WO2017094832A1 - 蛍光体シート、それを用いた発光体、光源ユニット、ディスプレイ、および発光体の製造方法 - Google Patents
蛍光体シート、それを用いた発光体、光源ユニット、ディスプレイ、および発光体の製造方法 Download PDFInfo
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- WO2017094832A1 WO2017094832A1 PCT/JP2016/085710 JP2016085710W WO2017094832A1 WO 2017094832 A1 WO2017094832 A1 WO 2017094832A1 JP 2016085710 W JP2016085710 W JP 2016085710W WO 2017094832 A1 WO2017094832 A1 WO 2017094832A1
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Images
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- C—CHEMISTRY; METALLURGY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the present invention relates to a phosphor sheet, a light emitter using the phosphor sheet, a light source unit, a display, and a method for manufacturing the light emitter.
- LEDs Light-emitting diodes
- LCD liquid crystal display
- LEDs Light Emitting Diodes
- LCD Liquid Crystal Display
- LEDs are expected to form a huge market in the general lighting field because of their low environmental impact.
- Patent Document 1 discloses a Mn-activated double fluoride phosphor, which is a red phosphor having a narrow emission peak half-value width, and a Eu 2 + -activated alkaline earth siliconitride phosphor, which is a yellow phosphor or a green phosphor. A method for obtaining white light emission by use is described.
- An object of the present invention is to solve such problems.
- the phosphor sheet according to the present invention includes a phosphor layer including a red phosphor, a ⁇ -type sialon phosphor, and a resin.
- It is Mn activation double fluoride represented by Formula (1), It is characterized by the above-mentioned.
- a 2 MF 6 Mn (1)
- A is one or more alkali metals selected from the group consisting of Li, Na, K, Rb and Cs and containing at least one of Na and K
- M is Si
- one or more tetravalent elements selected from the group consisting of Ti, Zr, Hf, Ge and Sn.
- the phosphor layer is composed of a single layer or a plurality of layers including the red phosphor, the ⁇ -type sialon phosphor, and the resin.
- the ⁇ -sialon phosphor and the resin are contained in the same layer.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin is 1.45 or more and 1.7 or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the resin is a silicone resin.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the proportion of the red phosphor in the total solid content in the phosphor layer is 20 wt% or more and 60 wt% or less. To do.
- the total of the proportion of the red phosphor and the proportion of the ⁇ -sialon phosphor in the total solid content in the phosphor layer is 50% by weight or more. 90% by weight or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the D50 of the red phosphor is 10 ⁇ m or more and 40 ⁇ m or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, D10 of the red phosphor is 3 ⁇ m or more.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, (D90-D10) / D50 of the red phosphor is 0.5 or more and 1.5 or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the porosity in the phosphor layer is 0.1% or more and 3% or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the phosphor layer contains fine particles.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the fine particles are silicone fine particles.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, a transparent resin layer is further laminated on the phosphor layer.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin contained in the transparent resin layer is 1.3 or more and 1.6 or less.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the refractive index of the resin contained in the transparent resin layer is not more than the refractive index of the resin contained in the phosphor layer.
- the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the transparent resin layer contains fine particles.
- the fine particles contained in the transparent resin layer are one or more selected from silica fine particles, alumina fine particles, and silicone fine particles.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the transparent resin layer has a minimum transmittance of 80% or more at a wavelength of 400 nm to 800 nm.
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the proportion of fine particles in the total solid content in the transparent resin layer is 0.1 wt% or more and 30 wt% or less. .
- the phosphor sheet according to the present invention is characterized in that, in the above invention, the average particle size of the fine particles contained in the transparent resin layer is 1 nm or more and 1000 nm or less.
- the manufacturing method of the light-emitting body which concerns on this invention picks up the said fluorescent substance sheet separated into the individualization process which separates the fluorescent substance sheet as described in any one of said invention, and individualized It includes a pick-up step and a pasting step of pasting the separated phosphor sheet to a light source.
- a light emitter according to the present invention includes the phosphor sheet according to any one of the above inventions.
- a light source unit according to the present invention is characterized by including the phosphor sheet according to any one of the above inventions.
- a display according to the present invention is characterized by comprising the light source unit described in the above invention.
- the present invention it is possible to provide a phosphor sheet that achieves both improved color reproducibility and high luminous flux.
- the light emitting body, the light source unit, and the display including the phosphor sheet according to the present invention have an effect that both improvement in color reproducibility and high luminance can be achieved.
- FIG. 1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
- FIG. 1B is a side view showing another example of the phosphor sheet according to the embodiment of the present invention.
- FIG. 2 is a process diagram showing an example of a method for manufacturing a light emitter using the phosphor sheet according to the embodiment of the present invention.
- a phosphor sheet according to the present invention a light emitter using the phosphor sheet, a light source unit, a display, and a method for producing the light emitter will be described in detail.
- the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application.
- the phosphor sheet according to the embodiment of the present invention includes a phosphor layer containing a red phosphor, a ⁇ -type sialon phosphor, and a resin.
- the red phosphor is a Mn-activated bifluoride represented by the general formula (1).
- a 2 MF 6 Mn (1)
- A is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and at least one of Na and K is selected.
- M is at least one tetravalent element selected from the group consisting of silicon (Si), titanium (Ti), zirconium (Zr), hafnium (Hf), germanium (Ge), and tin (Sn).
- FIG. 1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
- the phosphor sheet 4 according to the embodiment of the present invention includes a phosphor layer 2 containing a phosphor 1 and a resin 14 on a support 3.
- the phosphor layer 2 is a layer containing a plurality of phosphors 1 in the resin 14.
- the phosphor layer 2 contains, as the phosphor 1, a red phosphor represented by the general formula (1) and a ⁇ -type sialon phosphor.
- the phosphor layer 2 is formed on a support 3 to constitute a phosphor sheet 4.
- the phosphor layer 2 may be composed of a single layer containing the red phosphor and the ⁇ -type sialon phosphor as the phosphor 1 and the resin 14.
- the phosphor layer 2 may be composed of a plurality of layers containing the phosphor 1 and the resin 14.
- the phosphor layer 1 contains a first phosphor layer containing the red phosphor as the phosphor 1 and the resin 14, and a ⁇ -sialon phosphor as the phosphor 1 and the resin 14.
- One or more second phosphor layers may be laminated to form a plurality of layers of the phosphor layer 2.
