composite light of a desired color. .

For example, Patent Document 1 discloses a semiconductor light-emitting device which uses a red LED of an LED chip having a red-emitting color, a green LED using an LED chip having a green color, and a blue color using a light-emitting color. The blue LED of the LED chip adjusts the driving current supplied to each LED, synthesizes the light emitted from each LED, and emits the desired white light.

Originally, the LED chip itself has a relatively narrow luminescence spectral width. Therefore, when the light emitted from the LED chip itself is directly used for illumination, the color rendering property which is more important in general illumination light is reduced. Therefore, in order to eliminate such a problem, the industry has developed an LED that converts the wavelength of light emitted from an LED chip by a wavelength conversion member such as a phosphor and emits light obtained by wavelength conversion, as disclosed in Patent Document 2, for example. There is a semiconductor light-emitting device in which such an LED is combined.

In the semiconductor light-emitting device disclosed in Patent Document 2, it is contacted and covered A transparent resin is provided in such a manner as to emit a blue light LED chip, and the inside of the transparent resin contains a yellow phosphor. That is, the semiconductor light-emitting device disclosed in Patent Document 2 is provided with a wavelength conversion member so as to directly cover the LED chip. However, in the semiconductor light-emitting device having such a configuration, the semiconductor light-emitting device has uneven brightness and color unevenness. In order to solve such a problem, in recent years, a semiconductor light-emitting device having a structure in which a resin containing a phosphor (i.e., a wavelength converting member) is disposed apart from an LED wafer has been actively developed and produced. For example, Patent Document 3 discloses a semiconductor light-emitting device having such a configuration.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-4839

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-122950

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-159813

However, the configuration in which the wavelength conversion member is provided apart from the LED wafer is larger than the configuration in which the wavelength conversion member is provided in contact with and covering the LED wafer, and the size of the wavelength conversion member is large, thereby causing fluorescence contained in the resin. The amount of body increases. In general, when the wavelength conversion member is separated from the LED wafer, in order to obtain the same luminous efficiency as in the case where the LED chip is directly coated with the wavelength conversion member, a phosphor which is several times or more larger than the previous one is required. Therefore, it is desired to reduce the amount of phosphor used in the wavelength conversion member.

Therefore, the semiconductor light-emitting device having the structure in which the wavelength conversion member is disposed apart from the LED wafer has a problem that the amount of the phosphor increases as compared with the prior art, and the cost of the wavelength conversion member and the semiconductor light-emitting device increases. Especially in the case where a single wavelength conversion member is provided for a large number of LED chips, the product cost increases.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a semiconductor light-emitting device capable of reducing the content of a phosphor and reducing the cost without reducing the luminous efficiency of the semiconductor light-emitting device. Wavelength conversion member, And a semiconductor light-emitting device using the wavelength conversion member.

In order to achieve the above object, a wavelength conversion member according to the present invention is characterized in that at least a part of wavelength of incident light is converted to emit light having a wavelength different from that of the incident light, and is characterized in that at least a part of the incident light is absorbed to emit a wavelength and the incident. a phosphor that emits light different in light, a light diffusing element that diffuses the incident light and the emitted light, and a base material that holds the light diffusing element, and satisfies 0.01 ≦| (refractive index of light diffusing element) - (mother The refractive index of the material is × × (thickness of the wavelength conversion member [mm]) × (volume fraction of the light diffusing element [vol%]) ≦ 1.0.

Further, in the above-described wavelength conversion member, | (the refractive index of the light diffusion element) - (the refractive index of the base material) | × (the thickness of the wavelength conversion member [mm]) × (the volume fraction of the light diffusion element) The value of the rate [vol%] is preferably 0.6 or less, and more preferably 0.2 or less.

Further, in the wavelength conversion member, the value of | (the refractive index of the light diffusion element) - (the refractive index of the base material) | in the above formula is preferably 0.07 or more.

Further, in the wavelength conversion member, the phosphor is contained in a case where a wavelength conversion member that emits light of the same chromaticity without the light diffusion element is produced, and the phosphor concentration is based on the concentration [wt%] of the phosphor. The reduction ratio of the concentration [wt%] may be from 3.0% to 86%.

Further, in the above-described wavelength conversion member, | (the refractive index of the light diffusion element) - (the refractive index of the base material) | × (the thickness of the wavelength conversion member [mm]) × (the volume fraction of the light diffusion element) The value of the rate [vol%] is preferably 0.04 or more, and more preferably 0.05 or more.

The above wavelength conversion member can also satisfy the following formula: 28≦dy/dx≦447

x:|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength converting member [mm])×(volume fraction of light diffusing element [vol%])

y: the concentration of the phosphor (% by weight) based on the concentration [wt%] of the phosphor when the wavelength conversion member that emits the same chromaticity is emitted without the light diffusing element ] The reduction rate.

In the wavelength conversion member, the phosphor and the light diffusion element may be The mixture is present in the above base material. Further, the phosphor and the light diffusing element may be separated from each other and contained in the base material to form a phosphor layer and a light diffusing layer. In this case, the phosphor layer and the light diffusion layer may be in contact with each other and laminated, or the base material may have a void layer separating the phosphor layer from the light diffusion layer.

In the wavelength conversion member, it is preferable that the light diffusion element has a refractive index of 1.0 or more and 1.9 or less, and the base material has a refractive index of 1.3 or more and 1.7 or less.

In the wavelength conversion member, it is preferable that the light diffusion element contains an inorganic light-diffusing material selected from at least one element selected from the group consisting of ruthenium, aluminum, titanium, and zirconium, or an organic light-diffusing material. In this case, it is more preferable that the organic light diffusing material contains an organic light diffusing material or an acrylic light diffusing material.

In the wavelength conversion member, the light diffusion element may include air bubbles.

In the wavelength conversion member, it is preferable that the base material contains a resin or glass. In this case, it is more preferable that the resin is at least one selected from the group consisting of a polycarbonate resin, a polyester resin, an acrylic resin, an epoxy resin, and a polyoxymethylene resin.

More preferably, in the wavelength conversion member, the base material is a polycarbonate resin, and the light diffusion element is polymethylsesquioxane particles.

In order to achieve the above object, a semiconductor light-emitting device according to the present invention includes a wiring substrate, a semiconductor light-emitting device disposed on a mounting surface of the wiring substrate, and a light-emitting portion that converts at least a portion of incident light to emit a wavelength different from the incident light. In the wavelength conversion member, the wavelength conversion member includes a phosphor that absorbs at least a part of incident light and emits light having a wavelength different from the incident light, and a light diffusing element that diffuses the incident light and the emitted light. And maintaining the base material of the light diffusing element, and satisfying 0.01 ≦| (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × (light diffusing element Volume fraction [vol%]) ≦ 1.0 number formula.

Further, in the above semiconductor light-emitting device, | (the refractive index of the light diffusing element) - (the refractive index of the base material) | × (the thickness of the wavelength converting member [mm]) × (the volume fraction of the light diffusing element) The value of the rate [vol%] is preferably 0.6 or less, more preferably 0.2 or less.

Further, in the above semiconductor light-emitting device, in the above formula, | The refractive index of the element (the refractive index of the base material)| is preferably 0.07 or more.

In the above semiconductor light-emitting device, the case where the light diffusion element is not included In the case of the luminous efficiency (lm/W), the luminous efficiency (lm/W) is maintained at a rate of 90% or more, and the concentration of the above-mentioned phosphor is higher than that in the case where the above-mentioned light-diffusing element is not contained. ] can be reduced.

Further, in the above semiconductor light emitting device, the semiconductor light emitting element and the upper surface The wavelength conversion members can be separated.

Further, in the above semiconductor light-emitting device, the phosphor and the optical expansion The scattered elements may be mixed and present in the above base material. Further, in the above semiconductor light-emitting device, the phosphor and the light diffusing element may be separated from each other and contained in the base material, and a laminated structure including a phosphor layer and a light diffusion layer may be formed. In this case, the distance from the semiconductor light emitting element to the phosphor layer may be smaller or larger than the distance from the semiconductor light emitting element to the light diffusion layer.

In the above semiconductor light emitting device, preferably, the light diffusing element is refracted The ratio of the base material is 1.0 or more and 1.9 or less, and the refractive index of the base material is 1.3 or more and 1.7 or less.

In the above semiconductor light-emitting device, it is preferable that the base material contains a resin or a glass Glass. In this case, it is more preferable that the resin is at least one selected from the group consisting of a polycarbonate resin, a polyester resin, an acrylic resin, an epoxy resin, and a polyoxymethylene resin.

In the above semiconductor light-emitting device, it is further preferred that the base material is polycarbonate In the ester resin, the light diffusing element is polymethylsilsesquioxane particles.

In the above semiconductor light-emitting device, the wavelength conversion member is not used The light emitted from the semiconductor light-emitting element of the wavelength conversion and the light converted by the wavelength conversion member may be mixed to emit white light. The semiconductor light-emitting device preferably has a reflector provided on the wiring board, and an area having a reflectance of 80% or more is 50% or more of an area on the wiring board. Further, the semiconductor light-emitting device preferably has a casing, and a reflector is provided on the wiring board and the inner wall surface of the casing, and an area having a reflectance of 80% or more is the inner wall surface of the casing and 50% or more of the area on the wiring board.

In order to achieve the above object, a semiconductor light-emitting device according to the present invention includes a wiring substrate, a semiconductor light-emitting device disposed on a mounting surface of the wiring substrate, and a light-emitting portion that converts at least a portion of incident light to emit a wavelength different from the incident light. In the wavelength conversion member, the wavelength conversion member includes a phosphor that absorbs at least a part of incident light and emits light having a wavelength different from the incident light, and a light diffusing element that diffuses the incident light and the emitted light. And maintaining the base material of the light diffusing element, and satisfying 0.01 ≦| (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × (light diffusing element The volume fraction [vol%]) ≦ 1.0 is a formula of the above formula (the volume fraction of the light diffusing element [vol%]) is an image analysis result using the cross-sectional SEM image of the wavelength converting member, and Calculated by the formula of C=N×4 π/3×(D/2) ³ /(S×D)×100,

C: volume fraction of light diffusing elements [vol%]

N: the total number of light diffusion elements in the wavelength conversion member calculated by the binarization processing of the cross-sectional SEM image [a]

D: the average particle diameter of the light diffusion element in the cross-sectional SEM image calculated by the binarization processing of the cross-sectional SEM image, and the particle of the light diffusion element obtained by multiplying the average diameter of the circle calculated by the circle by π/4 Trail [μm]

S: total area of the cross-sectional SEM image [μm ² ].

In the wavelength conversion member of the present invention, 0.01 ≦| (refractive index of the light diffusion element) - (refractive index of the base material) | × (thickness of the wavelength conversion member [mm]) × (volume fraction of the light diffusion element) [vol%]) ≦ 1.0 is a numerical formula. Therefore, when it is provided on a semiconductor light-emitting device, the content of the phosphor can be reduced without reducing the luminous efficiency of the semiconductor light-emitting device, and the cost can be reduced. It is presumed that the reason is that the ratio of the light emitted by the wavelength-converted semiconductor light-emitting element per unit weight of the phosphor contained in the wavelength conversion member can be increased. In this case, | (refractive index of light diffusing element) - (refractive index of base material) | × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) When it is 0.6 or less, this effect (lower luminous efficiency and cost reduction) is remarkably exhibited, and if it is 0.2 or less, this effect will exhibit more remarkable.

Further, in the wavelength conversion member of the present invention, | (refraction of the light diffusion element) When the value of (the refractive index of the base material) × × (thickness of the wavelength conversion member [mm]) × (the volume fraction of the light diffusion element [vol%]) is 0.02 or more, the fluorescence reduction can be reduced. The unevenness of the luminous efficiency of the semiconductor light-emitting device caused by the uneven content of the body. Further, since the conversion efficiency of light emitted from the semiconductor light-emitting element changes, in the above case, light emitted from the semiconductor light-emitting element (for example, blue light) is mixed with light (for example, yellow light) converted by the wavelength conversion member. The chromaticity unevenness of light emitted from the semiconductor light-emitting device (for example, white light) can be reduced. In this case, | (refractive index of light diffusing element) - (refractive index of base material) | × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) When the ratio is 0.04 or more, the effect (decreased unevenness in luminous efficiency) is remarkably exhibited, and if it is 0.05 or more, the effect is more prominently exhibited.

Further, in the semiconductor light-emitting device of the present invention, the wavelength conversion member Satisfy 0.01 ≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) ≦ 1.0 Therefore, the content of the phosphor can be reduced without lowering the luminous efficiency, and the cost can be reduced.

Further, when verifying and evaluating the wavelength conversion member included in the semiconductor light-emitting device, the image analysis result of the scanning electron micro-scope (SEM) image of the wavelength conversion member is used, and C=N×4 π/ 3 × (D / 2) ³ / (S × D) × 100 (here, C: the volume fraction of the light diffusing element [vol%], N: the wavelength calculated by the binarization processing of the cross-sectional SEM image The total number of light diffusing elements in the conversion member [1], D: the average diameter of the circle calculated from the cross-sectional SEM image calculated by the binarization processing of the cross-sectional SEM image, and assumed to be a circle Calculating the volume fraction of the light diffusing element [vol%] in the above formula by multiplying the particle diameter [μm] of the light diffusing element obtained by π/4 and S: the total area of the SEM image of the cross section [μm 2] ]), thereby achieving verification and evaluation with the same high precision as in the case of verifying and evaluating the true value of the volume fraction of the light diffusing element.

1, 21, 31‧‧‧ semiconductor light-emitting devices

2‧‧‧ wiring substrate

2a‧‧‧ wafer mounting surface

3‧‧‧LED chip (semiconductor light-emitting element)

4, 24, 34‧‧‧ wavelength conversion components

4a, 24a, 34a‧‧‧ phosphor

4b, 24b, 34b‧‧‧Light diffusion elements

4c, 24c, 34c‧‧‧ resin (base metal)

5‧‧‧p electrode

6‧‧‧n electrode

7‧‧‧Wiring pattern 7

8‧‧‧ wiring pattern 8

24d, 34d‧‧‧ fluorescent layer

24e, 34e‧‧‧Light diffusion layer

34f‧‧‧void layer

100‧‧‧Semiconductor light-emitting device

101‧‧‧LED chip (semiconductor light-emitting element)

102‧‧‧ wiring substrate

102a‧‧‧ wafer mounting surface

103‧‧‧wavelength conversion component

Fig. 1 is a view showing the outline of the overall configuration of a semiconductor light-emitting device according to a first embodiment; Stereo picture.

Fig. 2 is a plan view showing the semiconductor light-emitting device of the first embodiment.

Figure 3 is a cross-sectional view of the semiconductor light emitting device taken along line III-III of Figure 2.

Figure 4 is an enlarged cross-sectional view showing an important part of Figure 3.

Fig. 5 is a graph showing a simulation result in the semiconductor light-emitting device of the first embodiment.

Fig. 6 is a graph showing a simulation result in the semiconductor light-emitting device of the first embodiment.

Fig. 7 is an enlarged cross-sectional view showing an essential part of the semiconductor light-emitting device of the second embodiment, similarly to Fig. 4 .

Fig. 8 is an enlarged cross-sectional view showing another aspect of an important part of the semiconductor light-emitting device of the second embodiment, similarly to Fig. 4 .

Fig. 9 is an enlarged cross-sectional view showing an essential part of the semiconductor light-emitting device of the third embodiment, similarly to Fig. 4 .

Fig. 10 is an enlarged cross-sectional view showing another aspect of an important part of the semiconductor light-emitting device of the third embodiment, similarly to Fig. 4;

FIG. 11 is a view showing the amount of phosphor used when the value of [(the refractive index of the light diffusing element - the refractive index of the base material) × the thickness of the wavelength converting member × the volume fraction of the light diffusing element] is changed in the second embodiment. A graph of changes in changes in luminous flux values.

Fig. 12 is a conceptual diagram showing the configuration of a semiconductor light-emitting device according to an embodiment of the present invention.

Fig. 13 is a conceptual view showing the configuration of a semiconductor light-emitting device according to an embodiment of the present invention.

Embodiments of the present invention will be described in detail below with reference to the drawings. The present invention is not limited to the contents described below, and may be arbitrarily changed without departing from the spirit and scope of the invention. In addition, the semiconductor light-emitting device of the present invention is schematically illustrated in the drawings, and the semiconductor light-emitting device of the present invention is partially emphasized, enlarged, reduced, or omitted, and the scale of each constituent member is not accurately indicated. Or the shape of the case. Further, various numerical values used in the respective embodiments are examples, and various changes can be made as needed.

<First embodiment> (Composition of semiconductor light-emitting device)

1 is a perspective view showing an overall configuration of a semiconductor light-emitting device 1 according to a first embodiment, and FIG. 2 is a plan view showing the semiconductor light-emitting device 1 of FIG. In FIGS. 1 and 2, one direction of the plan view of the semiconductor light-emitting device 1 is defined as the X direction, and the direction orthogonal to the X direction in the plan view is defined as the Y direction, and the height direction of the semiconductor light-emitting device 1 is defined. (The normal direction of the wiring substrate) is defined as the Z direction.