- the red phosphor and ⁇ -sialon phosphor as the phosphor 1 and the resin 14 are included in the same layer. This is due to the following reason.
- the phosphor layer 2 is a laminate of a layer containing a red phosphor (first phosphor layer) and a layer containing a ⁇ -type sialon phosphor (second phosphor layer), color reproducibility Although it is possible to achieve both improvement and high luminous flux, in the phosphor layer 2, it is necessary to control the film thickness of each layer separately. For this reason, the chromaticity dispersion
- FIG. 1B is a side view showing another example of the phosphor sheet according to the embodiment of the present invention.
- the phosphor sheet 4 may further include a transparent resin layer 5 on the phosphor layer 2 formed on the support 3.
- the transparent resin layer 5 is formed on the upper surface (surface opposite to the support 3) of the phosphor layer 2 composed of a single layer or a plurality of layers, for example. The presence of the transparent resin layer 5 as described above improves the durability of the phosphor sheet 4.
- the phosphor sheet 4 is provided with a single layer or a plurality of phosphor layers 2 or is provided with the phosphor layer 2 and the transparent resin layer 5. From the standpoints of shape maintenance and ease of handling, it is normally in a state of being supported by the support 3. That is, in the present embodiment, the phosphor sheet 4 and the support 3 may be collectively referred to as “phosphor sheet”.
- the phosphor layer 2 is a layer mainly including the phosphor 1 and the resin 14.
- the phosphor 1 include at least a red phosphor represented by the general formula (1) and a ⁇ -type sialon phosphor.
- the red phosphor is a phosphor having an emission peak at a wavelength of 590 nm to 750 nm.
- the phosphor layer 2 includes a Mn-activated double fluoride (A 2 ) represented by the general formula (1) described above. It is necessary to include a red phosphor that is MF 6 : Mn).
- the red phosphor which is this Mn activated double fluoride is referred to as “Mn activated double fluoride complex phosphor”.
- the Mn-activated double fluoride complex phosphor is abbreviated as “red phosphor” as appropriate.
- the Mn-activated double fluoride complex phosphor is a phosphor having manganese (Mn) as an activator and an alkali metal or alkaline earth metal fluoride complex salt as a base crystal.
- the coordination center of the fluoride complex forming the host crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, Sn),
- the number of coordinated fluorine atoms is preferably 6.
- a preferred Mn-activated bifluoride complex phosphor is one in which A is K (potassium) and M is Si (silicon) in the general formula (1), that is, K 2 SiF 6 : Mn. This is called a KSF phosphor.
- the ratio of the red phosphor (that is, the Mn-activated bifluoride complex phosphor) in the total solid content in the phosphor layer 2 is preferably 10% by weight or more, and more preferably 20% by weight or more. Further, this ratio is preferably 80% by weight or less, and more preferably 60% by weight or less. When this ratio is equal to or greater than the preferable lower limit value, the color reproduction range of the phosphor sheet 4 is further improved. On the other hand, when this ratio is 80% by weight or less, the chromaticity variation of the phosphor sheet 4 is improved, and when this ratio is 60% by weight or less, the chromaticity variation of the phosphor sheet 4 is further improved.
- the D50 of the red phosphor as the phosphor 1 is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more. Further, D50 of the red phosphor is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less. When the D50 of the red phosphor is 5 ⁇ m or more, the phosphor sheet 4 having a high luminous flux can be obtained. When the D50 of the red phosphor is 40 ⁇ m or less, the chromaticity variation of the phosphor sheet 4 is improved.
- D10 of the red phosphor as the phosphor 1 is preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more. Thereby, the durability of the phosphor sheet 4 is improved.
- D10 of this red fluorescent substance it is preferable that it is 15 micrometers or less, and it is more preferable that it is 12 micrometers or less.
- the value x is an index of the particle size distribution of the red phosphor.
- a small value x means that there are few red phosphors having a small particle size (for example, KSF phosphor) that cause a decrease in durability, and a red phosphor having a large particle size that causes chromaticity variation (for example, KSF). This means that there is little phosphor.
- the value x is 1.5 or less, the durability and chromaticity variation of the phosphor sheet 4 are further improved.
- Yellow ring is a phenomenon in which the color appears different when the light emitter is viewed from the front and when viewed from an oblique direction. This yellow ring is a remarkable phenomenon when light scattering in the phosphor layer 2 is small.
- the value x is preferably 0.5 or more.
- D10, D50, and D90 are particle sizes measured by the following method.
- the cross section of the phosphor layer 2 is observed with an SEM, and in the obtained two-dimensional image, the maximum distance among the distances between the two intersections of the straight line that intersects the outer edge of the particles of the phosphor 1 at two points. Is defined as the individual particle size of the particles.
- the particle size of accumulated 10% from the small particle size side is D10
- the particle size (average particle size) of accumulated 50% is D50.
- a particle diameter of 90% of the accumulated portion is D90.
- this fluorescence can be obtained by any of mechanical polishing, microtome, CP (Cross-section Polisher) and focused ion beam (FIB) processing.
- CP Cross-section Polisher
- FIB focused ion beam
- the ⁇ -type sialon phosphor is a solid solution of ⁇ -type silicon nitride.
- Aluminum (Al) is substituted and dissolved in the Si position of ⁇ -type silicon nitride crystal, and oxygen (O) is substituted and dissolved in the nitrogen (N) position. It is what. Since there are two types of atoms in the unit cell (unit cell) of the ⁇ -type sialon used in the ⁇ -type sialon phosphor, Si 6-z Al z O z N 8-z is used as a general formula of the ⁇ -type sialon. It is done. In this general formula, z is a value greater than 0 and less than 4.2.
- the solid solution range of ⁇ -type sialon is very wide, and the molar ratio of (Si, Al) / (N, O) must be maintained at 3/4. is there.
- a general method for producing ⁇ -sialon is a method in which, in addition to silicon nitride, silicon oxide and aluminum nitride, or aluminum oxide and aluminum nitride are added and heated.
- ⁇ -type sialon is a ⁇ -type sialon that emits green light with a wavelength of 520 nm to 560 nm when excited by ultraviolet to blue light by incorporating a light emitting element such as rare earth (Eu, Sr, Mn, Ce, etc.) into the crystal structure. Becomes a phosphor. This is preferably used as a green light emitting component of a light emitting body such as a white LED.
- europium is ⁇ -sialon phosphor which contains the Eu 2+ activated ⁇ -sialon phosphor, since the emission spectrum is very sharp, blue, green, red narrow band emission It is a material suitable for the backlight light source of the required image processing display device or liquid crystal display panel.
- the D50 of the ⁇ -type sialon phosphor as the phosphor 1 is preferably 1 ⁇ m or more, and more preferably 10 ⁇ m or more. Further, D50 of this ⁇ -type sialon phosphor is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- D50 limiting in particular as a shape of (beta) type
- the content of the ⁇ -sialon phosphor as the phosphor 1 in the phosphor layer 2 is preferably 3% by weight or more of the entire phosphor layer 2 from the viewpoint of expanding the color reproduction range. More preferably, it is 5% by weight or more. Further, the content of the ⁇ -type sialon phosphor is preferably 50% by weight or less of the entire phosphor layer 2, and more preferably 40% by weight or less of the entire phosphor layer 2.
- the total of the proportion of the red phosphor and the proportion of the ⁇ -sialon phosphor in the total solid content in the phosphor layer 2 is preferably 50% by weight or more and 90% by weight or less.
- the lower limit of the sum of these ratios is more preferably 65% by weight or more, and even more preferably 70% by weight or more.
- the upper limit of the sum of these two ratios is more preferably 85% by weight or less, and further preferably 80% by weight or less.
- the porosity in the phosphor layer 2 is preferably 3% or less. % Or less, more preferably 1% or less, still more preferably 0.5% or less. This is because, as the porosity in the phosphor layer 2 is smaller, the light extraction efficiency from the phosphor layer 2 is improved, so that the phosphor sheet 4 that gives a high luminous flux can be obtained. . Further, the porosity of the phosphor layer 2 is not particularly limited to a lower limit, but is preferably 0.1% or more.
- the porosity is the ratio of the voids in the phosphor layer 2.
- This porosity can be measured by the following method.
- the phosphor sheet 4 and the cross section of the phosphor layer 2 are observed by any one of a mechanical polishing method, a microtome method, a CP method (Cross-section Polisher), and a focused ion beam (FIB) processing method. Grind. Thereafter, an area corresponding to the gap of the phosphor layer 2 is calculated from a two-dimensional image obtained by observing the obtained cross-section with an SEM, and the calculated area of the gap is calculated for the entire phosphor layer 2 in the section. Divide by area. Thereby, the porosity of the phosphor layer 2 is obtained.
- the above-mentioned value x (see formula (11)) that is an index of the particle size distribution of the red phosphor is small. By doing so, the porosity of the phosphor layer 2 tends to be small.
- the phosphor layer 2 may further contain a phosphor other than the phosphor 1 described above.
- phosphors other than the phosphor 1 described above include other red phosphors, other green phosphors, yellow phosphors, and blue phosphors.
- the green phosphor is a phosphor having an emission peak at a wavelength of 500 nm to 560 nm.
- the yellow phosphor is a phosphor having an emission peak at a wavelength of 560 nm to 590 nm.
- the blue phosphor is a phosphor having an emission peak at a wavelength of 430 nm to 500 nm.
- red phosphors are other than the red phosphor (Mn-activated bifluoride complex phosphor) represented by the general formula (1).
- examples of such other red phosphors include Y 2 O 2 S: Eu, La 2 O 2 S: Eu, Y 2 O 3 : Eu, and Gd 2 O 2 S: Eu.
- green phosphors are other than ⁇ -type sialon phosphors.
- SrAl 2 O 4 Eu
- Y 2 SiO 5 Ce
- Tb Ce
- MgAl 11 O 19 Ce
- Tb Ce
- Sr 7 Al 12 O 25 Eu
- (Mg, Ca , Sr, and Ba, at least one element) Ga 2 S 4 Eu, and the like.
- yellow phosphors include yttrium / aluminum oxide phosphors activated with at least cerium, yttrium / gadolinium / aluminum oxide phosphors consolidated with at least cerium, and at least cerium-activated yttrium / gallium / Examples thereof include aluminum oxide phosphors.
- blue phosphor for example, Sr 5 (PO 4 ) 3 Cl: Eu, (SrCaBa) 5 (PO 4 ) 3 Cl: Eu, (BaCa) 5 (PO 4 ) 3 Cl: Eu, (Mg, Ca, Sr , Ba, at least one element) 2 B 5 O 9 Cl: Eu, Mn, (at least one element of Mg, Ca, Sr, Ba) (PO 4 ) 6 Cl 2 : Eu, Mn Etc.
- Examples of phosphors that emit light corresponding to the current mainstream blue LEDs include Y 3 (Al, Ga) 5 O 12 : Ce, (Y, Gd) 3 Al 5 O 12 : Ce, Lu 3 Al 5.
- YAG phosphors such as O 12 : Ce, Y 3 Al 5 O 12 : Ce
- TAG phosphors such as Tb 3 Al 5 O 12 : Ce
- (Ba, Sr) 2 SiO 4 Eu phosphors
- the refractive index of the resin 14 contained in the phosphor layer 2 is 1.45 or more and 1.7 or less.
- the refractive index of the resin 14 is more preferably 1.5 or more, and more preferably 1.65 or less. Since the refractive index of the resin 14 is 1.45 or more, the refractive index of the Mn-activated double fluoride complex phosphor (red phosphor as the phosphor 1) having an average refractive index of around 1.4. The difference is increased, and light is easily scattered in the phosphor layer 2. Therefore, the optical path length from when light enters the phosphor layer 2 to when it exits becomes longer. By increasing the optical path length, the blue light emitted from the LED chip is easily color-converted by the phosphor 1 in the phosphor layer 2, so that the amount of phosphor for expressing desired chromaticity is reduced. Can do.
- the refractive index of the resin 14 exceeds 1.7, the optical path length becomes longer than necessary due to excessive scattering of light in the phosphor layer 2. For this reason, the emitted light emitted from the phosphor 1 in the phosphor layer 2 is easily absorbed by the phosphor 1, and as a result, the intensity of the light emitted from the phosphor is reduced.
- the material of the resin 14 is not particularly limited as long as the phosphor (such as the phosphor 1 shown in FIG. 1A) can be uniformly dispersed therein and the phosphor layer 2 can be formed.