In the present embodiment, the semiconductor light-emitting device 1 emits a light source of virtual white light. As shown in FIG. 1, the semiconductor light-emitting device 1 includes a wiring board 2 including an alumina-based ceramic which is excellent in electrical insulating properties, has excellent heat dissipation properties, and has a high reflectance (preferably, a reflectance of 80% or more). Four LEDs (Light Emitting Diode) wafers 3 are arranged in the X direction of the wafer mounting surface 2a of the wiring board 2, and three LEDs are arranged in the Y direction. . As shown in FIG. 1, a wiring pattern for supplying electric power to the LED chips 3 is formed on the wiring board 2 to constitute an electric circuit.

In addition, the material of the wiring board 2 is not limited to the alumina-based ceramics. For example, a material excellent in electrical insulation can be used to form a wiring using a material selected from the group consisting of a resin, a glass epoxy, and a composite resin containing a filler in a resin. The body of the substrate 2. Alternatively, in order to improve the light-emitting efficiency of the semiconductor light-emitting device 1 by improving the light reflectivity of the wafer mounting surface 2a of the wiring board 2, it is preferable to use a white pigment containing alumina powder, cerium oxide powder, magnesium oxide, or titanium oxide. Polyoxygenated resin. On the other hand, in order to obtain more excellent heat dissipation and reflectivity, the body of the wiring board 2 may be made of a metal such as silver. In this case, the wiring pattern or the like of the wiring board 2 needs to be electrically insulated from the metal body.

The wafer mounting surface 2a of the wiring board 2 preferably has a reflectance of 90% or more, and more preferably has a reflectance of 90% or more. % or more, further preferably 70% or more, and particularly preferably 80% or more. Further, the reflectance refers to the reflectance of light in the visible light region. As a material for achieving such a reflectance, a reflective material in which a resin contains a filler is exemplified. Specifically, it is preferably a polyoxyxylene resin, a polycarbonate resin, or a polyphthalamide resin. A reflective material such as a metal oxide filler such as alumina, titania, cerium oxide, zinc oxide or magnesium oxide, or a reflective material obtained by containing a metal oxide in a ceramic. Examples of the reflective material in which the polycarbonate resin contains a metal oxide such as titanium oxide include, for example, Iupilon EHR3100 and EHR3200. Examples of the reflective material in which the polyoxynene resin contains a metal oxide such as alumina or titanium oxide include a reflective material described in WO2011/078239 and WO2011/136302. Moreover, a reflective material in which polyphthalamide contains a metal oxide such as alumina or titanium oxide is preferably exemplified.

Moreover, as shown in FIG. 1, the wiring substrate 2 on which the LED chip 3 is mounted is shown. The wafer mounting surface 2a is provided with a wavelength converting member 4 that converts at least a part of the wavelength of the incident light incident from the LED chip 3 into a different wavelength, and radiates the wavelength-converted light as an outgoing light to the semiconductor light emitting device. 1 outside. The wavelength conversion member 4 has a hemispherical shape and a dome shape (ie, a bowl shape) in which a void is formed. Further, the wavelength conversion member 4 is spaced apart from the twelve LED chips 3, and covers all of the LED chips 3.

Figure 3 is a cross-sectional view of the semiconductor light-emitting device 1 taken along line III-III of Figure 2; FIG. 4 is an enlarged view of an important part of the cross-sectional view shown in FIG. 3. The LED chip 3 and the wavelength conversion member 4 will be described in detail below with reference to FIGS. 3 and 4.

(LED chip)

In the LED wafer 3 of the present embodiment, an LED chip emitting blue light having a peak wavelength of 460 nm is used. Specifically, as such an LED wafer, for example, a GaN-based LED wafer in which an InGaN semiconductor is used for a light-emitting layer is used. Further, the type of the LED chip 3 or the light-emitting wavelength characteristic is not limited thereto, and various semiconductor light-emitting elements such as LED chips can be used without departing from the gist of the present invention. In this embodiment, the peak wavelength of the light emitted by the LED chip 3 is preferably in the wavelength range of 360 nm to 480 nm, more preferably in the wavelength range of 390 nm to 430 nm or a wavelength of 430 nm to 480 nm. Within the scope.

As shown in FIG. 4, a p-electrode 5 and an n-electrode 6 are provided on the surface of the LED chip 3 facing the wiring board 2 side. In the case of the LED chip 3 shown in FIG. 4, the p-electrode 5 is bonded to the wiring pattern 7 formed on the wafer mounting surface 2a of the wiring substrate 2, and the wiring pattern formed on the wafer mounting surface 2a is also formed in the same manner. 8 is connected to the n electrode 6. The connection of the p-electrode 5 and the n-electrode 6 on the wiring pattern 7 and the wiring pattern 8 is via Metal bumps (not shown) are formed by soldering. In the other LED chips 3 (not shown), the p-electrodes 5 and the n-electrodes 6 are similarly bonded to the wiring pattern formed on the wafer mounting surface 2a of the wiring board 2 corresponding to each of the LED chips 3. Here, the LED chips 3 may be connected in series via the wiring pattern 7 and the wiring pattern 8, or may be connected in parallel, or may be connected in series or in parallel.

Furthermore, the mounting method of the LED chip 3 on the wiring substrate 2 is not limited. Here, a suitable method can be selected according to the type or structure of the LED chip 3. For example, after the LED chip 3 is subsequently fixed to a specific position of the wiring substrate 2, two electrodes of the LED chips 3 are connected to the corresponding wiring patterns by wire bonding, and one of the electrodes may be as described above. The method is bonded to the corresponding wiring pattern while the other electrode is connected to the corresponding wiring pattern by wire bonding.

(wavelength conversion member)

As described above, the wavelength conversion member 4 partially converts the wavelength of the incident light radiated from the LED wafer 3, and emits the emitted light having a wavelength different from the incident light. More specifically, the wavelength conversion member 4 includes a phosphor 4a that absorbs incident light emitted from the LED chip 3 and excites it, and emits light having a wavelength different from the incident light when returning to the ground state; the light diffusing element 4b, which diffuses the emitted light emitted from the phosphor 4a and guides it to the exit surface side of the semiconductor light-emitting device 1; the resin 4c disperses and holds the phosphor 4a and the light diffusing element 4b, and serves as the mother of the wavelength converting member 4 Functionality. 4 is an enlarged view of an essential part of a cross-sectional view of the semiconductor light-emitting device 1 in the case where a resin is used as a base material. In the wavelength conversion member 4 of the embodiment of FIG. 4, the phosphor 4a is mixed in the resin 4c. Light diffusing element 4b.

Further, in the semiconductor light-emitting device 1 of the present embodiment, since the wavelength conversion member 4 is separated from the LED wafer, the wavelength conversion member 4 is not heated by the heat generated by the LED wafer 3, and the wavelength of the wavelength conversion member 4 can be suppressed. The conversion function and the reduction in luminous efficiency of the semiconductor light-emitting device 1 are reduced. In the present embodiment, the wavelength conversion member 4 is spaced apart from the LED chip 3 by about 25 mm. In the aspect in which the wavelength conversion member is separated from the LED chip, the separation distance is appropriately set depending on the size of the device, etc., and is usually 1 mm or more apart, preferably 5 mm or more, and usually 500 mm or less. Good for less than 300 mm.

[fluorescent body]

In the present embodiment, since the LED chip 3 emitting blue light is used as the semiconductor light-emitting element, in order to obtain white light from the semiconductor light-emitting device 1, a part of the blue light is converted into yellow light by the yellow light and White light is synthesized without mixing of wavelength-converted blue light. Therefore, in the phosphor 4a of the present embodiment, a yellow phosphor that converts the wavelength of blue light into yellow light is used.

Further, in order to adjust the chromaticity or color temperature of white light or to improve color rendering, there is a case where one wavelength of the blue light is converted into red light or green light. In this case, in addition to the yellow phosphor, a red phosphor or a green phosphor may be used, or a red phosphor and a green phosphor may be used instead of the yellow phosphor.

The luminescence peak wavelength of the specific yellow phosphor is preferably 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably It is in the wavelength range below 580 nm. Among them, as the yellow phosphor, for example, Y ₃ Al ₅ O ₁₂ :Ce[YAG phosphor], Lu ₃ Al ₅ O ₁₂ :Ce[LuAG phosphor], (Y,Gd) ₃ Al is preferable. ₅ O ₁₂ :Ce, (Sr,Ca,Ba,Mg) ₂ SiO ₄ :Eu, (Ca,Sr)Si ₂ N ₂ O ₂ :Eu, α-Sialon, La ₃ Si ₆ N ₁₁ :Ce (where , a part of it can be replaced by Ca or O).

In the case of using a red phosphor, it is preferred that the luminescence peak wavelength is usually 565 nm or more, preferably 575 nm or more, more preferably 580 nm or more, and usually 780 nm or less, preferably 700 nm. The following, more preferably in the wavelength range below 680 nm. As such a red phosphor, for example, CaAlSiN ₃ :Eu [CASN phosphor] described in JP-A-2006-008721, and JP-A-2008-7751 can be used. (Sr, Ca) AlSiN ₃ :Eu [SCASN phosphor], and Ca _1-x Al _1-x Si _1+x N _3-x O _x :Eu[CASON described in Japanese Patent Laid-Open Publication No. 2007-231245 Eu-activated oxide, nitride or oxynitride phosphor such as phosphor], Mn-activated citrate phosphor such as 3.5MgO‧0.5gF ₂ ‧GeO ₂ :Mn, Mn ⁴⁺ activating fluoride complex Fluorescent body, etc.

Further, in the case of using a green phosphor, the luminescence peak wavelength is usually more than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, and preferably 540. Below nm, and further preferably in the range of 535 nm or less. If the wavelength of the luminescence peak is too short, there is a tendency for bluish blue. On the other hand, if it is too long, there is a tendency to be yellowish, and both of them have a possibility that the characteristics of green light are lowered. As such a green phosphor, for example, Y ₃ (Al,Ga) ₅ O ₁₂ :Ce[G-YAG phosphor], and (Pa,Ca,Sr) described in International Publication No. 2007/091687 may be used. (Mg) ₂ SiO ₄ : Eu-expressed alkaline earth silicate-based phosphor [BSS phosphor], and Si _6-z Al _z N _8-z O _z described in Japanese Patent No. 3921545 :Eu (in which 0<z≦4.2), etc., Eu-activated oxynitride phosphor [β-SiAlON phosphor], and M ₃ Si ₆ O ₁₂ N ₂ :Eu described in International Publication No. 2007/088966 (E), an Au-activated oxynitride phosphor [BSON phosphor], such as an alkaline earth metal element, and a BaMgAl ₁₀ O ₁₇ :Eu, Mn-activated aluminate described in JP-A-2008-274254 Fluorescent body [GBAM phosphor].

Regarding the particle diameter of the phosphor 4a, it is generally preferable to use a volume-based median diameter D _50v of 0.1 μm or more, and more preferably a D _50v of 1 μm or more. Further, it is preferable to use a D _50v of 30 μm or less, and more preferably a D _50v of 20 μm or less. Here, the volume-based median diameter D _50v is defined as follows: When a sample is measured using a particle size distribution measuring apparatus using a laser diffraction or scattering method as a measurement principle, and a particle size distribution (cumulative distribution) is obtained The relative particle amount of the volume reference reaches a particle size of 50%. As a measuring method, for example, a phosphor 4a is added to ultrapure water, and an ultrasonic disperser (manufactured by KAIJO) is used, and the frequency is set to 19 KHz, and the intensity of the ultrasonic wave is set to 5 W. After dispersing the sample for 25 seconds by ultrasonic wave, the flow rate was adjusted to be in the range of 88% to 92% using a launder, and it was confirmed that after the non-aggregation, the laser diffraction type particle size distribution measuring device (Marunouchi Co., Ltd.) was used. LA-300), measured in the particle size range of 0.1 μm to 600 μm. In the above method, when the phosphor particles are aggregated, a dispersing agent may be used. As an example, the phosphor 4a may be added to an aqueous solution containing 0.0003 wt% of Tamol (manufactured by BASF Corporation). The method is similarly dispersed by ultrasonic waves, and then measured.

As an index indicating the degree of particle size distribution, there is a ratio (D _v /D _n ) of the volume average reference particle diameter D _{v of the} phosphor 4a to the number average reference particle diameter D _n . In the invention of the present application, D _v /D _{n is} preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.4 or more. On the other hand, D _v / D _{n is} preferably 25 or less, more preferably 10 or less, and still more preferably 5 or less. When D _v /D _{n is} too large, there are phosphor particles having different weights, and the dispersion of the phosphor particles in the phosphor layer tends to be uneven.

Further, as the phosphor 4a, those whose surface is previously coated by the third component may be used. The type of the third component to be applied and the method of application are not particularly limited, and any of the known third components and methods may be used.

Examples of the third component include an organic acid, an inorganic acid, a decane treating agent, eucalyptus oil, and liquid paraffin. By using the third component, the phosphor 4a is surface-treated and coated, and the affinity for the resin 4c, the dispersibility, the thermal stability, the fluorescent color rendering property, and the like tend to be improved. The surface treatment and the coating amount are usually 0.01 to 10 parts by weight per 100 parts by weight of the phosphor 4a, and if less than 0.01 part by weight, it is difficult to obtain affinity, dispersibility, thermal stability, and fluorescence coloration. When the effect of the improvement is more than 10 parts by weight, problems such as thermal stability, mechanical properties, and deterioration in fluorescence coloration are likely to occur.

The content of the phosphor 4a in the wavelength conversion member 4 depends on the type of the light diffusing element 4b and the resin 4c. For example, when the resin 4c is a polycarbonate resin, it is usually 100 parts by weight based on the polycarbonate resin. 0.1 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, further preferably 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the content of the phosphor 4a is too small, it is difficult to obtain the wavelength conversion effect of the phosphor, and if it is too large, the mechanical properties are deteriorated, which is not preferable.

[Light diffusion element]

In the present embodiment, as the light diffusing element 4b, an inorganic light diffusing material, an organic light diffusing material, or a bubble is preferably used.

As the inorganic light-diffusing material, for example, an inorganic light-diffusing material such as ruthenium, aluminum, titanium, zirconium, calcium or lanthanum can be used, and it is preferable to use a group selected from the group consisting of ruthenium, aluminum, titanium, and zirconium. An inorganic light diffusing material of at least one element. As the organic light-diffusing material, an acrylic-based, styrene-based, polyamide-based or organic-based light-diffusing material containing a lanthanum element can be used. Among them, an acrylic light-diffusing material or an organic system containing lanthanum element is preferably used. Light diffusing material.

Specific examples of the inorganic light-diffusing material include cerium oxide. (silica), white carbon, talc, magnesium oxide, zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, boron oxide, calcium carbonate, barium carbonate, magnesium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium sulfate Calcium citrate, magnesium citrate, aluminum citrate, sodium aluminum citrate, zinc citrate, glass, mica, and the like.

Examples of the organic light-diffusing material include styrene-based (co)polymers and C. An olefinic (co)polymer, a decane-based (co)polymer, a polyamine-based (co)polymer, or the like. Some or all of the molecules of the organic diffusing materials may or may not be crosslinked. Here, the term "(co)polymer" means both "aggregate" and "co-aggregate".

Among the above light diffusing elements, in order to increase the light diffusing effect by a small amount, it is preferred. A light diffusing element having a large difference between the refractive index of the base material and the refractive index of the selected light diffusing element is selected. Further, in order not to greatly reduce the luminous efficiency, it is preferred to select a light diffusing element having high transparency.

For example, when the resin 4c is a polycarbonate resin, it acts as a light diffusion. The element 4b is preferably a crosslinked particle obtained by using a crosslinked acrylic (co)polymer particle, a copolymer of an acrylic compound and a styrene compound, a pyrithion-based (co)polymer particle, an acrylic compound, and the like. More preferably, the mixed crosslinked particles of the compound of the ruthenium atom are crosslinked acrylic (co)polymer particles and siloxane oxide (co)polymer particles.

As the crosslinked acrylic (co)polymer particles, it is more preferred to contain non-crosslinking The polymer particles of the acrylic monomer and the crosslinkable monomer are more preferably polymer particles obtained by crosslinking methyl methacrylate with trimethylolpropane tri(meth)acrylate. The polyoxane-based (co)polymer is more preferably a polyorganosilsesquioxane particle, and more preferably a polymethylsesquioxane particle.

In the present invention, in terms of excellent thermal stability, it is particularly preferred to be a polymethyl group. Sesquiterpene oxide particles.

The dispersed shape of the light diffusing element 4b in the resin 4c may be a spherical shape or a plate Any of the shape, the needle shape, and the indefinite shape is preferably a spherical shape in terms of the non-anisotropy of the light scattering effect. The average size of the light-diffusing element 4b is usually 100 μm or less, preferably 30 μm or less, more preferably 10 μm or less, and is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. Average size of light diffusing element 4b When the inch is not in the above range, there is a case where the light diffusibility is greatly changed by the difference in the subtle content or the difference in particle diameter of the light diffusing element 4b, and it is difficult to stably control the light diffusibility, and it is difficult to exert the present. Adequate light diffusibility necessary for the invention. Further, there is a possibility that it is difficult to stably control the wavelength conversion efficiency within a preferable range. Here, the average size of the light diffusing element 4b is a 50% average size obtained from a volume basis, and is a value of a volume-based particle size distribution median diameter (D50) measured by a laser or a diffraction scattering method. .