- the resin 14 include silicone resin, epoxy resin, polyarylate resin, PET-modified polyarylate resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, modified acrylic resin, Examples thereof include polystyrene resin and acrylonitrile / styrene copolymer resin. Of these, silicone resins and epoxy resins are preferred from the viewpoint of transparency. Furthermore, a silicone resin is particularly preferable from the viewpoint of heat resistance.
- a curable silicone resin is preferable.
- the curable silicone resin used as the resin 14 may be of one liquid type or two liquid type (three liquid type).
- the curable silicone resin includes a dealcohol type, a deoxime type, a deacetic acid type, a dehydroxylamine type and the like as a type that causes a condensation reaction with moisture in the air or a catalyst.
- the curable silicone resin includes an addition reaction type as a type that causes a hydrosilylation reaction by a catalyst. Any of these types of curable silicone resins may be used as the resin 14.
- an addition reaction type silicone resin is more preferable because it has no by-products associated with the curing reaction, has a small curing shrinkage, and can easily be cured by heating.
- the addition reaction type silicone resin as an example of the resin 14 is formed by, for example, a hydrosilylation reaction between a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom.
- Examples of the “compound containing an alkenyl group bonded to a silicon atom” include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane Etc.
- Examples of the “compound having a hydrogen atom bonded to a silicon atom” include, for example, methyl hydrogen polysiloxane, dimethyl polysiloxane-CO-methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, methyl hydrogen polysiloxane-CO-methyl. Examples thereof include phenyl polysiloxane. Examples of the addition reaction type silicone resin include those formed by hydrosilylation reaction of such materials. In addition, as the resin 14, other well-known resins as described in, for example, JP 2010-159411 A can be used.
- a resin 14 it is also possible to use a commercially available product, for example, a general silicone sealing material for LED use.
- a commercially available product for example, a general silicone sealing material for LED use.
- Specific examples thereof include OE-6630A / B and OE-6336A / B manufactured by Toray Dow Corning, and SCR-1012A / B and SCR-1016A / B manufactured by Shin-Etsu Chemical Co., Ltd.
- the silicone resin as the resin 14 may have heat-fusibility. This is because, when the resin 14 of the phosphor layer 2 is a silicone resin having heat-fusibility, the phosphor sheet 4 provided with the phosphor layer 2 has heat-fusibility. This is because the phosphor sheet 4 having the above can be heated and attached to the LED chip.
- the heat fusibility here is a property of softening by heating. In the case where the phosphor sheet 4 has heat-fusibility, it is not necessary to use an adhesive for attaching the phosphor sheet 4 to the LED chip, so that the manufacturing process of the light emitter and the like can be simplified.
- the storage elastic modulus at 25 ° C. is 0.1 MPa or more, and the storage elastic modulus at 100 ° C. is less than 0.1 MPa.
- a cross-linked product obtained by hydrosilylation reaction of a cross-linkable silicone composition including the following components (A) to (D) is particularly preferable.
- This crosslinked product can be preferably used as a matrix resin for the phosphor sheet 4 that does not require an adhesive because the storage elastic modulus decreases at 60 ° C. to 250 ° C. and high adhesive strength is obtained by heating.
- the component (A) is an organopolysiloxane represented by the following average unit formula (21). (R 1 2 SiO 2/2 ) a (R 1 SiO 3/2 ) b (R 2 O 1/2 ) c (21)
- R 1 is a phenyl group, an alkyl or cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
- 65 mol% to 75 mol% of R 1 is a phenyl group
- 10 mol% to 20 mol% of R 1 is an alkenyl group.
- R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the component (B) is an organopolysiloxane represented by the following general formula (2).
- This organopolysiloxane has a content of 5 to 15 parts by weight per 100 parts by weight of component (A).
- R 3 is a phenyl group, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, or an alkenyl group having 2 to 6 carbon atoms.
- 40 mol% to 70 mol% of R 3 is a phenyl group, at least one R 3 is an alkenyl group.
- m is an integer in the range of 5-50.
- Component (C) is an organotrisiloxane represented by the following general formula (3).
- the molar ratio of silicon-bonded hydrogen atoms in component (C) to the sum of alkenyl groups in component (A) and alkenyl groups in component (B) is in the range of 0.5 to 2.
- R 4 is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms. However, 30 mol% to 70 mol% of R 4 is a phenyl group.
- component is a catalyst for hydrosilylation reaction.
- This catalyst for hydrosilylation reaction is of an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in component (A) and component (B) and the silicon-bonded hydrogen atom in component (C). .
- component (A) when the values of a, b, and c satisfy the above conditions, sufficient hardness at room temperature of the resulting crosslinked product is obtained, and at the high temperature of this crosslinked product. Can be obtained.
- the resulting crosslinked product In the general formula (2) of the component (B), when the phenyl group content is less than the lower limit of the above range, the resulting crosslinked product is not sufficiently softened at high temperature. On the other hand, if the phenyl group content exceeds the upper limit of the above range, the resulting crosslinked product loses its transparency and its mechanical strength also decreases.
- at least one of R 3 is an alkenyl group.
- m is an integer in the range of 5-50.
- the numerical range of m is a range in which handling workability can be maintained while maintaining the mechanical strength of the obtained cross-linked product.
- the content of the component (B) is an amount in the range of 5 to 15 parts by weight with respect to 100 parts by weight of the component (A). This range of content is a range for obtaining sufficient softening of the obtained crosslinked product at a high temperature.
- R 4 is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms.
- alkyl group for R 4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a heptyl group.
- cycloalkyl group represented by R 4 include a cyclopentyl group and a cycloheptyl group.
- the phenyl group content is in the range of 30 mol% to 70 mol%. The range of the content is a range in which the obtained crosslinked product can be sufficiently softened at a high temperature, and the transparency and mechanical strength of the crosslinked product can be maintained.
- the content of the component (C) is such that the molar ratio of silicon-bonded hydrogen atoms in the component (C) is 0. 0 with respect to the sum of the alkenyl groups in the component (A) and the alkenyl groups in the component (B).
- the amount is in the range of 5 to 2.
- the range of this content is a range in which sufficient hardness at room temperature of the obtained crosslinked product is obtained.
- Component (D) is a hydrosilylation catalyst for promoting a hydrosilylation reaction between an alkenyl group in component (A) and component (B) and a silicon atom-bonded hydrogen atom in component (C).
- component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Of these, platinum-based catalysts are preferred because they can significantly accelerate the curing of the silicone composition.
- the platinum catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex.
- the platinum-based catalyst is preferably a platinum-alkenylsiloxane complex.
- alkenyl siloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
- 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good.
- the content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in the component (A) and the component (B) and the silicon atom-bonded hydrogen atom in the component (C).
- the content of the component (D) is such that the metal atom in the component (D) is in the range of 0.01 ppm to 500 ppm in terms of mass unit with respect to the silicone composition.
- the content of the component (D) is preferably such that the metal atom is in the range of 0.01 ppm to 100 ppm, and in particular, the metal atom is in the range of 0.01 ppm to 50 ppm.
- An amount is preferred. This range of content is a range in which the resulting silicone composition is sufficiently crosslinked and does not cause problems such as coloring.
- the ratio of the resin 14 to the total solid content in the phosphor layer 2 is preferably 10% by weight or more and 60% by weight or less. This is because, by setting the ratio of the resin 14 in the above range, both improvement in color reproducibility and high durability of the phosphor sheet 4 can be achieved.
- the refractive index of the resin 14 can be measured by measuring the refractive index of the refractive index measurement sample using a refractive index / film thickness measuring device “Prism Coupler MODEL 2010 / M” (Metricon).
- the refractive index measurement sample was prepared by stirring and defoaming the resin 14 for 10 minutes at 1000 rpm using a planetary stirring and degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to prepare a dispersion of the resin 14. After 5 cc of this dispersion is dropped on a PET film, it can be obtained by heating in an oven at 150 ° C. for 1 hour.
- the phosphor sheet 4 according to the embodiment of the present invention contains fine particles in the phosphor layer 2 for the purpose of improving the dispersion stability of the phosphor 1 in the phosphor layer 2 in the resin 14. Also good.
- the fine particles include fine particles composed of titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, barium titanate, and the like. These may be used alone or in combination of two or more.
- the fine particles contained in the phosphor layer 2 are preferably silica fine particles, alumina fine particles, and silicone fine particles from the viewpoint of easy availability, and silicone fine particles are particularly preferable from the viewpoint of low hardness. Since the hardness of the fine particles is low, there is an effect of suppressing the crushing of the red phosphor in the step of dispersing the phosphor 1, and as a result, the phosphor sheet 4 having higher emission intensity can be obtained.
- silicone fine particles include hydrolyzing and then condensing organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane.
- organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane.
- silicone fine particles obtained by the method.
- organotrialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-proxysilane, methyltri-i-proxysilane, methyltri-n-butoxysilane, methyltri-i-butoxysilane, and methyltri-s.
- organodialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- ( 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, Examples thereof include vinyl methyldiethoxysilane.
- organotriacetoxy silane examples include methyl triacetoxy silane, ethyl triacetoxy silane, vinyl triacetoxy silane, and the like.
- organodiacetoxysilane examples include dimethyldiacetoxysilane, methylethyldiacetoxysilane, vinylmethyldiacetoxysilane, vinylethyldiacetoxysilane, and the like.
- organotrioxime silane include methyl trismethyl ethyl ketoxime silane and vinyl trismethyl ethyl ketoxime silane.
- organodioxime silane examples include methyl ethyl bismethyl ethyl ketoxime silane.
- Such fine particles are specifically the method reported in Japanese Patent Laid-Open No. 63-77940 and the method reported in Japanese Patent Laid-Open No. 6-248081. It can be obtained by the method reported in JP-A No. 2003-342370, the method reported in JP-A No. 4-88022, and the like. Also, at least one of organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and partial hydrolysates thereof is added to the alkaline aqueous solution.
- organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and partial hydrolysates thereof is added to the alkaline aqueous solution.
- At least one hydrolysis of the organosilane and its partial hydrolyzate by adding at least one of the organosilane and its partial hydrolyzate to water or an acidic solution.
- a method in which alkali is added and the condensation reaction proceeds to obtain fine particles at least one of organosilane and a hydrolyzate thereof is used as an upper layer, and an alkali or a mixture of an alkali and an organic solvent is used as a lower layer
- the method or the like to obtain the emissions and at least one by hydrolyzing and polycondensing microparticles hydrolyzate thereof are also known. In any of these methods, fine particles contained in the phosphor layer 2 can be obtained in the present invention.
- organosilane and its partial hydrolyzate is hydrolyzed / condensed to produce spherical organopolysilsesquioxane fine particles, as reported in JP-A-2003-342370. It is preferable to use silicone fine particles obtained by a method in which a polymer dispersant is added to a reaction solution.
- the average particle size of the silicone fine particles is represented by D50.
- the lower limit of the average particle diameter is preferably 0.05 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
- an upper limit of this average particle diameter it is preferable that it is 2.0 micrometers or less, and it is further more preferable that it is 1.0 micrometers or less.
- the average particle diameter (D50) of the silicone fine particles can be obtained by the same method as the average particle diameter of the red phosphor as the phosphor 1 described above.
- the proportion of fine particles in the total solid content in the phosphor layer 2 is preferably 0.1% by weight or more and 10% by weight or less.
- the proportion of the fine particles is within the above range, the dispersion stability of the phosphor 1 in the phosphor layer 2 (in the resin 14) can be improved.
- the color reproducibility of the phosphor sheet 4 is improved. Can achieve both high luminous flux and high durability.
- the contents of the phosphor 1, the resin 14, and the silicone fine particles in the phosphor layer 2 in the present invention can also be obtained from the prepared phosphor layer 2 and the LED luminous body on which the phosphor layer 2 is mounted.
- the phosphor layer 2 is embedded and cut with a predetermined resin, a sample whose cross section is polished is prepared, and the exposed cross section is observed with a scanning electron microscope (SEM). It is possible to clearly discriminate the particle portion of the phosphor 1, the silicone fine particle portion, and the resin 14 portion. From the area ratio of the cross-sectional image, it is possible to accurately measure the volume ratios of phosphor 1 (phosphor particles), silicone fine particles, and resin 14 occupying the entire phosphor layer 2.
- the weight ratio of the phosphor 1 to the phosphor layer 2 can be calculated by dividing each volume ratio by the specific gravity. .
- the composition of each component forming the phosphor layer 2 can be determined by analyzing the cross-section of the phosphor layer 2 with high-resolution micro-infrared spectroscopy or IPC emission analysis. . If the composition of each of these components is clarified, the specific gravity specific to the substance of the resin 14 or the phosphor 1 can be estimated with a considerable degree of accuracy, and the weight ratio can be obtained using this.