Moreover, the particle size distribution of the light diffusing element 4b may be a monodisperse system or A multi-dispersion system having a plurality of peaks, and may be a peak top, the particle size distribution may be narrower or wider, preferably a narrow particle size distribution and a substantially single particle size (monodisperse or close) Monodisperse particle size distribution).

As the light diffusing element represents the degree of particle size distribution index 4b, the light diffusing element ratio of the volume-based average particle diameter D of the _n-4b of the average particle diameter D _v of the reference number (D _v / D _n). In the invention of the present application, D _v / D _n is preferably 1.0 or more. On the other hand, D _v / D _n is preferably 5 or less. When D _v /D _{n is} too large, light diffusing elements 4b having different weights tend to be present, and dispersion of light diffusing elements 4b in wavelength converting member 4 tends to be uneven.

Inorganic light diffusing material or organic system used as the light diffusing element 4b described above The light-diffusing material and the air bubbles may be used singly or in combination of two or more materials or different sizes. When two or more types are used in combination, the refractive index of the light diffusing element 4b is calculated from the volume average of a plurality of kinds of light diffusing elements.

The refractive index of the light diffusing element 4b is usually 1.0 or more, and is usually 1.9 or less. The reason for this is explained when referring to the following evaluation results. Further, the light diffusing element 4b preferably has high transparency and excellent light transmittance, and for example, the extinction coefficient may be 10 ^{- 2} or less, preferably 10 ^{- 3} or less, more preferably 10 ^{- 4} or less, and particularly preferably It is 10 ^-6 or less. Further, the refractive index of the light diffusing element 4b can be measured by a liquid immersion method by YOSHIYAMA et al. (Aerosol Research Vol. 9, No. 1 Spring pp. 44-50 (1994)). The measurement temperature was 20 ° C and the measurement wavelength was 450 nm.

Table 1 below describes materials commonly used as the light diffusing element 4b. Refractive index. In addition, the refractive index of each material in Table 1 is a normal reference value, and the refractive index of each material is not necessarily limited to the value in Table 1.

[Table 1]

The content of the light diffusing element 4b in the wavelength converting member 4 depends on the type of the phosphor 4a and the resin 4c. For example, the resin 4c is a polycarbonate resin, and the light diffusing element 4b is a polymethylsesquioxane particle. In the case of 100 parts by weight of the polycarbonate resin, it is usually 0.1 part by weight or more, preferably 0.3 part by weight or more, more preferably 0.5 part by weight or more, and usually 10.0 parts by weight or less, preferably 7.0% by weight. The remainder is more preferably 3.0 parts by weight or less. When the content of the light diffusing element 4b is too small, the effect of diffusion is insufficient, and it is also difficult to obtain an effect of reducing the amount of the phosphor 4a. If the amount is too large, the mechanical specificity is lowered, which is not preferable.

Further, in the above-described phosphor 4a, yellow light is diffused. In the calculation of the volume fraction of the light diffusing element of the present invention, the phosphor 4a is not included as a part of the light diffusing element 4b.

[base material]

The base metal is a light diffusing element. Further, it is preferable to disperse the light diffusing element in the base material. In the present embodiment, it is preferable that the base material holds the phosphor and the phosphor is dispersed in the base material. As the base material, a resin, glass, or the like is usually used.

[resin]

The resin 4c in which the phosphor 4a and the light diffusing element 4b are dispersed and held usually has a refractive index of 1.3 or more and 1.7 or less. The reason for this is explained when referring to the following evaluation results. In addition, the measuring method of the refractive index of the resin 4c is as follows. The measurement temperature was 20 ° C, and the measurement was carried out by a 稜鏡 coupler method. The measurement wavelength is 450 nm.

Table 2 below describes the refractive index of a resin which is usually used as a base material. Further, the refractive index of each resin in Table 2 is a usual reference value, and the refractive index of each resin is not necessarily limited to the value in Table 2.

[Table 2]

As the more specific resin 4c, a polycarbonate resin, a polyester resin (for example, polyethylene terephthalate resin, polybutylene terephthalate resin), or an acrylic resin (for example, polymethyl) is preferably used. Methyl acrylate resin), epoxy resin, and polyoxynene resin. Further, it is preferable that the resin 4c does not absorb light emitted from the semiconductor light emitting element (for example, ultraviolet light, near ultraviolet light, or blue light) or visible light emitted from the wavelength conversion member. Further, it is preferable to have sufficient transparency and durability for blue light emitted from the LED chip 3.

These resins which are used as the resin 4c may be used alone or in combination of two or more. Further, it may be a copolymer of these resins, and may be used in combination of two or more layers. When two or more types are used in combination, the refractive index of the resin 4c is calculated from the volume average of a plurality of resins.

As the resin 4c, a polycarbonate resin is preferably used in terms of transparency, heat resistance, mechanical properties, and flame retardancy. The polycarbonate resin will be described in detail below.

The polycarbonate resin used in the present invention is a polymer having a basic structure of a carbonic acid bond represented by the following chemical formula (1).

In the chemical formula (1), X ¹ is usually a hydrocarbon, and in order to impart various properties, X ¹ into which a hetero atom or a hetero bond is introduced may be used.

Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon bonded directly to a carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin which is an aliphatic carbon, and any of them can be used. Among them, from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like, an aromatic polycarbonate resin is preferred.

The specific type of the polycarbonate resin is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method in which carbon dioxide is used as a carbonate precursor to react with a cyclic ether can also be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer having one repeating unit or a copolymer having two or more repeating units. In this case, the copolymer may be in various copolymerization forms such as a random copolymer or a block copolymer. Further, usually such a polycarbonate polymer is a thermoplastic resin.

Among the monomers which are raw materials of the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include 1,2-dihydroxybenzene and 1,3-dihydroxybenzene (that is, resorcin), and 1 Dihydroxybenzenes such as 4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl; 2,2 '-Dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-di Hydroxynaphthalene, 1,7- Dihydroxynaphthalenes such as dihydroxynaphthalene and 2,7-dihydroxynaphthalene; 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, etc. Dihydroxydiaryl ethers; 2,2-bis(4-hydroxyphenyl)propane (ie bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3- Methyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy- 4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane , 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α' - bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl) Methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyl) Phenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1-bis(4-hydroxyl) Ethylene, 2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl) 1-naphthylethane, 1-bis(4-hydroxyphenyl)butane, 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1 , 1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1-bis(4-hydroxyphenyl)octane, 2-bis(4-hydroxybenzene) Octane, 1-bis(4-hydroxyphenyl)hexane, 2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2- Bis(4-hydroxyphenyl)decane, 10-bis(4-hydroxyphenyl)decane, 1-bis(4-hydroxyphenyl)dodecane, etc. bis(hydroxyaryl)alkane; 1-double (4-hydroxyphenyl)cyclopentane, 1-bis(4-hydroxyphenyl)cyclohexane, 4-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3, 5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-di Methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-double (4-hydroxyphenyl)-3- Tributylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane , bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; 9,9-bis(4-hydroxyphenyl)anthracene, 9,9- Bisphenols containing cardo structure such as bis(4-hydroxy-3-methylphenyl)anthracene; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-di Dihydroxydiaryl sulfides such as methyl diphenyl sulfide; 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Dihydroxy diaryl fluorenes; 4,4'-dihydroxydiphenyl Dihydroxy diaryl hydrazines such as hydrazine and 4,4'-dihydroxy-3,3'-dimethyldiphenyl hydrazine.

Among these, bis(hydroxyaryl)alkanes are preferred, of which bis(4-hydroxyphenyl)alkanes are preferred, and 2,2- are particularly preferred in terms of impact resistance and heat resistance. Bis(4-hydroxyphenyl)propane (i.e., bisphenol A).

In addition, one type of the aromatic dihydroxy compound may be used, or two or more types may be used in combination and in any ratio.

Moreover, examples of the monomer which is a raw material of the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, and 2 , 2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5- Alkanediols such as diol, hexane-1,6-diol, decane-1,10-diol; cyclopentane-1,2-diol, cyclohexane-1,2-diol, Cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, 2,2,4,4-tetramethylcyclobutane-1 a cycloalkanediol such as a 3-diol; a glycol such as 2,2'-oxydiethanol (i.e., ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol or spirodiol; 2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-double (2-hydroxyethoxy)benzene, 2,3-bis(hydroxymethyl)naphthalene, 1,6-bis(hydroxyethoxy)naphthalene, 4,4'-biphenyldimethanol, 4,4'- An aralkyl group such as biphenyldiethanol, 1,4-bis(2-hydroxyethoxy)biphenyl, bisphenol A bis(2-hydroxyethyl)ether, bisphenol S bis(2-hydroxyethyl)ether Glycols; 1,2-ethylene oxide (ie ethylene oxide), 1,2- Propylene oxide (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl-1,2-epoxy Cyclohexane, 2,3-epoxy drop A cyclic ether such as an alkane or a 1,3-epoxypropane may be used alone or in combination of two or more kinds in any combination and in any ratio.

Among the monomers which are raw materials of the aromatic polycarbonate resin, examples of the carbonate precursor include a carbonyl halide, a carbonate, and the like. Further, one type of the carbonate precursor may be used, or two or more types may be used in any combination and in any ratio.

Specific examples of the carbonyl halide include carbonium chloride, a bischloroformate of a dihydroxy compound, and a haloformate such as a monochloroformate of a dihydroxy compound.

Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. a base ester; a dicarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, a carbonate of a dihydroxy compound such as a cyclic carbonate, or the like.

The method for producing the polycarbonate resin is not particularly limited and may be any one. law. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, the interfacial polymerization method and the melt transesterification method which are particularly preferable in the methods will be specifically described.

(Interfacial polymerization method)

The interfacial polymerization method is generally carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually maintained at 9 or higher, and the dihydroxy compound is reacted with a carbonate precursor (preferably carbon ruthenium chloride). Interfacial polymerization was carried out in the presence of a polymerization catalyst, whereby a polycarbonate resin was obtained. Further, a molecular weight modifier (terminal terminator) may be present in the reaction system as needed, and an antioxidant may be present in order to prevent oxidation of the dihydroxy compound.

The dihydroxy compound and the carbonate precursor are as described above. Further, it is preferable to use carbonium chloride in the carbonate precursor, and the method in the case of using carbonium chloride is specifically called the carbonium chloride method.

Examples of the organic solvent which is inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene, and xylene; Hydrocarbons, etc. In addition, one type of the organic solvent may be used, or two or more types may be used in any combination and in any ratio.

Examples of the basic compound contained in the alkaline aqueous solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate, and alkaline earth metal compounds. Among them, sodium hydroxide and hydroxide are preferred. Potassium. In addition, one type of the basic compound may be used, or two or more types may be used in combination and in any ratio.

The concentration of the basic compound in the alkaline aqueous solution is not limited, and the pH in the alkaline aqueous solution of the reaction is usually controlled to 10 to 12, and is used in an amount of 5 to 10% by weight. Further, for example, when carbonium chloride is blown, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11, the molar ratio of the bisphenol compound to the basic compound is usually 1:1.9 or more. Among them, it is preferably 1:2.0 or more, and is usually set to 1:3.2 or less, and preferably 1:2.5 or less.

Examples of the polymerization catalyst include trimethylamine, triethylamine, and tributylamine. An aliphatic tertiary amine such as tripropylamine or trihexylamine; an alicyclic tertiary amine such as N,N'-dimethylcyclohexylamine or N,N'-diethylcyclohexylamine; N,N'-di An aromatic tertiary amine such as methylaniline or N,N'-diethylaniline; a quaternary ammonium salt such as trimethylbenzylammonium chloride, tetramethylammonium chloride or triethylbenzylammonium chloride; Pyridine, guanine, salt of sputum, and the like. Further, one type of the polymerization catalyst may be used, or two or more types may be used in combination and in any ratio.

Examples of the molecular weight modifier include a monohydric phenolic hydroxyl group. An aromatic phenol; an aliphatic alcohol such as methanol or butanol; a mercaptan; phthalimide; and the like, among which aromatic phenol is preferred. Specific examples of such an aromatic phenol include an alkyl group such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, or a long-chain alkyl-substituted phenol. a substituted phenol, a vinyl group-containing phenol, an epoxy group-containing phenol, an o-(8-hydroxyquinoline) benzoic acid, a 2-methyl-6-hydroxyphenyl acetate or the like, and a carboxyl group-containing phenol. In addition, one type of the molecular weight modifier may be used, or two or more types may be used in combination and in any ratio.

The molecular weight modifier is used in an amount of 100 moles relative to the dihydroxy compound. It is usually 0.5 mole or more, preferably 1 mole or more, and is usually 50 moles or less, preferably 30 moles or less. By setting the amount of the molecular weight modifier to be in this range, the thermal stability and hydrolysis resistance of the polycarbonate resin composition can be improved.

In the reaction, mixing the reaction substrate, the reaction medium, the catalyst, the additive, etc. The order may be any as long as the desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, in the case where carbonium chloride is used as the carbonate precursor, the molecular weight modifier may be mixed at any time from the reaction of the dihydroxy compound to the carbonium chloride (carbonium chloride) to the start of the polymerization reaction. . Further, the reaction temperature is usually from 0 to 40 ° C, and the reaction time is usually from several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

(melt transesterification method)

In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is carried out.

The dihydroxy compound is as described above. On the other hand, as a carbonic acid diester, an example Examples thereof include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dibutyl butyl carbonate. An ester compound; diphenyl carbonate; a substituted diphenyl carbonate such as ditolyl carbonate. Among them, diphenyl carbonate and diphenyl carbonate are preferred, and diphenyl carbonate is preferred. Further, the carbonic acid diester may be used alone or in combination of two or more kinds in any combination.

The ratio of dihydroxy compound to carbonic acid diester as long as the desired aggregation is obtained The carbonate resin is arbitrary, and it is preferable to use a carbonic acid diester or more in an amount equal to or more than the molar amount of the dihydroxy compound, and more preferably 1.01 mole or more. Further, the upper limit is usually 1.30 m or less. By setting it as such a range, the terminal hydroxyl group can be adjusted to a preferable range.

In polycarbonate resin, the amount of terminal hydroxyl groups is stable to heat and hydrolysis. Qualitative, hue, etc. have a tendency to have a large influence. Therefore, the amount of terminal hydroxyl groups can be adjusted by any known method as needed. In the transesterification reaction, a polycarbonate resin having a terminal hydroxyl group-adjusted amount is usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction during the transesterification reaction, and the like. Further, by this operation, the molecular weight of the obtained polycarbonate resin can usually also be adjusted.

Adjusting the mixing ratio of carbonic acid diester and dihydroxy compound In the case of the amount of terminal hydroxyl groups, the mixing ratio thereof is as described above. Further, as a more aggressive adjustment method, a method of separately mixing a terminal terminator during the reaction can be mentioned. Examples of the terminal terminator at this time include monohydric phenols, monocarboxylic acids, and carbonic acid diesters. In addition, one type of terminal terminator may be used, or two or more types may be used in combination and in any ratio.

When a polycarbonate resin is produced by a melt transesterification method, an ester is usually used. Exchange catalyst. Any one can be used for the transesterification catalyst. Among them, for example, an alkali metal compound and/or an alkaline earth metal compound is preferably used. Further, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound may be used in combination. Further, one type of the transesterification catalyst may be used, or two or more types may be used in combination and in any ratio.

In the melt transesterification method, the reaction temperature is usually from 100 to 320 °C. Again The pressure at that time is usually a decompression condition of 2 mmHg or less. As a specific operation, the melt condensation condensation reaction may be carried out while removing by-products such as aromatic hydroxy compounds under the above conditions.

The melt polycondensation reaction can be carried out by any one of batch type and continuous type. Row. In the case of the batch type, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive, and the like may be any desired, and any appropriate order may be arbitrarily set as long as the desired aromatic polycarbonate resin is obtained. However, in consideration of the stability of the polycarbonate resin and the polycarbonate resin composition, etc., the melt polycondensation reaction is preferably carried out in a continuous manner.

In the melt transesterification method, a catalyst deactivator may be used as needed. As a catalyst As the deactivating agent, a compound which neutralizes the transesterification catalyst can be used arbitrarily. As an example, an acidic compound containing sulfur, a derivative thereof, etc. are mentioned. Further, one type of the catalyst deactivator may be used, or two or more types may be used in combination and in any ratio.

The amount of the catalyst deactivator used is relative to the above-mentioned transesterification catalyst. The alkali metal or alkaline earth metal is usually 0.5 equivalent or more, preferably 1 equivalent or more, and usually 10 equivalents or less, preferably 5 equivalents or less. Further, the amount is usually 1 ppm or more, and usually 100 ppm or less, and preferably 20 ppm or less, based on the aromatic polycarbonate resin.

The molecular weight of the polycarbonate resin is arbitrary, and it can be determined by appropriate selection. The viscosity average molecular weight [Mv] in terms of the viscosity of the solution is usually 10,000 or more, preferably 16,000 or more, more preferably 18,000 or more, and usually 40,000 or less, preferably 30,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and it is more preferable when it is used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is equal to or less than the upper limit of the above range, the fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the moldability can be improved, and the molding process can be easily performed. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be used in combination, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed.