- the phosphor layer 2 is preferably blended with a hydrosilylation reaction retarder in order to suppress curing at room temperature and lengthen the pot life.
- a hydrosilylation reaction retarder examples include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol and the like.
- Alcohol derivatives having a carbon-carbon triple bond enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, tetramethyltetravinylcyclotetrasiloxane, tetramethyl Low molecular weight siloxane containing alkenyl groups such as tetrahexenylcyclotetrasiloxane, methyl-tris (3-methyl-1-butyne-3-oxy) silane, vinyl-tris (3-methyl-1-butyne-3-oxy) silane, etc. And alkyne-containing silanes.
- the phosphor layer 2 has an inorganic filler such as fumed silica, glass powder, quartz powder, etc., an inorganic filler such as zinc oxide, a flame retardant, and the like, as long as the effects of the present invention are not impaired.
- the transparent resin layer 5 (see FIG. 1B) is a resin layer that has a total light transmittance of 90% or more at a wavelength of 450 nm and does not include the phosphor 1.
- the transparent resin layer 5 is laminated on the phosphor layer 2 as shown in FIG. 1B, for example.
- the minimum transmittance of the transparent resin layer 5 at a wavelength of 400 nm to 800 nm is preferably 80% or more.
- the minimum transmittance is the smallest value of the light transmittance at wavelengths of 400 nm to 800 nm.
- the phosphor sheet 4 can easily achieve both high luminous flux and high durability.
- the presence of the transparent resin layer 5 on the phosphor layer 2 improves the durability of the phosphor 1 (for example, a red phosphor) in the phosphor layer 2, and as a result, the durability as the phosphor sheet 4. Will improve.
- the transparent resin layer 5 may further contain fine particles. Since the transparent resin layer 5 contains fine particles, the film thickness uniformity of the transparent resin layer 5 is improved, so that the phosphor sheet 4 can be accurately picked up in the phosphor sheet 4 pick-up process described later. .
- One of the causes for the non-uniform thickness of the transparent resin layer 5 is the flow of resin in the drying process when the transparent resin layer 5 is formed. In this drying step, the resin contained in the transparent resin layer 5 is easy to flow because the viscosity is lowered by being heated.
- the resin contained in the transparent resin layer 5 is a silicone resin having heat-fusibility, since the viscosity of the resin is significantly reduced, the film thickness of the transparent resin layer 5 tends to be non-uniform.
- a silicone resin having heat-fusibility is used for the transparent resin layer 5, it is particularly important that the transparent resin layer 5 contains fine particles in order to maintain the uniformity of the film thickness of the transparent resin layer 5.
- Improvement of the uniformity of the film thickness of the transparent resin layer 5 also has an effect of enhancing the function of the transparent resin layer 5 as a protective layer.
- this thin portion does not sufficiently function as a protective layer, so that the durability of the obtained light emitter is inferior. According to the present invention, such a situation can be suppressed.
- the resin used for the transparent resin layer 5 examples include silicone resin, fluororesin, epoxy resin, polyarylate resin, PET-modified polyarylate resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, One or more resins selected from a modified acrylic resin, a polystyrene resin, and an acrylonitrile / styrene copolymer resin are preferable. Among these, one or more kinds of resins selected from silicone resins, fluororesins, and epoxy resins are more preferable, and silicone resins are particularly preferable from the viewpoint of heat resistance.
- the silicone resin may have a heat-fusibility.
- this silicone resin has heat-fusibility, when forming the transparent resin layer 5 by the transparent resin sheet method mentioned later, the fluorescent substance layer 2 and the transparent resin layer 5 can be adhere
- the fine particles used for the transparent resin layer 5 are preferably those that absorb little visible light or emit light.
- the fine particles include fine particles such as titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate.
- one or more types of fine particles selected from silica fine particles, alumina fine particles, and silicone fine particles are more preferable from the viewpoint of easy availability, and silicone fine particles are particularly preferable from the viewpoint of easy control of the refractive index and particle size. .
- the minimum transmittance of the transparent resin layer 5 at a wavelength of 400 nm to 800 nm is reduced. It can be 80% or more.
- the average particle size of the fine particles contained in the transparent resin layer 5 is preferably 1 nm or more, and more preferably 3 nm or more.
- the average particle size of the fine particles is preferably 1000 nm or less, and more preferably 300 nm or less.
- the average particle diameter of the fine particles is equal to or more than a preferable lower limit value, the fine particles can be stably dispersed in the transparent resin layer 5. Since the average particle diameter of the fine particles is 1000 nm or less, light scattering in the transparent resin layer 5 can be suppressed, so that the high light transmittance of the transparent resin layer 5 can be maintained.
- the average particle diameter of the fine particles is a median diameter (D50).
- the average particle diameter of the fine particles can be obtained by the same method as the average particle diameter of the red phosphor as the phosphor 1 described above.
- the proportion of fine particles in the total solid content in the transparent resin layer 5 is preferably 0.1% by weight or more, and more preferably 1% by weight or more. Further, the proportion of the fine particles is preferably 30% by weight or less, and more preferably 10% by weight or more.
- the variation in the film thickness of the transparent resin layer 5 can be suppressed when the ratio of the fine particles is equal to or more than a preferable lower limit value. When the proportion of the fine particles is equal to or less than the preferable upper limit value, the high light transmittance of the transparent resin layer 5 can be maintained.
- the light transmittance of the transparent resin layer 5 containing fine particles can be measured using a spectrophotometer.
- a spectrophotometer For example, when U-4100 Spectrophotometer manufactured by Hitachi, Ltd. is used, the light transmittance of the sample of the transparent resin layer 5 can be measured with a basic configuration using an integrating sphere attached to this measuring apparatus.
- the slit is 2 nm and the scanning speed is 600 nm / min.
- the sample for light transmittance measurement of the transparent resin layer 5 (hereinafter referred to as “transmittance measurement sample”) can be prepared by the following method. For example, the resin and fine particles used for the transparent resin layer 5 are stirred and degassed to prepare a dispersion. The dispersion is applied onto quartz glass with a blade coater and then heated in an oven at 150 ° C. for 1 hour. In this way, a transmittance measurement sample can be produced.
- the film thickness of the transmittance measurement sample can be measured by the following method. For example, the thickness at a predetermined position of quartz glass is measured in advance with a micrometer, and the measured position is marked. Next, after forming a transmittance measurement sample of the transparent resin layer 5 on the quartz glass by the above-described method, the thickness of the marking portion is again measured with a micrometer. By subtracting the previously measured thickness of the quartz glass from the obtained thickness, the film thickness of this transmittance measurement sample can be obtained.
- the refractive index difference between the resin and the fine particles contained in the transparent resin layer 5 is preferably 0.5 or less, more preferably 0.3 or less, and particularly preferably 0.1 or less.
- the refractive index of the resin contained in the transparent resin layer 5 is preferably 1.3 or more, and preferably 1.6 or less. Since the refractive index difference of the resin is 1.3 or more, the difference in refractive index between the transparent resin layer 5 and the phosphor layer 2 becomes relatively small. Therefore, the light extraction efficiency from the phosphor layer 2 to the transparent resin layer 5 is improved. Can be improved.
- the refractive index of the resin is 1.6 or less, the difference in refractive index between the transparent resin layer 5 and the air layer becomes relatively small, so that the light extraction efficiency from the transparent resin layer 5 to the air layer is improved. Can be made. Further, from the viewpoint of further improving the light extraction efficiency, the refractive index of the resin contained in the transparent resin layer 5 is preferably equal to or lower than the refractive index of the resin contained in the phosphor layer 2.
- the refractive index of the resin contained in the transparent resin layer 5 is measured by measuring the refractive index of the refractive index measurement sample using a refractive index / film thickness measuring device “Prism Coupler Model 2010 / M” (made by Metricon). can do.
- this resin was stirred for 10 minutes at 1000 rpm using a planetary stirring deaerator “Mazerustar KK-400” manufactured by Kurabo Industries, and defoamed to prepare a dispersion. After dropping 5 cc on the film, it can be obtained by heating at 150 ° C. for 1 hour in an oven.
- the phosphor sheet 4 according to the embodiment of the present invention may include another phosphor layer or a diffusion layer different from the phosphor layer 2 on at least one of the top and bottom of the phosphor layer 2.
- the transparent resin layer formed under the phosphor layer 2 or another phosphor layer does not use an adhesive for the LED chip. It is preferable to have heat-fusibility so that it can be affixed to.
- the refractive index of this LED chip surface and the transparent resin layer located under any phosphor layer As the refractive index difference is smaller, the light extraction efficiency from the LED chip surface to the transparent resin layer can be improved. Therefore, in this case, the refractive index of the transparent resin layer is preferably 1.56 or more.
- the diffusion layer is a layer containing a predetermined resin and a diffusion material such as silica, titania or zirconia. By forming the diffusion layer, the directivity of emitted light can be weakened and more isotropic emitted light can be obtained. Therefore, the diffusion layer is preferably formed in the upper layer of the phosphor layer 2.
- One method for producing the phosphor sheet 4 is to apply the phosphor layer 2 directly on the support 3.
- a coating solution for forming the phosphor layer 2 a solution in which the phosphor 1 is dispersed in the resin 14 (hereinafter, referred to as “phosphor layer preparation resin solution”) is prepared.
- the resin liquid for producing a phosphor layer is obtained by mixing phosphor 1 and resin 14 in a solvent.
- the type of the solvent is not particularly limited as long as the viscosity of the resin 14 in a fluid state can be adjusted.
- the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexane, acetone, terpineol, butyl carbitol, butyl carbitol acetate, glyme, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. Can be mentioned.
- a resin solution for preparing a phosphor layer can be obtained by homogeneously mixing and dispersing with a stirrer / kneader such as a three-roller, ball mill, planetary ball mill, or bead mill. Defoaming is preferably performed after this mixing and dispersion or in the process of mixing and dispersion under vacuum or reduced pressure conditions.
- the Mn-activated bifluoride complex phosphor as the phosphor 1 has properties of low hardness and brittleness as compared with a phosphor produced by firing at a high temperature such as a ⁇ -type sialon phosphor. Therefore, when the Mn-activated double fluoride complex phosphor is dispersed with a stirrer / kneader or the like, the Mn-activated double fluoride complex phosphor can be dispersed by setting the dispersion conditions so that the impact applied to the Mn-activated double fluoride complex phosphor is as small as possible. It is preferable to suppress crushing of the fluoride complex phosphor. By suppressing the crushing of the Mn-activated double fluoride complex phosphor, the phosphor sheet 4 having a high emission intensity can be obtained.
- the phosphor layer preparation resin solution prepared as described above is applied onto the support 3 and dried.
- the phosphor layer 2 obtained on the support 3 is produced by heat curing.
- Application of the resin liquid for preparing the phosphor layer on the support 3 is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, screen printing, natural roll coater, air knife coater, roll.
- a blade coater, two stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater or the like can be used.
- a slit die coater In order to obtain the uniformity of the film thickness of the phosphor layer 2, it is preferable to apply with a slit die coater.
- the phosphor layer 2 can also be produced by using a printing method such as screen printing, gravure printing, or lithographic printing. In particular, screen printing is preferably used.
- the drying of the phosphor layer forming resin liquid can be performed using a general heating device such as a hot air dryer or an infrared dryer.
- a general heating device such as a hot air dryer or an infrared dryer is used.
- the heat curing condition is usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 minutes to 3 hours.
- the phosphor sheet 4 provided with at least the phosphor layer 2 can be produced by the method described above. As illustrated in FIG. 1A, the phosphor sheet 4 is in a state of being supported by the support body 3 as a single sheet.
- the support 3 used in the present invention is not particularly limited, and examples thereof include known metals, resin films, glass, ceramics, paper, and cellulose acetate.
- glass and a resin film are preferably used from the viewpoint of easy preparation of the phosphor sheet 4 and easy separation of the phosphor sheet 4.
- the support 3 is preferably in the form of a flexible film because of the adhesion when the phosphor sheet 4 is attached to the LED chip.
- a film having high strength is preferable as the support 3 so that there is no fear of breakage or the like when the film-shaped support 3 is handled.
- a resin film is preferable as the support 3 in terms of these required characteristics and economy.
- a plastic film selected from the group consisting of polyethylene terephthalate, polyphenylene sulfide, polypropylene, and polyimide is preferable from the viewpoints of economy and handleability.
- a polyimide film is preferable from the viewpoint of heat resistance.