In addition, the viscosity average molecular weight [Mv] refers to the use of methylene chloride as a solvent, and the ultimate viscosity [η] (unit: dl/g) at a temperature of 20 ° C is obtained by a Ubum viscosity meter, according to the viscosity type of Schnell, That is, η = 1.23 × 10 ^-4 Mv ^0.83 calculated value. In addition, the ultimate viscosity [η] is a value calculated by the following formula (1) by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g/dl).

The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary, and it is determined by appropriate selection. That is, it is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the retention heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. Further, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more. Thereby, the decrease in molecular weight can be suppressed, and the mechanical properties of the polycarbonate resin composition of the present invention can be further improved. Further, the unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group in ppm relative to the weight of the polycarbonate resin. The measurement method is the colorimetric quantification by the titanium tetrachloride/acetic acid method (method described in Macromol. Chem. 88215 (1965)).

Polycarbonate resin can be used alone or in any combination and ratio. Use two or more types.

For polycarbonate resin, polycarbonate resin can be used alone (so-called separate The polycarbonate resin is not limited to the one containing only one type of polycarbonate resin, and includes, for example, a meaning including a plurality of polycarbonate resins having a monomer composition or a molecular weight different from each other, or It is used in combination with a dopant (mixture) of polycarbonate resin and other thermoplastic resins. Further, for example, the polycarbonate resin may be in the form of a copolymer having a polycarbonate resin as a main component as follows: for the purpose of further improving flame retardancy or impact resistance and having a structure of a naphthene. a copolymer of a polymer or a polymer; a copolymer with a monomer, oligomer or polymer containing a phosphorus atom for the purpose of further improving thermal oxidation stability or flame retardancy; for the purpose of improving thermal oxidation stability a copolymer having a monomer, an oligomer or a polymer having a dihydroxyanthracene structure; a copolymer having an oligomer or a polymer having an olefin structure such as polystyrene for the purpose of improving optical properties; A copolymer of a polyester resin oligomer or a polymer for the purpose of chemical resistance. In the case of being used in combination with other thermoplastic resins, the ratio of the polycarbonate resin in the resin component is preferably 50% by weight or more, more preferably 60% by weight, still more preferably 70% by weight or more.

Moreover, in order to improve the appearance of the molded article or improve the fluidity, the poly The carbonate resin may also contain a polycarbonate oligomer. The polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Further, the polycarbonate oligomer to be contained is preferably 30% by weight or less of the polycarbonate resin (polycarbonate-containing oligomer).

Furthermore, the polycarbonate resin is not only a pure raw material but also used. The recycled polycarbonate resin (a polycarbonate resin which is recycled by the so-called material). Examples of the above-mentioned used products include optical recording media such as optical disks, light guide plates, vehicle transparent members such as automobile window glass, automobile headlight light distribution mirrors, and windshields; containers such as water bottles; lenses; soundproof walls and glass windows. Building components such as corrugated sheets. Further, it is also possible to use a pulverized product obtained from a defective product, a sprue, a flow path, or the like of the product, or a granule obtained by melting the same.

Wherein the recycled polycarbonate resin is in the polycarbonate resin group of the present invention The polycarbonate resin contained in the product is preferably 80% by weight or less, more preferably 50% by weight or less. The reason for this is that the recycled polycarbonate resin is highly likely to be deteriorated by thermal deterioration or deterioration over time, and therefore, when such a polycarbonate resin is used in a range larger than the above range, there is a decrease in hue or mechanical properties. The possibility.

In the above resin 4c, it is possible to not detract from the characteristics of the present invention. The internal vision needs to contain various known additives. Examples thereof include heat stabilizers, antioxidants, mold release agents, flame retardants, flame retardant aids, ultraviolet absorbers, slip agents, light stabilizers, plasticizers, antistatic agents, thermal conductivity improvers, and conductivity improvers. A coloring agent, an impact resistance improver, an antibacterial agent, a chemical resistance improver, a reinforcing agent, a laser mark improver, a refractive index adjuster, and the like. The specific kind or amount of the additives may be selected from those known for the resin 4c.

Here, preferred additives formulated in a polycarbonate resin are exemplified.

As a heat stabilizer, a phosphorus compound is mentioned, for example. Any known one can be used as the phosphorus compound. Specific examples thereof include phosphorus oxyacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acid pyrophosphate such as acid sodium pyrophosphate, acid potassium pyrophosphate, and acid calcium pyrophosphate. Metal salt; potassium phosphate, sodium phosphate, a phosphate of a Group 1 or Group 10 metal such as strontium phosphate or zinc phosphate; an organic phosphate compound, an organic phosphite compound, an organic phosphonite compound, or the like.

Among them, preferred is triphenyl phosphite, tris(monodecylphenyl) phosphite, Tris(monodecyl/didecyl-phenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, monooctyl diphenyl phosphite, dioctyl phosphite Phenyl ester, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylene bis (4 , an organic phosphite such as 6-di-t-butylphenyl)octyl phosphite.

The content of the heat stabilizer is usually 100 parts by weight relative to the polycarbonate resin. It is 0.001 part by weight or more, preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, further preferably 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.3 part by weight or less, and further preferably It is 0.1 parts by weight or less. If the amount of the heat stabilizer is too small, it is difficult to obtain a heat stability improving effect, and if it is too large, there is a case where the heat stability is lowered.

As an antioxidant, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 3-(3,5-di-t-butyl-4-hydroxyl). Phenyl) octadecyl propionate, thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane -1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6-(1-methylpentadecane Phenyl, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5' , 5"-hexa-t-butyl-a, a', a"-(mesitylene-2,4,6-triyl)tris-cresol, 4,6-bis(octylthiomethyl) O-cresol, exoethyl bis(oxyvinyl)bis[3-(5-tributyl-4-hydroxym-tolyl)propionate], hexamethylenebis[3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-three -2-ylamino)phenol and the like.

Among them, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3-(3,5-di-t-butyl-4-hydroxyphenyl) is preferred. ) Octadecyl propionate.

The content of the antioxidant is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 1 part by weight based on 100 parts by weight of the polycarbonate resin. Hereinafter, it is preferably 0.5 parts by weight or less, more preferably 0.3 parts by weight or less. When the content of the antioxidant is less than or equal to the lower limit of the above range, there is a possibility that the effect as an antioxidant is insufficient, and when the content of the antioxidant exceeds the upper limit of the above range, the effect is reached. Uneconomic possibility.

Examples of the release agent include aliphatic carboxylic acids, aliphatic carboxylic acids, and alcohols. The ester, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, a polyoxyalkylene-based eucalyptus oil or the like.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic mono-, di- or tricarboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the aliphatic carboxylic acid is preferably a mono- or dicarboxylic acid having 6 to 36 carbon atoms, and more preferably an aliphatic saturated monocarboxylic acid having 6 to 36 carbon atoms. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lauric acid, wax acid, beeswaxic acid, and tetradecanoic acid. , montanic acid, adipic acid, sebacic acid, and the like.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same as the above aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include a saturated or unsaturated mono- or polyhydric alcohol. These alcohols may also contain a substituent such as a fluorine atom or an aryl group. Among these, a saturated alcohol having one or more carbon atoms of 30 or less is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having a carbon number of 30 or less is further preferable.

Specific examples of the alcohol include octanol, decyl alcohol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, and 2,2-dihydroxyperfluoropropane. Alcohol, neopentyl glycol, bis(trimethylolpropane), dipentaerythritol, and the like.

Specific examples of the ester of the aliphatic carboxylic acid and the alcohol include beeswax (a mixture containing bee stearate as a main component), stearyl stearate, behenyl behenate, and stearic acid. Ester, glycerol monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol Tristearate, pentaerythritol tetrastearate, and the like.

Examples of the aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch Waxes, and α-olefin having a carbon number of 3 to 12. Polymer, etc. Furthermore, here, as an aliphatic hydrocarbon, Also included are alicyclic hydrocarbons.

Among these, a part of oxides of paraffin wax, polyethylene wax or polyethylene wax is preferable, and paraffin wax and polyethylene wax are further preferable.

Further, the number average molecular weight of the above aliphatic hydrocarbon is preferably 5,000 or less.

Examples of the polyoxyalkylene-based eucalyptus oil include dimethyl hydrazine oil, phenylmethyl hydrazine oil, diphenyl sulfonium oil, and fluorinated alkyl polyfluorene.

The content of the releasing agent is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 100 parts by weight or more based on 100 parts by weight of the polycarbonate resin. 1 part by weight or less, further preferably 0.5 part by weight or less. When the content of the release agent is below the lower limit of the above range, the release effect may be insufficient. When the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance may occur. The possibility of reducing or injecting mold contamination during molding.

Examples of the flame retardant include a halogen-based, phosphorus-based, organic acid metal salt-based, and polyfluorene-based flame retardant. Examples of the flame retardant auxiliary include a fluororesin-based flame retardant auxiliary. The flame retardant and the flame retardant auxiliary may be used in combination, or may be used in combination of a plurality of types. Among them, preferred are phosphorus-based flame retardants, organic acid metal salt-based flame retardants, and fluororesin-based flame retardant additives.

Examples of the phosphorus-based flame retardant include an aromatic phosphate or a phosphazene compound. The organic acid metal salt-based flame retardant is preferably an organic sulfonic acid metal salt, and more preferably a fluorine-containing organic sulfonic acid metal salt. Specific examples thereof include potassium perfluorobutanesulfonate. The fluorine-based flame retardant auxiliary agent is preferably a fluoroolefin resin, and examples thereof include a tetrafluoroethylene resin having a fibril structure. The fluorine-based flame retardant auxiliary agent may be in the form of a powder, a dispersion liquid, or a powder of a fluororesin coated with another resin.

The blending ratio of the flame retardant and the flame retardant auxiliary may be adjusted to achieve the desired flame retardancy level, and is usually in the case of a phosphorus-based flame retardant with respect to 100 parts by weight of the polycarbonate. It is preferably formulated in the range of 1 to 20 parts by weight, preferably in the range of 0.01 to 1 part by weight in the case of the organic acid metal salt, and preferably in the case of the fluororesin-based flame retardant. It is formulated in a range of 0.01 to 1 part by weight. Within the above range, one type or two or more types of flame retardant and flame retardant auxiliary agent can be used. If it is less than this range, it is difficult to exhibit the effect of improving the flame retardancy, and if it is more than this range, it is thermally stable and mechanical. The tendency to reduce the characteristics is therefore not good. Further, the flame retardance level can be determined by a combustion test represented by, for example, UL94.

Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, diphenyl ketone compounds, salicylate compounds, cyanoacrylate compounds, and the like. An organic ultraviolet absorber such as a compound, a grassy anilide compound, a malonic ester compound or a hindered amine compound. Among these, an organic ultraviolet absorber is preferred, and among them, a benzotriazole compound is more preferred. The transparency or mechanical properties of the polycarbonate resin composition of the present invention tend to be good by selecting an organic ultraviolet absorber.

Specific examples of the benzotriazole compound include, for example, 2-(2'-hydroxyl group). -5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 2- (2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)- 5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-di-p-pentyl)benzotriazole, 2-(2'-hydroxy-5'-th-octylphenyl)benzotriazole, 2,2'-methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], among which 2-(2'-hydroxy-5'-third is preferred Octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2- Phenyl], more preferably 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole.

Specific examples of such a benzotriazole compound include Shipro. "Seesorb 701", "Seesorb 702", "Seesorb 703", "Seesorb 704", "Seesorb 705", "Seesorb 709" manufactured by Kasei Corporation (product name, the same below), "Viosorb 520" manufactured by Kokusai Pharmaceutical Co., Ltd. "Viosorb 580", "Viosorb 582", "Viosorb 583", "Chemisorb 71" and "Chemisorb 72" manufactured by Chemipro Kasei, "Cyasorb UV5411" manufactured by Cytec Industries, and "LA-32" manufactured by Adeka "LA-38", "LA-36", "LA-34", "LA-31", "TINUVIN P", "TINUVIN 234", "TINUVIN 326", "TINUVIN 327" manufactured by Ciba Specialty Chemicals , "TINUVIN 328" and so on.

The preferred content of the ultraviolet absorber is relative to the polycarbonate resin 100 The amount is 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and further, 5 weights. The amount is preferably 3% by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 part by weight or less. When the content of the ultraviolet absorber is less than or equal to the lower limit of the above range, the effect of improving the weather resistance may be insufficient. When the content of the ultraviolet absorber exceeds the upper limit of the above range, there is a case where the ultraviolet absorber is insufficient. Produce mold deposits, etc., causing the possibility of mold contamination. In addition, one type of the ultraviolet absorber may be contained, and two or more types may be contained in any combination and in any ratio.

[Method of Manufacturing Resin Composition constituting Wavelength Conversion Member 4]

The method for producing the resin composition constituting the wavelength conversion member 4 and the method for processing the wavelength conversion member 4 are not particularly limited, and a method known as a processing method of the resin 4c may be used. For example, a general manufacturing method of the resin composition in the case where the resin 4c is a polycarbonate resin is as follows.

Adding the phosphor 4a, the light diffusing element 4b, and the polycarbonate resin The other components to be blended as needed are mixed by various mixers such as a tumbler mixer or a Henschel mixer. The mixing may be a one-time mixing of all the raw materials, or may be divided into several raw materials for mixing. Thereafter, the mixture is melt-kneaded by a Banbury mixer, a roll, a Brabender machine, a uniaxial kneading extruder, a biaxial kneading extruder, a kneader, or the like to obtain resin composition pellets.

Using the obtained resin composition particles, extruded by a sheet/film or the like Any of various molding methods such as extrusion molding, vacuum molding, injection molding, blow molding, injection blow molding, rotational molding, and foam molding to form the wavelength conversion member 4 having a desired shape. Among them, an injection molding method is preferably employed. Further, the molded body may be subjected to processing such as welding, subsequent cutting, or the like as needed. Further, when the light diffusing element 4b is a bubble, the bubble may be formed in the member by a method such as a foaming agent blending, a nitrogen gas injection, or a supercritical gas injection.

Regarding the case where the resin 4c is a polycarbonate resin, the light diffusing element 4b Preferred conditions are further exemplified in the case of bubbles.

The polycarbonate resin and the phosphor 4a and the light are diffused by a roller mixer After mixing 4b and other additives, the mixture is melted and kneaded using a uniaxial or twin screw extruder. As a condition of melt kneading, the screw system is constructed using a screw element that is sequentially conveyed. Become a screw without excessively applying shear. It is often unfavorable to use a screw element such as a threaded screw or a rotary screw element that is reversely conveyed to load a strong shear force, which causes discoloration of the resin. Further, when the phosphor 4a is hard, it is preferable to use a material which is hard to be worn and which is subjected to abrasion treatment as a material of the screw or the cylinder.

Further, the kneading temperature is preferably in the range of 230 to 340 °C. When the measured resin temperature exceeds 340 ° C, the color is liable to be discolored, which is not preferable. If the resin temperature is less than 230 ° C, the melt viscosity of the polycarbonate resin is too high, and the mechanical load on the extruder is increased, which is not preferable. The better mixing temperature is 240~300 °C.

The screw rotation speed and the discharge amount may be appropriately selected depending on the production speed, the load on the extruder, and the state of the resin pellets. Moreover, it is preferable to provide one or more vent hole structures in which the air which is wound together with the raw material and the gas generated by heating are discharged to the outside of the extruder system in the extruder.

The polycarbonate resin composition particles obtained by the above method can be formed into a desired shape by any processing method.

The semiconductor light-emitting device 1 of the present embodiment having the above configuration can be used as general illumination. In this case, the light emitted by the semiconductor light-emitting device 1 (specifically, the combined light of blue light and yellow light, that is, white light) preferably has a deviation duv of -0.0200 to 0.0200 from the black body radiation track, and the color temperature is preferably at Within the range of 1,600 K to 7,000 K.

Further, the semiconductor light-emitting device 1 of the present embodiment having the above-described configuration can be used as a backlight in addition to general illumination. In the case of an LED light source used as a backlight of a display, the color temperature of the light emitted by the semiconductor light-emitting device 1 (specifically, the combined light of blue light and yellow light, that is, white light) is usually in the range of 5,000 K to 20,000 K. .

(evaluation by simulation)

In the semiconductor light-emitting device 1 of the present embodiment, the materials and characteristics of the YAG (Yttrium Aluminum Garnet) phosphor 4a, the light diffusing element 4b, and the resin 4c are changed and calculated by simulation. The calculation results (simulation results) of the luminous efficiency of each semiconductor light-emitting device were evaluated. As a more specific condition, the characteristics (refractive index, extinction coefficient, and quantum efficiency) of the phosphor 4a are referred to the well-known publication "Zongyuan Liu, three other, "YAG: Ce fluorescent for packaging of white light-emitting diodes" Measurement and numerical studies of optical properties of YAG (Ce phosphor for white light-emitting diode packaging), Applied Optics (APPLIED OPTICS), January 10, 2010, Vol. 49 , No. 2, p.247~257』. Moreover, the reflectance of visible light of the wiring board 2 is 90%, the extinction coefficient of the light-diffusion element 4b is ^10-6 or less, and the extinction coefficient of the light absorption rate of the resin 4c is ^10-6 or less. Further, the target chromaticity of the semiconductor light-emitting device 1 is set to x=0.30 and y=0.31. Then, regarding the average particle diameter and particle size distribution of the light diffusing element 4b, and the average particle diameter and particle size distribution of the phosphor 4a, it is assumed that Light Suite (Light Tools (or Synopsis) is used in the illumination design analysis software of the ORA company (now Synopsis). Registered trademark), simulation is performed by ray tracing method. The simulation results will be described in detail with reference to Tables 3 to 8, and Figs. 5 and 6, and the favorable conditions of the wavelength conversion member 4 will be described. In addition, in Tables 3 to 8, the value of the "volume fraction of the light diffusing element" is rounded off to the third digit after the decimal point and recorded to the second digit after the decimal point, and the "refractive index difference × thickness × volume fraction" is calculated. In the case of the value of the "rate", since the "volume fraction of the light diffusing element" is calculated using the value of the fourth digit after the decimal point, the recorded value and the actual value of the "refractive index difference x thickness x volume fraction" are present. A situation in which a deviation occurs between the calculated values.

As the first sample group, it is assumed that the light diffusing element 4b uses cerium oxide, In the case where the resin 4c is a polycarbonate resin, the luminous efficiency (lm/W) of each of the semiconductor light-emitting devices when the amount of use (volume fraction) of the ceria as the light-diffusing element 4b is changed is calculated by simulation. As a specific condition, in the sample 1-1, the wavelength conversion member 4 does not contain ceria as the light diffusion element 4b, and the phosphor 4a and the polycarbonate resin as the resin 4c constitute the wavelength conversion member 4. . Further, the wavelength conversion member 4 of the sample 1-2 to the sample 1-20 contains cerium oxide as the light diffusing element 4b, and is composed of the phosphor 4a, the light diffusing element 4b, and the polycarbonate resin as the resin 4c. The wavelength conversion member 4 increases the content of the light diffusion element 4b as the sample number becomes larger, and increases the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the first sample group, it is assumed that the light diffusing element 4b is made of cerium oxide and the resin 4c is made of a polycarbonate resin. Therefore, the refractive index at 450 nm at a measurement temperature of 20 ° C is set by the light diffusing element 4b. The resin 4c was set to 1.58. Further, the density of the light diffusing element 4b was set to 2.20 g/cm ³ , and the density of the resin 4c was set to 1.20 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

Table 3 below shows the "volume fraction (vol%) of the light diffusing element 4b" in each sample (semiconductor light-emitting device 1), "the refractive index difference × the thickness of the wavelength converting member 4 itself × the volume of the light diffusing element 4b" Fraction", "Use concentration of phosphor 4a (wt%)", "Reduction rate (%) of the concentration of phosphor 4a", "Luminous efficiency (lm/W)", and "Maintenance of luminous efficiency" rate(%)". Here, the "reduction rate (%) of the use concentration of the phosphor 4a" is the use concentration of the phosphor 4a in the sample 1-1 and the use concentration of the phosphor 4a in each of the other samples. The difference is divided by the use concentration of the phosphor 4a in the sample 1-1, and the obtained value is multiplied by 100. In addition, the "luminescence efficiency retention rate (%)" is based on the luminous efficiency in the sample 1-1 (100%), and the luminous efficiency of each of the other samples is divided by the luminescence in the sample 1-1. Efficiency, then multiply the value obtained by 100.

[table 3]

As shown in Table 3, in the first sample group, when the refractive index difference between the light diffusing element and the base material is × the thickness of the light conversion member × the volume fraction of the light diffusing element is 0.743, the phosphor 4a can be used. The use concentration was reduced by 85.8%, and the luminous efficiency retention rate was 91.5%.

Further, when the refractive index difference between the light diffusing element and the base material × the thickness of the light converting member × the volume fraction of the light diffusing element is 2.463, the use concentration of the phosphor 4a can be reduced by 91.1%, and the light is emitted at this time. The efficiency maintenance rate was 75.7%. That is, in this case, it is also possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

Further, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element exceeds 3.467, the reduction ratio of the use concentration of the phosphor 4a can be reduced by 90.7%. However, the maintenance rate of luminous efficiency is less than 70%.

In other words, in the first sample group, the refractive index difference between the light diffusion element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusion element is set to an appropriate range, and the fluorescence can be reduced. The concentration of the body 4a is used, and the luminous efficiency can be sufficiently maintained.

In the second sample group, when the light diffusing element 4b is made of cerium oxide or the resin 4c, the amount of the cerium oxide used as the light diffusing element 4b (volume fraction) is calculated by simulation. The luminous efficiency (lm/W) of each semiconductor light-emitting device at that time. As a specific condition, in the sample 2-1, the wavelength conversion member 4 does not contain ceria as the light diffusion element 4b, and the phosphor 4a and the polyoxyl resin as the resin 4c constitute the wavelength conversion member 4. . Further, the wavelength conversion member 4 of the sample 2-2 to the sample 2-19 contains cerium oxide as the light diffusion element 4b, and the phosphor 4a, the light diffusion element 4b, and the polyoxyl resin as the resin 4c. The wavelength conversion member 4 is configured to increase the content of the light diffusion element 4b as the sample number increases, and increase the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the second sample group, it is assumed that the light diffusing element 4b is made of cerium oxide or the resin 4c, and the light diffusing element 4b is set as the refractive index at 450 nm at a measurement temperature of 20 ° C. The resin 4c was set to 1.40. Further, the density of the light diffusing element 4b was set to 2.20 g/cm ³ , and the density of the resin 4c was set to 1.00 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

Table 4 below shows "light expansion" of each sample (semiconductor light-emitting device 1) Volume fraction (vol%) of the bulk element 4b, "refractive index difference x thickness of the wavelength converting member 4 itself × volume fraction of the light diffusing element 4b", "concentration (% by weight) of the phosphor 4a", "Reduction rate (%) of the use concentration of the phosphor 4a", "luminance efficiency (lm/W)", and "maintenance rate (%) of luminous efficiency". In addition, the "reduction rate (%) of the use concentration of the phosphor 4a" and the "maintenance rate (%) of the luminous efficiency" are the same as those defined in Table 3.

[Table 4]

As shown in Table 4, in the second sample group, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element is 0.240, the phosphor 4a can be used. The use concentration was reduced by 55.0%, and the luminous efficiency retention rate was 95.2%.

Further, when the refractive index difference between the light diffusing element and the base material × the thickness of the light converting member × the volume fraction of the light diffusing element is 1.563, the use concentration of the phosphor 4a can be reduced by 82.1%, and the light is emitted at this time. The efficiency maintenance rate was 90.4%. That is, in this case, it is also possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

In other words, in the second sample group, the refractive index difference between the light diffusing element and the base material, the thickness of the light conversion member, and the volume fraction of the light diffusing element are set to an appropriate range. 1 sample group-like luminous efficiency maintenance effect, but can also reduce fluorescence The concentration of the body 4a is used, and the luminous efficiency can be sufficiently maintained.

As the third sample group, it is assumed that the light diffusing element 4b uses alumina, a tree. In the case where a polycarbonate resin is used as the grease 4c, the luminous efficiency (lm/W) of each of the semiconductor light-emitting devices when the amount of alumina used as the light-diffusing element 4b (volume fraction) is changed by simulation is calculated. As a specific condition, in the sample 3-1, the wavelength conversion member 4 does not contain alumina as the light diffusion element 4b, and the phosphor 4a and the polycarbonate resin as the resin 4c constitute the wavelength conversion member 4. Further, the wavelength conversion member 4 of the sample 3-2 to the sample 3-20 contains alumina as the light diffusion element 4b, and the wavelength is composed of the phosphor 4a, the light diffusion element 4b, and the polycarbonate resin as the resin 4c. The conversion member 4 increases the content of the light diffusion element 4b as the sample number increases, and increases the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the third sample group, it is assumed that the light diffusing element 4b is made of alumina and the resin 4c is made of a polycarbonate resin. Therefore, the light diffusing element 4b is set to 1.75 as the refractive index at a measurement temperature of 20 ° C at 450 nm. The resin 4c was set to 1.58. Further, the density of the light diffusing element 4b was set to 4.00 g/cm ³ , and the density of the resin 4c was set to 1.20 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

Table 5 below shows "light expansion" of each sample (semiconductor light-emitting device 1) Volume fraction (vol%) of the bulk element 4b, "refractive index difference x thickness of the wavelength converting member 4 itself × volume fraction of the light diffusing element 4b", "concentration (% by weight) of the phosphor 4a", "Reduction rate (%) of the use concentration of the phosphor 4a", "luminance efficiency (lm/W)", and "maintenance rate (%) of luminous efficiency". In addition, the "reduction rate (%) of the use concentration of the phosphor 4a" and the "maintenance rate (%) of the luminous efficiency" are the same as those defined in Table 3.

[table 5]

As shown in Table 5, in the third sample group, when the refractive index difference between the light diffusing element and the base material is × the thickness of the light converting member × the volume fraction of the light diffusing element is 0.548, the phosphor 4a can be used. The use concentration was reduced by 87.2%, and the retention rate of luminous efficiency was 90.1%.

Further, when the refractive index difference between the light diffusing element and the base material × the thickness of the light converting member × the volume fraction of the light diffusing element is 1.186, the use concentration of the phosphor 4a can be reduced by 91.2%, and the light is emitted at this time. The efficiency maintenance rate was 84.1%. That is, in this case, it is also possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

Further, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element exceeds 1.937, the reduction ratio of the use concentration of the phosphor 4a exceeds 91.7%, but The luminous efficiency maintenance rate is less than 70%.

In other words, in the third sample group, the refractive index difference between the light diffusing element and the base material, the thickness of the light conversion member, and the volume fraction of the light diffusing element are set to an appropriate range, and the first test is performed. Similarly, the concentration of the phosphor 4a can be reduced, and the luminous efficiency can be sufficiently maintained.

As the fourth sample group, it is assumed that the light diffusing element 4b uses alumina and a tree. In the case where the grease 4c is a polyoxyxylene resin, the luminous efficiency (lm/W) of each semiconductor light-emitting device when the amount of use (volume fraction) of the alumina as the light-diffusing element 4b is changed is calculated by simulation. As a specific condition, in the sample 4-1, the wavelength conversion member 4 does not contain alumina as the light diffusion element 4b, and the wavelength conversion member 4 is composed of the phosphor 4a and the polyoxymethylene resin as the resin 4c. Further, the wavelength conversion member 4 of the sample 4-2 to the sample 4-19 contains alumina as the light diffusion element 4b, and the wavelength is composed of the phosphor 4a, the light diffusion element 4b, and the polyoxyl resin as the resin 4c. The conversion member 4 increases the content of the light diffusion element 4b as the sample number increases, and increases the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the fourth sample group, it is assumed that the light diffusing element 4b is made of alumina and the resin 4c is made of polyoxynoxy resin. Therefore, the refractive index at 450 nm is 20 ° C, and the light diffusing element 4b is set to 1.75. The resin 4c was set to 1.40. Further, the density of the light diffusing element 4b was set to 4.00 g/cm ³ , and the density of the resin 4c was set to 1.00 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

In the following Table 6, the "volume fraction (vol%) of the light diffusing element 4b" and the "refractive index difference x the thickness of the wavelength converting member 4 itself × the volume of the light diffusing element 4b" of each sample (semiconductor light-emitting device 1) are shown. Fraction", "Use concentration of phosphor 4a (wt%)", "Reduction rate (%) of the concentration of phosphor 4a", "Luminous efficiency (lm/W)", and "Maintenance of luminous efficiency" rate(%)". In addition, the "reduction rate (%) of the use concentration of the phosphor 4a" and the "maintenance rate (%) of the luminous efficiency" are the same as those defined in Table 3.

[Table 6]

As shown in Table 6, in the fourth sample group, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element is 0.178, the phosphor 4a can be used. The use concentration was reduced to 80.4%, and the luminous efficiency retention rate was 91.1%.

Further, when the refractive index difference between the light diffusing element and the base material is × the thickness of the light converting member × the volume fraction of the light diffusing element is 0.946, the use concentration of the phosphor 4a can be reduced by 93.0%, and the light is emitted at this time. The efficiency maintenance rate was 71.7%. That is, in this case, it is also possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

Further, when the refractive index difference between the light diffusing element and the base material, the thickness of the light conversion member, and the volume fraction of the light diffusing element exceed 0.946, the reduction ratio of the use concentration of the phosphor 4a exceeds 93.0%. The luminous efficiency maintenance rate is less than 70%.

In other words, in the fourth sample group, the refractive index difference between the light diffusing element and the base material, the thickness of the light conversion member, and the volume fraction of the light diffusing element are set to an appropriate range, and the first test is performed. Similarly, the concentration of the phosphor 4a can be reduced, and the luminous efficiency can be sufficiently maintained.

As the fifth sample group, it is assumed that the light diffusing element 4b uses bubbles and resin. In the case of using a polycarbonate resin in 4c, the luminous efficiency (lm/W) of each of the semiconductor light-emitting devices when the content (volume fraction) of the bubbles as the light-diffusing element 4b is changed is calculated by simulation. As a specific condition, in the sample 5-1, the wavelength conversion member 4 does not contain the bubble as the light diffusion element 4b, and the phosphor 4a and the polycarbonate resin as the resin 4c constitute the wavelength conversion member 4. Further, the wavelength conversion member 4 of the sample 5-2 to the sample 5-7 contains bubbles as the light diffusion element 4b, and the wavelength is composed of the phosphor 4a, the light diffusion element 4b, and the polycarbonate resin as the resin 4c. The conversion member 4 increases the content of the light diffusion element 4b as the sample number increases, and increases the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the fifth sample group, it is assumed that the light diffusing element 4b is a bubble and the resin 4c is a polycarbonate resin. Therefore, the light diffusing element 4b is set to 1.00 as a refractive index at a measurement temperature of 20 ° C at 450 nm. The resin 4c was set to 1.58. Further, the density of the light diffusing element 4b was set to 0.001 g/cm ³ , and the density of the resin 4c was set to 1.2 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

Table 7 below shows "volume fraction (vol%) of light diffusing element 4b" in each sample (semiconductor light-emitting device 1), "refractive index difference × thickness of wavelength converting member 4 itself × volume of light diffusing element 4b" Fraction", "Use concentration of phosphor 4a (wt%)", "Reduction rate (%) of the concentration of phosphor 4a", "Luminous efficiency (lm/W)", and "Maintenance of luminous efficiency" rate(%)". In addition, the "reduction rate (%) of the use concentration of the phosphor 4a" and the "maintenance rate (%) of the luminous efficiency" are the same as those defined in Table 3.

[Table 7]

As shown in Table 7, in the fifth sample group, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element is 0.415, the phosphor 4a can be used. The use concentration was reduced to 88.0%, and the luminous efficiency retention rate was 90.2%.

In addition, when the refractive index difference between the light diffusing element and the base material, the thickness of the light conversion member, and the volume fraction of the light diffusing element exceed 0.415, the reduction ratio of the use concentration of the phosphor 4a exceeds 88.0%. The maintenance rate of luminous efficiency is less than 90%. However, even in this case, it is possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

In the sixth sample group, when the light-diffusing element 4b is a barium fluoride and the resin 4c is a polyoxyxene resin, the content (volume fraction) of the barium fluoride as the light diffusing element 4b is changed by simulation. The luminous efficiency (lm/W) of each of the semiconductor light-emitting devices. As a specific condition, in the sample 6-1, the wavelength conversion member 4 does not contain cesium fluoride as the light diffusion element 4b, and the phosphor 4a and the polyoxyl resin as the resin 4c constitute the wavelength conversion member 4. . Further, the wavelength conversion member 4 of the sample 6-2 to the sample 6-20 contains cesium fluoride as the light diffusion element 4b, and the phosphor 4a, the light diffusion element 4b, and the polyoxyl resin as the resin 4c. The wavelength conversion member 4 is configured to increase the content of the light diffusion element 4b as the sample number increases, and increase the volume fraction (vol%) of the light diffusion element 4b.

In the simulation of the sixth sample group, it is assumed that the light diffusing element 4b is made of barium fluoride and the resin 4c is made of polyfluorene oxide. Therefore, the light diffusing element 4b is set to have a refractive index at 450 nm at a measurement temperature of 20 ° C. 1.48, the resin 4c was set to 1.40. Further, the density of the light diffusing element 4b was 4.9 g/cm ³ , and the density of the resin 4c was 1.0 g/cm ³ . Further, the thickness of the wavelength conversion member 4 itself (that is, the thickness of the resin 4c) was set to 1.00 mm.

Table 8 below shows "volume fraction (vol%) of light diffusing element 4b" in each sample (semiconductor light-emitting device 1), "refractive index difference × thickness of wavelength converting member 4 itself × volume of light diffusing element 4b" Fraction", "Use concentration of phosphor 4a (wt%)", "Reduction rate (%) of the concentration of phosphor 4a", "Luminous efficiency (lm/W)", and "Maintenance of luminous efficiency" rate(%)". In addition, the "reduction rate (%) of the use concentration of the phosphor 4a" and the "maintenance rate (%) of the luminous efficiency" are the same as those defined in Table 3.

[Table 8]

As shown in Table 8, in the sixth sample group, when the refractive index difference between the light diffusing element and the base material × the thickness of the light conversion member × the volume fraction of the light diffusing element is 0.760, the phosphor 4a can be used. The use concentration was reduced to 80.8%, and the luminous efficiency retention rate was 92.0%.

Further, when the refractive index difference between the light diffusing element and the base material, the thickness of the light converting member, and the volume fraction of the light diffusing element exceed 1.5, the reduction ratio of the use concentration of the phosphor 4a exceeds 85.0%. The maintenance rate of luminous efficiency is less than 90%. However, even in this case, it is possible to ensure a value (70% or more) of the maintenance rate of the luminous efficiency in which good characteristics are generally obtained.

Based on the results of Tables 3 to 8, "the absolute value of the refractive index difference between the light diffusion element 4b and the resin 4c" in each of the samples from the first sample group to the sixth sample group × (wavelength conversion member) The relationship between the thickness of 4 itself (the volume fraction of the light diffusing element 4b) and the "concentration of the phosphor 4a" (the thickness of the wavelength converting member 4 itself) and "(the light diffusing element 4b and The relationship between the absolute value of the refractive index difference of the resin 4c (the thickness of the wavelength conversion member 4 itself) × (the volume fraction of the light diffusion element 4b) and the "luminous efficiency" is shown in the graph. Fig. 5 is a diagram showing the former, and Fig. 6 is a diagram showing the latter.

According to the simulation result, when the wavelength conversion member 4 does not contain the light diffusion element 4b, the retention rate of the luminous efficiency of 70% or more can be secured, and the content of the phosphor 4a can be lowered. Under the conditions, the conditions shown in the following formula (2) were found.

0.01 ≦ | (refractive index of light diffusing element) - (refractive index of base material) × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) ≦ 1.0 (2)

In addition, in the case where the wavelength conversion member 4 does not include the light diffusing element 4b, the retention rate of the luminous efficiency of 80% or more can be ensured, and the phosphor 4a can be lowered. Under the conditions of the content rate, the conditions shown in the following formula (3) were found.

0.01 ≦ | (refractive index of light diffusing element) - (refractive index of base material) | × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) ≦ 0.6 (3)

Further, according to the simulation result, when the wavelength conversion member 4 does not include the light diffusion element 4b, the maintenance ratio of the luminous efficiency of 90% or more can be secured, and the phosphor 4a can be lowered. Under the conditions of the content rate, the conditions shown in the following formula (4) were found.

0.01 ≦ | (refractive index of light diffusing element) - (refractive index of base material) | × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element [vol%]) ≦ 0.2 (4)

In addition, it is preferable to select one of the above equations (2) to (4), and based on the above simulation result, it is preferable to select a refractive index of 1.0 or more and 1.9 or less as the light diffusion element 4b. The refractive index is 1.3 or more and 1.7 or less as the resin 4c. Further, the difference between the refractive index of the light diffusing element 4b and the refractive index of the resin 4c as the base material is preferably 0.07 or more, more preferably 0.10 or more.

Secondly, it is known that the above formula (2) and the light diffusing element 4b are satisfied. In the case of the condition of the refractive index of the resin 4c, the reduction ratio of the phosphor 4a is 3.0% to 93%. This value is based on the simulation results of Samples 2-4 and 4-16. This is because the sample 2-4 "(the absolute value of the difference in refractive index between the light diffusing element 4b and the resin 4c) × (the thickness of the wavelength converting member 4 itself) × (the volume fraction of the light diffusing element 4b) is The minimum value of the lower limit of the above formula (2) is satisfied, and "the absolute value of the refractive index difference between the light diffusing element 4b and the resin 4c" of the sample 4-16 × (the thickness of the wavelength converting member 4 itself) × (Volume fraction of light diffusing element 4b) is a maximum value that satisfies the upper limit of the above formula (2).

It is also known that the above equation (3) and the light diffusing element 4b are satisfied. In the case of the condition of the refractive index of the resin 4c, the reduction ratio of the phosphor 4a is 3.0% to 91%. This value is based on the simulation results of Samples 2-4 and 5-7. This is because the sample 2-4 "(the absolute value of the difference in refractive index between the light diffusing element 4b and the resin 4c) × (the thickness of the wavelength converting member 4 itself) × (the volume fraction of the light diffusing element 4b) is The minimum value of the lower limit of the above formula (3) is satisfied, and "the absolute value of the refractive index difference between the light diffusing element 4b and the resin 4c" of the sample 5-7 × (the thickness of the wavelength converting member 4 itself) × (Volume fraction of light diffusing element 4b) is a maximum value that satisfies the upper limit of the above formula (3).

Further, it is known that the above equation (4) and the light diffusing element 4b are satisfied. In the case of the condition of the refractive index of the resin 4c, the reduction ratio of the phosphor 4a is 3.0% to 86%. This value is based on the simulation results of Samples 2-4 and 5-4. This is because the sample 2-4 "(the absolute value of the difference in refractive index between the light diffusing element 4b and the resin 4c) × (the thickness of the wavelength converting member 4 itself) × (the volume fraction of the light diffusing element 4b) is The minimum value of the lower limit of the above formula (4) is satisfied, and "the absolute value of the refractive index difference between the light diffusing element 4b and the resin 4c" of the sample 5-4 × (the thickness of the wavelength converting member 4 itself) × (Volume fraction of light diffusing element 4b) is a maximum value that satisfies the upper limit of the above formula (4).

According to the above, if the above formula (4) and the light diffusing element are satisfied The condition of the refractive index of 4b and the resin 4c is based on the concentration [wt%] of the phosphor 4a when the wavelength conversion member 4 that emits the light of the same chromaticity is emitted without the light diffusing element 4b. The reduction ratio of the concentration [wt%] of the phosphor 4a must be at 3.0%. In the range of ~86%, even if the amount of use of the phosphor 4a is lowered, the maintenance efficiency of the semiconductor light-emitting device 1 can be ensured to be 90% or more.

Further, if the above formula (3) and the light diffusing element 4b and the resin are satisfied The condition of the refractive index of 4c lowers the minimum value of the luminous efficiency retention rate to 80%, but the range of the reduction ratio is expanded to 3.0% to 91%, and the amount of the phosphor 4a can be reduced. Further, when the conditions of the refractive index of the above formula (2) and the light diffusing element 4b and the resin 4c are satisfied, the minimum value of the luminous efficiency retention rate is lowered to 70%, but the range of the reduction ratio is expanded to 3.0%. ~93% can reduce the amount of phosphor 4a used. Further, it is considered that when the luminous efficiency retention rate is 70% or more, a light-emitting device having excellent characteristics can be provided, and it is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

Moreover, the value (x) of the horizontal axis in Fig. 5 is used as "(the light diffusion element 4b and the tree) The absolute value of the refractive index difference of the grease 4c is × (the thickness of the wavelength conversion member 4 itself) × (the volume fraction of the light diffusion element 4b) and the value of the vertical axis (y) in Fig. 5 is "(the phosphor) The concentration of 4a used (x (the thickness of the wavelength converting member 4 itself)" was evaluated for the slope (dy/dx) of each sample in Fig. 5, and the results of Table 9 below were obtained. As a method of calculating the specific slope, for each sample, the difference (dx) between the value of the horizontal axis of FIG. 5 corresponding to the following sample number and the value of the vertical axis (dy) are calculated, and the vertical axis is used. The difference (dy) is divided by the difference (dx) of the value of the horizontal axis to calculate the slope (dy/dx). Here, the difference (dy) of the value of the vertical axis is not the difference between the actual "concentration of the phosphor 4a" (the thickness of the wavelength conversion member 4 itself), and is replaced by the concentration of the phosphor used. The difference between the reduction rates (%). Further, in each sample group, the sample having the largest sample number (sample 1-20, sample 2-19, sample 3-20, sample 4-19, sample 5-7, sample) 6-20), the slope is not calculated. Furthermore, the value in which the slope becomes a negative number is always referred to as "0".

[Table 9]

Here, as shown in Table 9, the slope of the sample 2-4 having the minimum value satisfying the lower limit of the above formula (4) is 447, and has the upper limit value satisfying the above formula (4). The slope of the sample 5-4 of the maximum value was 19. Accordingly, the relatively small value of the slope, that is, the range in which the slope is moderately gentle, can suppress the unevenness of the chromaticity of the light emitted due to the change in the thickness of the wavelength converting member or the change in the use density of the phosphor. When the above equation (4) is expressed by the slope in FIG. 5, it can be expressed as the following equation (5).

19≦dy/dx≦447 (5)

In the above formula (5), x represents | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × (volume fraction of the light diffusing element) [vol%]), y represents a reduction ratio of the use concentration of the phosphor 4a.

In addition, in the first sample group, the third sample group, the fourth sample group, and the fifth sample group, "(the light diffusion element 4b and the light diffusion element 4b and The absolute value of the refractive index difference of the resin 4c) (the thickness of the wavelength conversion member 4 itself) × (the volume fraction of the light diffusion element 4b)" (the value of the horizontal axis (x) in Fig. 5) is 0~ In the range of 0.02, the value of "(concentration of the use of the phosphor 4a) × (thickness of the wavelength conversion member 4 itself)" (the value of the vertical axis (y) in Fig. 5) is particularly drastically reduced, in Fig. 5 The value of the horizontal axis (x) is at 0.02~ In the range of 0.04, the value of "(the concentration of the phosphor 4a used) × (the thickness of the wavelength conversion member 4 itself)" (the value of the vertical axis (y) in Fig. 5) sharply decreases, as shown in Fig. 5 When the value of the horizontal axis (x) is in the range of 0.04 to 0.05, the value of "(the concentration of the phosphor 4a used) × (the thickness of the wavelength converting member 4 itself)" (the value of the vertical axis in Fig. 5 (y) )) Although it is not as good as the reduction rate of the above range, it is also reduced. On the other hand, when the value (x) of the horizontal axis in Fig. 5 is in the range of 0.05 or more, the value (y) of the vertical axis in Fig. 5 is gently reduced or hardly decreased.

Accordingly, the value (x) of the horizontal axis in FIG. 5 is "(the light diffusion element 4b) The value of the absolute value of the difference in refractive index of the resin 4c) (the thickness of the wavelength conversion member 4 itself) × (the volume fraction of the light diffusing element 4b) is 0.02 or more, which is comparable to the case of less than 0.02. The unevenness of the luminous efficiency of the semiconductor light-emitting device 1 due to the uneven content of the phosphor 4a is reduced. Moreover, by setting the value of the horizontal axis (x) in FIG. 5 to 0.04 or more, unevenness in luminous efficiency of the semiconductor light-emitting device 1 due to uneven content of the phosphor 4a can be further reduced. Further, by setting the value of the horizontal axis (x) in FIG. 5 to 0.05 or more, semiconductor light emission due to uneven content of the phosphor 4a can be reliably reduced as compared with the case of less than 0.05. The unevenness of the luminous efficiency of the device 1. Thereby, the conversion efficiency of the light emitted from the semiconductor light-emitting element is changed, and the light emitted from the semiconductor light-emitting element (blue light) and the light converted by the wavelength conversion member (yellow light) are mixed to reduce the emission from the semiconductor light-emitting device. The chromaticity of the light (white light) is uneven. Therefore, the wavelength conversion member 4 is preferably | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × (volume fraction of the light diffusing element [vol%] The value of ]) is 0.02 or more, more preferably 0.04 or more, and particularly preferably the following formula (6) is satisfied.

0.05≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength conversion member [mm])×(volume fraction of light diffusing element [vol%])≦0.2 (6)

Here, as shown in Table 9, the slope (dy/dx) of the sample 1-7 was 233, the slope (dy/dx) of the sample 2-7 was 399, and the slope of the sample 4-5 (dy/dx) ) is 376, and the slope (dy/dx) of sample 5-2 is 176. When the slope is considered in consideration of the above equation (6) using the slope in FIG. 5, it can be expressed as the following equation (7).

400≦dy/dx≦447 (7)

Wherein, in the above formula (7), x represents | (refractive index of the light diffusing element) - (Refractive index of the base material) | × (thickness of the wavelength conversion member [mm]) × (volume fraction of the light diffusion element [vol%]), and y represents a reduction ratio of the use concentration of the phosphor 4a.

Further, in the case where the above-described phosphor 4a diffuses yellow light, the light diffusing element 4b does not include the phosphor 4a, and the phosphor 4a is not included as a part of the light diffusing element 4b. And consider it.

(actual sample evaluation)

<Examples 1-1, 1-2>

Then, in the semiconductor light-emitting device 1 of the present embodiment, the mixing ratio of the phosphor 4a and the use density (wt%) of the phosphor 4a are changed to achieve the target chromaticity point of the light emitted from the semiconductor light-emitting device 1. The adjustment is made in the manner of (x, y) = (0.46, 0.41). Further, the luminous efficiency of each semiconductor light-emitting device was actually measured, and the measurement result was evaluated. Further, as the wiring board 2, white alumina having a reflectance of 90% or more is used. This evaluation result will be described in detail with reference to Table 10.

The raw materials of the resin compositions of Examples 1-1 and 1-2 used for producing the wavelength converting member 4 are as follows. Light diffusing element 4b: polymethylsesquioxane spherical particles, manufactured by Momentive Co., Ltd., trade name "Tospearl 120", average particle diameter 2 μm, refractive index 1.42, density 1.3 g/cm ³ ; resin 4c: polycarbonate Ester resin (particles of polycarbonate resin produced by interfacial polymerization using bisphenol A as a starting material), manufactured by Mitsubishi Engineering-Plastics, trade name "Iupilon S-3000FN", viscosity average molecular weight 21,000, density =1.2 g/cm ³ (23 ° C), refractive index of 1.58; phosphor 4a: phosphor made by Mitsubishi Chemical Corporation, YAG (yellow phosphor), CASN (red phosphor), SCASN (short wavelength red) A mixture of phosphors, G-YAG (green phosphor). The mixing ratio is (YAG+G-YAG): (CASN + SCASN) = 8:2.

The manufacturing conditions of the resin composition used in the wavelength conversion member 4 and the molding conditions of the wavelength conversion member 4 are as follows.

The phosphor 4a, the light diffusing element 4b, and the resin 4c were mixed in a specific amount shown in Table 10, and after mixing by a tumbler, a 40 mm single-axis extruder (a full-screw screw manufactured by Isuzu Chemical Co., Ltd.) was used. Melting and kneading at a cylinder temperature of 280 ° C, a screw speed of 75 rpm, a production speed of 18 kg / h, and a vacuum vent of 0.08 MPa. The resin composition particles were obtained. Then, the obtained pellets were produced by an injection molding machine ("NS40" manufactured by Nissei Co., Ltd.) under the conditions of a cylinder temperature of 280 ° C, a mold temperature of 80 ° C, an injection dwell time of 3 sec, and a cooling time of 10 sec. The mm-wide wavelength conversion member 4.

In Table 10 below, "volume fraction (vol%) of light diffusing element 4b" and "refractive index difference × thickness of wavelength converting member 4 itself × volume of light diffusing element 4b" of each sample (semiconductor light-emitting device 1) Fraction", "concentration (% by weight) of phosphor 4a", and "luminescence efficiency (lm/W)".

[Table 10]

As shown in Table 10, even if the use concentration of the phosphor 4a is changed, as long as any of the above equations (2) to (4) is satisfied, a relatively high luminous efficiency can be obtained. Further, in the evaluation, when the concentration (wt%) of the phosphor used was decreased, the luminous efficiency was increased, which was different from the results of the above simulation. The reason for this is that the luminous efficiency of the semiconductor light-emitting device 1 is affected by other factors than the addition of the light-diffusing element 4b (for example, the mixing ratio of the phosphor 4a).

<Examples 2-1 to 2-4, Comparative Example 1>

The semiconductor light-emitting device 1 of the present embodiment evaluates the change in the use concentration of the phosphor caused by the presence or absence of the addition of the light-diffusing element 4b and the luminous efficiency of the semiconductor light-emitting device. The adjustment is performed such that the light emitted from the semiconductor light-emitting device 1 reaches the target chromaticity point (x, y) = (0.26, 0.25). Further, the luminous efficiency of each semiconductor light-emitting device was actually measured, and the measurement result was evaluated. Further, as the wiring board 2, white alumina having a reflectance of 90% or more is used. This evaluation result will be described in detail with reference to Table 11.

The materials of the resin compositions of Examples 2-1 to 2-4 used in the production of the wavelength conversion member 4 and Comparative Example 1 are as follows. Light diffusing element 4b: alumina particle, manufactured by Micron Corporation, trade name "AX3-32", average particle diameter 3 μm, refractive index 1.78, density 4.0 g/cm ³ ; resin 4c: polyoxyl resin, Dow Corning Toray Manufactured, trade name "OE6336A/B", density = 1.0 g/cm ³ (23 ° C), refractive index 1.42; phosphor 4a: phosphor, YAG (yellow phosphor) wavelength conversion member manufactured by Mitsubishi Chemical Corporation The manufacturing conditions of the resin composition used and the molding conditions of the wavelength converting member 4 are as follows.

The phosphor 4a, the light diffusing element 4b, and the resin 4c were blended in a specific amount (total weight: 10 g) as shown in Table 11, and a vacuum degassing kneader V-mini300 manufactured by EME Co., Ltd. was used, and defoamed at 1200 rpm at room temperature. The mixture was kneaded for 3 minutes to obtain a phosphor-containing polyoxymethylene resin composition. The obtained resin composition was cast into 62 mm Φ and a thickness of 1 mm, and heat-hardened at 150 ° C for 5 minutes, followed by heat curing at 200 ° C for 20 minutes, thereby performing molding to obtain the wavelength conversion member 4 .

Table 11 below shows "volume fraction (vol%) of light diffusing element 4b" in each sample (semiconductor light-emitting device 1), "refractive index difference × thickness of wavelength converting member 4 itself × volume of light diffusing element 4b" "Score", "relative phosphor usage (comparative example 1 is 1.00)", and "relative luminous flux value (comparative example 1 is 1.00)".

[Table 11]

When the light diffusing element is mixed in the state before the base material, the refractive index of the light diffusing element, the volume fraction of the light diffusing element, and the refractive index of the base material can be accurately calculated by grasping the amount of each material or the manufacturing step ( That is, the true value is calculated, and the above equation can be easily utilized. On the other hand, depending on the state in which the light diffusing element is mixed in the base material (that is, the state of the wavelength converting member), it is difficult to accurately calculate the refractive index of the light diffusing element, the volume fraction of the light diffusing element, and the refractive index of the base material. In particular, regarding the volume fraction of the light diffusing element, it is impossible to calculate the volume fraction of the actual light diffusing element based on the state in which the light diffusing element is mixed into the base material. However, even in a state in which the light diffusing element is mixed in the base material, the refractive index of the light diffusing element, the volume fraction of the light diffusing element, and the refractive index of the base material can be calculated by the following method. The value of the true value (actual value) is almost equal, and by substituting the calculated value into the above equation, the wavelength conversion member to be the target (that is, the member in which the light diffusion element is mixed into the base material) can be verified and evaluated. .

The verification and evaluation of the specific light diffusion elements are analyzed by the base metal (by The type of the base material is estimated to be a refractive index, the analysis of the light diffusing element (the refractive index is estimated from the type of the light diffusing element), and the quantification of the light diffusing element. Here, qualitative analysis of the base material is performed by infrared spectroscopy or the like, and qualitative analysis of the light diffusion element is performed by SEM-EDS and nuclear magnetic resonance (NMR: Nuclear Magnetic Resonance), and quantitative analysis of the light diffusion element is performed. It is performed by image analysis of the cross-sectional SEM image. Further, the qualitative analysis of the base material and the light diffusing element can also be carried out by a known method such as IR, or thermal decomposition GC/MS.

For the analysis of the base metal, a commercially available infrared spectroscopic device such as Thermo can be used. NEXUS670 and Nic-Plan manufactured by Fisher Scientific. The type of base metal can be determined by comparing the obtained spectrum with a database. Further, the refractive index of the identified base material can be determined by referring to Table 2 above.

The analysis and quantification of the light diffusing elements were carried out in the following order. specific In the cross-section polishing apparatus manufactured by JEOL Ltd., a cross section of the wavelength conversion member was produced, and an SEM image of the phosphor and the light diffusion element contained in the base material was imaged. The SEM can also use, for example, Ultra55 manufactured by Garl Zeiss.

Here, the difference between the phosphor and the light diffusing element is determined by SEM-EDS. In the case of analysis, it is preferable to reduce the candidates of the phosphor contained in the wavelength conversion member in advance by qualitative analysis by X-ray diffraction (XRD: X-ray Diffraction). When it is observed that the main element of the light diffusing element is yttrium or oxygen, it is estimated that the type of the light diffusing element is glass or polyoxymethylene resin. When it is observed that the main element of the light-diffusing element is carbon or oxygen, it is estimated to be an organic system, and any of the acrylic or styrene-based resins is used as the light-diffusing element (see Table 1). Here, in the case of acrylic acid, oxygen is detected in addition to carbon, and in the case of styrene, only carbon is detected (however, there is a possibility that trace oxygen is detected by the influence of impurities or the like). When it is difficult to distinguish the two by SEM-EDS, the species is determined by NMR or the like. In the case where it is difficult to distinguish between the phosphor and the light diffusing element by NMR or the like due to a small content, etc., it may be dissolved or filtered as needed. and then, Similarly to the determination of the refractive index of the base material, the refractive index of the determined light diffusing element can be determined by referring to Table 1 above.

Quantification of light diffusing elements by secondary electron image or reflected electricity of SEM The sub-composition image is analyzed by image analysis. Specifically, first, the contrast (brightness) of the composition image of the secondary electron image or the reflected electron is distinguished from the phosphor. Here, the light diffusion element may be determined according to the contrast of the secondary electron image or the reflected electron composition image. Therefore, it is not necessary to perform SEM-EDS analysis on all light diffusion elements. Further, the magnification of the photographed cross-sectional SEM image is such that the maximum particle size (diameter) of the observed light diffusing element is 20 times or more of the image pixel size. For example, in the case of a particle of a light diffusing element having a maximum diameter of 2 μm, a cross-sectional SEM image having a pixel of 0.1 μm or less is taken. Further, in order to reduce the statistical error, the number of sheets of the cross-sectional SEM image used for the quantification is set to be 1000 or more in total.

Then, image analysis is performed by binarization processing by a computer. For example, use ImageProPlus manufactured by Media Cybernetics. Specifically, the binarized SEM image binarization process extracts the total number N of light diffusing elements in the wavelength converting member and the average area of the light diffusing elements in the cross-sectional SEM image, and the average area is assumed to be The average diameter of the circle is calculated by circle, and the value obtained by multiplying the average diameter by π/4 is set as the particle diameter D [μm] of the light diffusion element, and the total area of the SEM image of the cross section calculated by the above is set to S [ Μm ² ], the concentration (volume fraction) C [vol%] of the light diffusing element was calculated according to the following formula (8).

Furthermore, the light diffusion calculated by the analysis of the base material described above (the refractive index is estimated from the type of the base material), the analysis of the light diffusion element (the refractive index is estimated from the type of the light diffusion element), and the quantification of the light diffusion element The value of the refractive index of the element, the volume fraction of the light diffusing element, and the refractive index of the base material are substituted into any of the above equations (2) to (4) and (6), whereby the verification and evaluation are targeted The wavelength conversion member (that is, the state after the light diffusion element is mixed into the base material) Component).

When the verification and evaluation of the target wavelength conversion member are performed by the above method, the wavelength is obtained after obtaining the refractive index of the light diffusion element, the volume fraction of the light diffusion element, and the true value of the refractive index of the base material. Compared with the case of verification and evaluation of the conversion member, the error is about 10% to about 20%. In the case where the error is 10%, the above equations (2) to (4) and (6) can be expressed as the following equations (2') to (4') and (6').

0.01±0.001≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength conversion member [mm])×(volume fraction of light diffusing element [vol%])≦1.0± 0.1 (2')

0.01±0.001≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength conversion member [mm])×(volume fraction of light diffusing element [vol%])≦0.6± 0.06 (3')

0.01±0.001≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength converting member [mm])×(volume fraction of light diffusing element [vol%])≦0.2± 0.02 (4')

0.05±0.005≦|(refractive index of light diffusing element)-(refractive index of base metal)|×(thickness of wavelength conversion member [mm])×(volume fraction of light diffusing element [vol%])≦0.2± 0.02 (6')

It is understood that even if the above-described methods are used to verify and evaluate the target wavelength conversion member according to the above equations (2') to (4') and (6'), the evaluation result is not inferior to the evaluation using the true value. As a result, it is possible to achieve an excellent evaluation accuracy at the same level as the evaluation using the true value.

(by the effect of this embodiment)

In the wavelength conversion member 4 of the present embodiment, 0.01 ≦| (refractive index of the light diffusion element 4b) - (refractive index of the resin 4c) | × (thickness of the wavelength conversion member 4 [mm]) × (light diffusion element) The volume fraction of 4b [vol%]) ≦ 1.0 is a numerical formula, so that when it is provided on the semiconductor light-emitting device 1, the content of the phosphor 4a can be reduced without lowering the luminous efficiency of the semiconductor light-emitting device 1. , to achieve cost reduction. In this case, if | (light diffusion element The effect of the refractive index of 4b) - (refractive index of resin 4c) | × (thickness of wavelength conversion member 4 [mm]) × (volume fraction of light diffusing element 4b [vol%]) is 0.6 or less, the effect is obtained. (The decrease in luminous efficiency and the cost reduction) is remarkably exhibited, and if it is 0.2 or less, the effect is more prominently exhibited.

Further, in the wavelength conversion member 4 of the present embodiment, | (light diffusion element) When the refractive index of 4b) - (refractive index of resin 4c) | × (thickness of wavelength conversion member 4 [mm]) × (volume fraction of light diffusing element 4b [vol%]) is 0.02 or more, The unevenness of the luminous efficiency of the semiconductor light-emitting device 1 due to the uneven content of the phosphor 4a can be reduced. In this case, if (the refractive index of the light diffusing element 4b) - (the refractive index of the resin 4c) | × (the thickness [mm] of the wavelength converting member 4) × (the volume fraction of the light diffusing element 4b [vol%] When the value of 0.0) is 0.04 or more, the effect (decreased unevenness in luminous efficiency) is remarkably exhibited, and if it is 0.05 or more, the effect is more prominently exhibited.

Further, in the semiconductor light-emitting device 1 of the present embodiment, the wavelength is changed. The replacement member 4 satisfies 0.01 ≦| (refractive index of the light diffusion element 4b) - (refractive index of the resin 4c) | × (thickness of the wavelength conversion member 4 [mm]) × (volume fraction of the light diffusion element 4b [vol%] ]) ≦ 1.0 is a numerical formula, so that the content of the phosphor 4a can be reduced without lowering the luminous efficiency, and the cost can be reduced.

Further, when verifying and evaluating the wavelength conversion member 4 included in the semiconductor light-emitting device 1, the image analysis result of the cross-sectional SEM image of the wavelength conversion member 4 is used, and C=N×4 π/3×(D) is used. /2) ³ / (S × D) × 100 (here, C: volume fraction of light diffusing element 4b [vol%], N: wavelength conversion member 4 calculated by binarization processing of cross-sectional SEM image The total number of the light diffusing elements 4b [a] and D: the average diameter of the circle calculated by the assumption of the circle based on the average area of the light diffusing elements 4b in the cross-sectional SEM image calculated by the binarization processing of the cross-sectional SEM image The numerical formula of the particle size [μm] of the light diffusing element 4b obtained by π/4 and the total area of the SEM image of the cross section [μm ² ]) is calculated as the volume fraction of the light diffusing element [ Vol%]) can be verified and evaluated with the same high precision as in the case of verification and evaluation using the true value of the volume fraction of the light diffusing element 4b.

Further, in the present embodiment, the resin 4c as described above is used as the above. The base material of the wavelength conversion member 4 is not limited thereto, and glass or the like may be used.

Further, in the present embodiment, the LED chip 3 emitting blue light is used. The light source of the semiconductor light-emitting device 1 is not limited to an LED chip that emits blue light, as long as it can emit white light from the semiconductor light-emitting device 1. For example, an LED chip that emits ultraviolet light can be used. In this case, the wavelength conversion member 4 is dispersed in a red phosphor that absorbs ultraviolet light and emits red light, a green phosphor that absorbs ultraviolet light and emits green light, and a blue phosphor that absorbs ultraviolet light and emits blue light. .

The wavelength of the luminescence peak of the specific red phosphor is preferably 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably It is within the wavelength range below 680 nm. Among them, as the red phosphor, for example, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca ,Sr,Ba)AlSi(N,O) ₃ :Eu,(Sr,Ba) ₃ SiO ₅ :Eu, (Ca,Sr)S:Eu,SrAlSi ₄ N ₇ :Eu,(La,Y) ₂ O ₂ S: Eu, Eu (benzhydrylmethane) ₃ ‧1, 10- phenanthroline complex and other β-diketone Eu complex, carboxylic acid Eu complex, K ₂ SiF ₆ : Mn, more Jia (Ca, Sr, Ba) ₂ Si ₅ (N,O) ₈ :Eu, (Sr,Ca)AlSi(N,O) ₃ :Eu,SrAlSi ₄ N ₇ :Eu,(La,Y) ₂ O ₂ S: Eu, K ₂ SiF ₆ : Mn (wherein one part of Si may be substituted with Al or Na).

The wavelength of the luminescence peak of the specific green phosphor is preferably 500 nm or more, preferably 510 nm or more, more preferably 515 nm or more, and usually less than 550 nm, preferably 542 nm or less. It is preferably in the wavelength range below 535 nm. Among them, as the green phosphor, for example, Y ₃ (Al, Ga) ₅ O ₁₂ :Ce, CaSc ₂ O ₄ :Ce, Ca ₃ (Sc,Mg) ₂ Si ₃ O ₁₂ :Ce, (Sr) is preferable. , Ba) ₂ SiO ₄ :Eu, (Si,Al) ₆ (O,N) ₈ :Eu(β-Sialon), (Ba,Sr) ₃ Si ₆ O ₁₂ :N ₂ :Eu, SrGa ₂ S ₄ :Eu, BaMgAl ₁₀ O ₁₇ :Eu, Mn.

The wavelength of the luminescence peak of the specific blue phosphor is preferably 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually less than 500 nm, preferably 490 nm or less. More preferably, it is in the wavelength range of 480 nm or less, more preferably 470 nm or less, and particularly preferably 460 nm or less. Among them, as the blue phosphor, for example, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ :Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu , (Ba, Ca, Mg, Sr) ₂ SiO ₄ :Eu, (Ba,Ca,Sr) ₃ MgSi ₂ O ₈ :Eu, more preferably (Ba,Sr)MgAl ₁₀ O ₁₇ :Eu, (Ca,Sr , Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, Ba ₃ MgSi ₂ O ₈ :Eu, more preferably Sr ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu, BaMgAl ₁₀ O ₁₇ :Eu.

Further, in the present embodiment, the blue light emitted from the LED chip 3 is emitted. The color light is combined with the yellow light radiated from the phosphor 4a as the yellow phosphor, and the white light is virtually radiated from the semiconductor light-emitting device 1. However, since the yellow light is combined with the green light and the green light, the wavelength conversion member 4 The phosphor contained may also be replaced by the above-described red phosphor and green phosphor. In this case, blue light emitted from the LED wafer 3, red light emitted from the red phosphor, and green light emitted from the green phosphor are combined, and white light is virtually emitted from the semiconductor light-emitting device 1.

Further, in the semiconductor light-emitting device 1 of the present embodiment, the LED is used The wafer 3 is disposed apart from the wavelength conversion member 4, but the wavelength conversion member 4 may be disposed so as to be covered with the LED wafer 3.

Even in the above-described modification, the above formula (2) and the light are satisfied. In the case of the conditions of the refractive indices of the diffusing element 4b and the resin 4c, the same effects as those of the above-described embodiment can be obtained.

Fig. 12 is a schematic view showing a light-emitting device according to an embodiment of the present invention. Illuminate The device 100 includes at least a blue semiconductor light emitting element 101 and a wavelength converting member 103 as constituent members thereof. The blue semiconductor light emitting element 101 emits excitation light for exciting the phosphor contained in the wavelength conversion member 103. The blue semiconductor light-emitting element 101 generally emits excitation light having a peak wavelength of 425 nm to 475 nm, preferably an excitation light having a peak wavelength of 430 nm to 470 nm. The number of blue semiconductor light-emitting elements 101 can be appropriately set depending on the intensity of the excitation light required for the device. On the other hand, a purple semiconductor light emitting element can be used instead of the blue semiconductor light emitting element 101. The violet semiconductor light-emitting element generally emits excitation light having a peak wavelength of 390 nm to 425 nm, preferably an excitation light having a peak wavelength of 395 to 415 nm.

The blue semiconductor light emitting element 1011 is mounted on the wiring substrate 102 The sheet mounting surface 102a. An electric circuit is formed on the wiring board 102 to form a wiring pattern (not shown) for supplying electrodes to the blue semiconductor light-emitting elements 101. Although the wavelength conversion member 103 is placed on the wiring board 102 in FIG. 12, the present invention is not limited thereto, and the wiring board 102 and the wavelength conversion member 103 may be disposed via other members. For example, in FIG. 13, the wiring board 102 and the wavelength conversion member 103 are arrange|positioned by the frame 104. In order to make the light The orientation of the frame 104 can also be tapered. Further, the frame body 104 may be a reflective material.

In terms of improving the luminous efficiency of the light-emitting device 100, the wiring substrate 102 is preferably excellent in electrical insulation, has good heat dissipation, and has high reflectance, and may be on the surface of the wiring substrate 102 where the blue semiconductor light emitting element 101 is not present, or the wiring substrate 102 is connected. At least a part of the inner surface of the other member of the wavelength conversion member 103 is provided with a reflector having a high reflectance. The reflectance of the reflecting plate used for the wiring board or the reflectance of the reflecting plate which is one part of the covered wiring board is preferably 80% or more, and more preferably the area of the portion having a reflectance of 80% or more is the wiring substrate. 50% or more of the area, more preferably 70% or more, still more preferably 80% or more, further preferably a portion having a reflectance of 90% or more, and more preferably an area having a reflectance of 90% or more. The area of the wiring board is 50% or more, more preferably 70% or more, and particularly preferably 80% or more. Further, the reflectance refers to the reflectance of light in the visible light region. Similarly, when the frame is used, the reflectance of the reflecting plate for the frame or the reflectance of the reflecting plate which is a part of the covering frame is preferably 80% or more, and more preferably 80%. The area of the portion above the % is 50% or more of the area of the frame and the wiring board, and more preferably 70% or more, and particularly preferably 80% or more. Further, it is preferable that the portion having the reflectance of 90% or more is more preferably 50% or more of the area of the frame and the wiring substrate, and more preferably 70% or more. Especially good is more than 80%. Further, the reflectance refers to the reflectance of light in the visible light region. As a material for achieving such a reflectance, a reflective material containing a filler in a resin can be mentioned. Specifically, it is preferable that a polyoxonium resin, a polycarbonate resin, a polyphthalamide resin or the like contains a metal oxide filler such as alumina, titania, cerium oxide, zinc oxide or magnesium oxide. The reflective material or a reflective material obtained by containing a metal oxide in the ceramic. Examples of the reflective material containing a metal oxide such as titanium oxide in the polycarbonate resin include, for example, Iupilon EHR3100 and EHR3200. Examples of the reflective material in which the metal oxide such as alumina or titanium oxide is contained in the polysiloxane resin include a reflective material described in WO2011/078239 and WO2011/136302. Moreover, a reflective material containing a metal oxide such as alumina or titanium oxide in polyphthalamide is preferably exemplified.

<Reference example: Light-emitting device using a reflective material having a high reflectance>

The same wavelength conversion member was used (the refractive index of the light diffusion element was 1.45, the refractive index of the resin was 1.58, the volume fraction of the light diffusion element was 0.5 vol%, and the thickness of the wavelength conversion member itself was 2.00 mm, (1.58-1.45) × 0.5×2=0.13), in the same light emission and measurement method as described above, it was confirmed that a reflection was provided on the wiring board of the light-emitting device (the reflectance was less than 80%) and the inner wall surface of the frame (the reflectance was less than 80%). The luminous efficiency is improved in the case of a 93 to 95% reflective material (in the case where the wiring substrate is on the surface where the semiconductor light emitting element is not present). The measurement results of the Lumen value of Lu, Ra (color rendering), and CCT (Luminescence color temperature) are shown in Table 12. The reflectance was measured using U-3310 manufactured by Hitachi High-Tech Co., Ltd. using barium sulfate as a standard sample.

[Table 12]

It has been found that high efficiency can be achieved in a light-emitting device using the present wavelength conversion member by using a certain proportion or more of a reflective material having a high reflectance.

<Second embodiment>

In the above-described first embodiment, the phosphor 4a and the light diffusing element 4b are mixed in the resin 4c. However, the structure is not limited to the structure of the wavelength converting member 4, and may be replaced with the structure shown in FIG. The wavelength conversion member 24 having such a configuration is described as a second embodiment, and will be described below. In addition, FIG. 7 is an enlarged cross-sectional view of an essential part of the semiconductor light-emitting device 21, which is the same as that of FIG. 4, and the same reference numerals are given to the same components as those in the first embodiment, and the description thereof is omitted.

As shown in FIG. 7, a plurality of phosphors 24a and a plurality of light diffusing elements 24b are contained in the resin 24c so as to be separated from each other. Further, the phosphor layer 24d is formed of a plurality of phosphors 24a and 24c, and the light diffusion layer 24e is formed of a plurality of light diffusion elements 24b and resin 24c. In other words, the wavelength conversion member 24 of the present embodiment has a two-layer structure in which the laminated resin 24c contains only the light diffusion element 24b on the phosphor layer 24d in a state where the resin 24c contains only the phosphor 24a. Light diffusion layer 24e.

Further, in the present embodiment, the phosphor layer 24d is disposed to face the LED wafer 3. That is, the distance from the LED chip 3 to the phosphor layer 24d is smaller than the distance from the LED chip to the light diffusion layer 24e.

Further, as shown in FIG. 8, the light diffusion layer 24e may be disposed to face the LED chip 3. That is, the distance from the LED chip 3 to the phosphor layer 24d is greater than the distance from the LED chip to the light diffusion layer 24e.

In the present embodiment, when the conditions of the above formula (2) and the refractive index of the light diffusing element and the resin are satisfied, the same effects as those of the first embodiment described above can be obtained. The semiconductor light-emitting device 21 of the present embodiment has relatively high luminous efficiency and is suitable for general illumination applications and backlight applications. Further, since the phosphor layer 24d and the light diffusion layer 24e are laminated to each other, it is easy to achieve miniaturization as the semiconductor light-emitting device 21.

<Third embodiment>

In the second embodiment, the wavelength conversion member 24 has a two-layer structure in which a phosphor layer 24d including a plurality of phosphors 24a and 24c and a light diffusion layer 24e including a plurality of light diffusion elements 24b and a resin 24c are laminated. However, the configuration of the wavelength conversion member 24 is not limited to the configuration, and the wavelength conversion member having the structure shown in FIG. 9 may be replaced. The wavelength conversion member 34 having such a configuration is used as the third embodiment, and the following is performed. Description. In addition, FIG. 9 is an enlarged cross-sectional view of an essential part of the semiconductor light-emitting device 31, which is the same as that of the first embodiment, and the same reference numerals are given to the same components as those in the first embodiment, and the description thereof is omitted.

As shown in Fig. 9, the resin 34c is separated into two layers via the void layer 34f. Further, a plurality of phosphors 34a are dispersed and held in one of the layers of the resin 34c, whereby the phosphor layer 34d is formed. Further, a plurality of light diffusion elements 34b are dispersed and held in the other layer of the resin 34c, whereby the light diffusion layer 34e is formed. In other words, the wavelength conversion member 34 of the present embodiment has a three-layer structure in which the phosphor layer 34d, the void layer 34f, and the light diffusion layer 34e are sequentially laminated.

Further, in the present embodiment, the phosphor layer 34d is disposed to face the LED wafer 3. That is, the distance from the LED chip 3 to the phosphor layer 34d is smaller than The distance from the LED chip to the light diffusion layer 34e.

Furthermore, as shown in FIG. 10, the light diffusion layer 34e can also be combined with an LED chip. 3 relative to the way configuration. That is, the distance from the LED chip 3 to the phosphor layer 34d is greater than the distance from the LED chip to the light diffusion layer 34e. In this case, compared with the semiconductor light-emitting device 31 shown in FIG. 9, it can be used for general illumination applications and backlight applications without reducing the light-emitting efficiency.

In the present embodiment, the above equation (2) and the light diffusion element are satisfied. In the case of the condition of the refractive index of the resin, the same effects as those of the first embodiment described above can be obtained. Further, in the present embodiment, the thickness of the wavelength conversion member in the above equations (2) to (6) is not the thickness of the entire wavelength conversion member 34, but the layer thickness and light diffusion of the phosphor layer 34d. The sum of the layer thicknesses of layer 34e. That is, the thickness obtained by subtracting the layer thickness of the void layer 34f is the thickness of the entire wavelength conversion member 34.

1‧‧‧Semiconductor light-emitting device

2‧‧‧ wiring substrate

2a‧‧‧ wafer mounting surface

3‧‧‧LED chip (semiconductor light-emitting element)

4‧‧‧wavelength conversion component

4a‧‧‧Fertior

4b‧‧‧Light diffusion elements

4c‧‧‧Resin (base metal)

5‧‧‧p electrode

6‧‧‧n electrode

7‧‧‧Wiring pattern 7

8‧‧‧ wiring pattern 8

Claims (37)

A wavelength conversion member that converts at least a portion of wavelength of incident light to emit an emitted light having a wavelength different from that of the incident light, and includes: absorbing at least a portion of the incident light to emit a wavelength different from the incident light a phosphor that emits light, a light diffusing element that diffuses the incident light and the emitted light, and a base material that holds the light diffusing element; and satisfies the following formula: 0.01≦|(refractive index of light diffusing element)-(par The refractive index of the material is × × (thickness of the wavelength conversion member [mm]) × (volume fraction of the light diffusion element [vol%]) ≦ 1.0. The wavelength conversion member according to the first aspect of the invention, wherein, in the above formula, | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × ( The value of the volume fraction [vol%] of the light diffusing element is 0.6 or less. The wavelength conversion member according to the first aspect of the invention, wherein, in the above formula, | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × ( The value of the volume fraction [vol%] of the light diffusing element is 0.2 or less. The wavelength conversion member according to any one of claims 1 to 3, wherein the value of | (the refractive index of the light diffusion element) - (the refractive index of the base material) | in the above formula is 0.07 or more. The wavelength conversion member according to any one of claims 1 to 4, wherein, in the case of producing a wavelength conversion member that does not include the light diffusion element and emits light of the same chromaticity, the phosphor is The reduction ratio of the concentration [wt%] of the above-mentioned phosphor is 3.0% to 86% based on the concentration [wt%]. The wavelength conversion member according to any one of claims 1 to 5, wherein, in the above formula, | (refractive index of light diffusing element) - (refractive index of base material) | × (thickness of wavelength converting member) The value of [mm]) × (volume fraction of light diffusing element [vol%]) is 0.04 or more. The wavelength conversion member according to claim 6, wherein in the above formula, | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm]) × ( The value of the volume fraction [vol%] of the light diffusing element is 0.05 or more. A wavelength conversion member according to any one of claims 1 to 7, which satisfies 28 ≦ dy / dx ≦ 447, x: | (refractive index of light diffusing element) - (refractive index of base metal) | × (thickness of wavelength converting member [mm]) × (volume fraction of light diffusing element) [vol%]) y: in the case of producing a wavelength conversion member that does not include the light diffusing element and emits light of the same chromaticity, the phosphor is based on the concentration [wt%] of the phosphor The reduction ratio of the concentration [wt%] is contained. The wavelength conversion member according to any one of claims 1 to 8, wherein the phosphor and the light diffusing element are mixed in the base material. The wavelength conversion member according to any one of claims 1 to 8, wherein the phosphor and the light diffusing element are separated from each other and contained in the base material, and a phosphor layer and a light diffusion layer are formed. The wavelength conversion member according to claim 10, wherein the phosphor layer and the light diffusion layer are in contact with each other and laminated. The wavelength conversion member according to claim 10, wherein the base material has a void layer separating the phosphor layer from the light diffusion layer. The wavelength conversion member according to any one of claims 1 to 12, wherein the refractive index of the light diffusing element is 1.0 or more and 1.9 or less, and the refractive index of the base material is 1.3 or more and 1.7 or less. The wavelength conversion member according to any one of claims 1 to 13, wherein the light diffusion element contains inorganic light selected from at least one element selected from the group consisting of ruthenium, aluminum, titanium, and zirconium. A diffusing material, or an organic light diffusing material. The wavelength conversion member according to claim 14, wherein the organic light diffusing material contains an organic light diffusing material or an acrylic light diffusing material. The wavelength conversion member according to any one of claims 1 to 13, wherein the light diffusion element comprises a bubble. The wavelength conversion member according to any one of claims 1 to 16, wherein the base material comprises a resin or a glass. The wavelength conversion member according to claim 17, wherein the resin is selected from the group consisting of polycarbonate resin, polyester resin, acrylic resin, epoxy resin, and polyfluorene. At least one resin selected from the group consisting of oxygen resins. The wavelength conversion member according to claim 17, wherein the resin is a polycarbonate resin, and the light diffusion element is polymethylsesquioxane particles. A semiconductor light-emitting device comprising: a wiring substrate; a semiconductor light-emitting device disposed on a mounting surface of the wiring substrate; and a wavelength conversion member that converts at least a part of wavelength of incident light to emit light having a wavelength different from that of the incident light In the semiconductor light-emitting device, the wavelength conversion member includes a phosphor that absorbs at least a portion of the incident light and emits light having a wavelength different from the incident light, and diffuses the light that diffuses the incident light and the emitted light. The element and the base material holding the light diffusing element, the wavelength conversion member satisfies the following expression: 0.01 ≦ | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm ]) × (volume fraction of light diffusing element [vol%]) ≦ 1.0. The semiconductor light-emitting device of claim 20, wherein, in the above formula, (the refractive index of the light diffusing element) - (the refractive index of the base material) | × (the thickness of the wavelength converting member [mm]) × ( The value of the volume fraction [vol%] of the light diffusing element is 0.6 or less. The semiconductor light-emitting device of claim 20, wherein, in the above formula, (the refractive index of the light diffusing element) - (the refractive index of the base material) | × (the thickness of the wavelength converting member [mm]) × ( The value of the volume fraction [vol%] of the light diffusing element is 0.2 or less. The semiconductor light-emitting device according to any one of claims 20 to 22, wherein the value of | (the refractive index of the light-diffusing element) - (the refractive index of the base material) | in the above formula is 0.07 or more. The semiconductor light-emitting device according to any one of claims 20 to 23, wherein the luminous efficiency (lm/W) is maintained based on the luminous efficiency (lm/W) in the case where the light diffusing element is not contained. The rate is 90% or more, and the concentration [wt%] of the above-mentioned phosphor is reduced as compared with the case where the light diffusing element is not contained. The semiconductor light-emitting device according to any one of claims 20 to 24, wherein the semiconductor light-emitting device is spaced apart from the wavelength conversion member. The semiconductor light-emitting device according to any one of claims 20 to 25, wherein the phosphor and the light diffusing element are mixed in the base material. The semiconductor light-emitting device according to any one of claims 20 to 25, wherein the phosphor and the light diffusing element are separated from each other and contained in the base material, and a phosphor layer and a light diffusion layer are formed. Laminated structure. The semiconductor light-emitting device of claim 27, wherein a distance from the semiconductor light-emitting device to the phosphor layer is smaller than a distance from the semiconductor light-emitting device to the light-diffusing layer. The semiconductor light-emitting device of claim 27, wherein a distance from the semiconductor light-emitting device to the phosphor layer is greater than a distance from the semiconductor light-emitting device to the light-diffusing layer. The semiconductor light-emitting device according to any one of claims 20 to 29, wherein the light-diffusing element has a refractive index of 1.0 or more and 1.9 or less, and the base material has a refractive index of 1.3 or more and 1.7 or less. The semiconductor light-emitting device according to any one of claims 20 to 30, wherein the base material comprises a resin or a glass. The semiconductor light-emitting device of claim 31, wherein the resin is at least selected from the group consisting of a polycarbonate resin, a polyester resin, an acrylic resin, an epoxy resin, and a polyoxymethylene resin. 1 resin. The semiconductor light-emitting device of claim 31, wherein the resin is a polycarbonate resin, and the light diffusing element is polymethylsesquioxane particles. The semiconductor light-emitting device according to any one of claims 20 to 33, wherein the light emitted from the semiconductor light-emitting element that is not wavelength-converted by the wavelength conversion member is mixed with light converted by the wavelength conversion member. And emit white light. The semiconductor light-emitting device according to any one of claims 20 to 34, wherein a reflector is provided on the wiring substrate of the semiconductor light-emitting device, and an area of a portion having a reflectance of 80% or more is the wiring substrate. More than 50% of the area above. The semiconductor light-emitting device of any one of claims 20 to 34, wherein The semiconductor light-emitting device has a casing, and a reflector is provided on the wiring board and the inner wall surface of the casing, and an area of a portion having a reflectance of 80% or more is 50% of an area on the inner wall surface of the casing and the wiring substrate. the above. A semiconductor light-emitting device comprising: a wiring substrate; a semiconductor light-emitting device disposed on a mounting surface of the wiring substrate; and a wavelength conversion member that converts at least a part of wavelength of incident light to emit light having a wavelength different from that of the incident light In the semiconductor light-emitting device, the wavelength conversion member includes a phosphor that absorbs at least a portion of the incident light and emits light having a wavelength different from the incident light, and diffuses the light that diffuses the incident light and the emitted light. The element and the base material holding the light diffusing element, the wavelength conversion member satisfies the following expression: 0.01 ≦ | (refractive index of the light diffusing element) - (refractive index of the base material) | × (thickness of the wavelength converting member [mm ]) × (volume fraction of light diffusing element [vol%]) ≦ 1.0, in the above formula (volume fraction of light diffusing element [vol%]) is an image of a cross-sectional SEM image using the above-described wavelength converting member The result of the analysis is calculated and calculated according to the following formula: C = N × 4 π / 3 × (D / 2) ³ / (S × D) × 100 C: Volume fraction of the light diffusing element [vol%] N: By binarization of the cross-sectional SEM image The total number of light diffusing elements in the calculated wavelength conversion member [D] D: the circle calculated based on the average area of the light diffusing elements in the cross-sectional SEM image calculated by the binarization processing of the cross-sectional SEM image, assuming a circle The particle diameter [μm]S of the light diffusing element obtained by multiplying the average diameter by π/4: the total area of the cross-sectional SEM image [μm ² ].