- the surface of the support 3 may be subjected to a release treatment in advance from the ease of peeling off the phosphor sheet 4 from the support 3.
- the forming method of the transparent resin layer 5 includes a direct coating method and a transparent resin sheet method.
- a resin solution whose viscosity is adjusted with a transparent resin solvent for the production of the transparent resin layer 5 (hereinafter referred to as “resin solution for producing a transparent resin layer”) is directly applied onto the phosphor layer 2. Thereafter, drying and heat curing are performed.
- the transparent resin layer preparation resin solution can be applied by the same method as the preparation of the phosphor layer 2 (application of the phosphor layer preparation resin solution).
- a resin solution for preparing a transparent resin layer with a slit die coater can be applied using a general heating device such as a hot air dryer or an infrared dryer.
- a general heating device such as a hot air dryer or an infrared dryer is used.
- the heat curing condition is usually 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 minutes to 3 hours.
- the transparent resin sheet method a transparent resin sheet is produced, and the phosphor layer 2 side of the phosphor sheet 4 and the transparent resin layer 5 side of the produced transparent resin sheet are bonded to each other on the phosphor layer 2.
- the transparent resin sheet can be produced by the same method as the phosphor sheet 4 provided with the phosphor layer 2 described above. That is, using the “transparent resin layer preparation resin liquid” instead of the “phosphor layer preparation resin liquid”, a method similar to the method of manufacturing the phosphor sheet 4 described above is performed, and a predetermined support (for example, a support)
- a transparent resin sheet can be produced by forming the transparent resin layer 5 on the same body 3.
- the resin of at least one of the phosphor layer 2 and the transparent resin layer 5 needs to be in a semi-cured state.
- the resin of at least one layer is in a semi-cured state, the phosphor layer 2 and the transparent resin layer 5 can be bonded.
- the transparent resin sheet method at least the resin of the transparent resin layer 5 is more preferably semi-cured, and both the resin 14 of the phosphor layer 2 and the resin of the transparent resin layer 5 are in a semi-cured state. Particularly preferred.
- the phosphor layer 2 and the transparent resin layer 5 are bonded together by heating.
- the viscosity of each resin of the phosphor layer 2 and the transparent resin layer 5 is lowered, so that the phosphor layer 2 and the transparent resin layer 5 can be firmly bonded.
- the heating condition is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher.
- the resin in a semi-cured state (for example, the resin of the transparent resin layer 5) is cured before the phosphor layer 2 and the transparent resin layer 5 are bonded.
- the heating condition is preferably 200 ° C. or less, more preferably 170 ° C. or less, and particularly preferably 150 ° C. or less.
- the phosphor layer 2 and the transparent resin layer 5 are preferably bonded together in a vacuum atmosphere.
- a vacuum atmosphere is an atmosphere whose pressure is a predetermined value or less. The pressure in this vacuum atmosphere is 100 hPa or less, more preferably 10 hPa or less, further preferably 5 hPa or less, and particularly preferably 1 hPa or less.
- FIG. 2 is a process diagram showing an example of a method for manufacturing a light emitter using the phosphor sheet according to the embodiment of the present invention.
- the following description is an example and the manufacturing method of the light-emitting body based on embodiment of this invention is not limited to what is demonstrated below.
- the manufacturing method of the light emitter using the phosphor sheet 4 roughly includes three steps.
- the first step is an individualization step for individualizing the phosphor sheet 4.
- the second step is a pickup step for picking up the individual phosphor sheet 4.
- the third step is a pasting step of pasting the picked up phosphor sheet 4 (individualized by the individualizing step) to a light source.
- the manufacturing method of this light-emitting body may include the other process as needed.
- the phosphor sheet 4 is composed of the phosphor layer 2 formed on the support 3, and the phosphor layer 2 as the phosphor sheet 4 is separated into individual pieces, and an LED chip which is an example of a light source A method for manufacturing a light emitter according to an embodiment of the present invention will be described with reference to FIG.
- the phosphor sheet 4 can be singulated by a method such as punching with a mold, processing with a laser, dicing or cutting.
- the phosphor layer 2 as the phosphor sheet 4 may be in a semi-cured state or may be cured in advance. Processing with a laser imparts high energy to the phosphor layer 2, so that the resin of the phosphor layer 2 (for example, the resin 14 shown in FIG. 1A) is burnt or the phosphor (for example, the phosphor 1 shown in FIG. 1A) is deteriorated. It is very difficult to avoid. Therefore, as a method for dividing the phosphor sheet 4 into pieces, cutting or cutting with a blade is desirable.
- the phosphor layer 2 as the phosphor sheet 4 is in a state of being supported by the support 3.
- the phosphor layer 2 on the support 3 is cut by the blade 6 (state S1).
- the phosphor layer 2 is divided into a plurality of pieces and processed into the individual phosphor layers 7 (state S2).
- the individualized phosphor layer 7 remains attached to the support 3.
- the blade 6 is, for example, a rotary blade.
- a device for cutting the phosphor layer 2 with a rotary blade a device called a dicer used for cutting (dicing) a semiconductor substrate into individual chips can be suitably used. If the dicer is used, the width of the dividing line of the phosphor layer 2 can be precisely controlled by the thickness of the rotary blade and the condition setting, so that higher processing accuracy can be obtained than cutting the phosphor layer 2 by pushing a simple blade. .
- the phosphor layer 2 may be singulated together with the support 3. Alternatively, the support 3 may not be cut while the phosphor layer 2 is separated. Under the present circumstances, it is preferable to perform what is called a half cut with respect to the support body 3 in which the notch line which does not penetrate enters.
- the phosphor layer 2 is preferably cut by dry cutting.
- Dry cutting is a cutting method that does not use liquid such as water during cutting.
- the cutting of the phosphor layer 2 in the singulation process is not limited to this, and examples thereof include cutting with a Thomson blade. Dry cutting is particularly effective when the phosphor layer 2 contains a phosphor whose luminous efficiency is reduced by reacting with water, such as K 2 SiF 6 : Mn.
- the phosphor sheet 4 may be subjected to perforation processing of the phosphor layer 2 before or after the individualization step or simultaneously with the individualization step.
- a known method such as laser processing or punching with a mold can be suitably used.
- laser processing causes scorching of the resin of the phosphor layer 2 and deterioration of the phosphor, punching with a mold is possible. Processing is more desirable.
- the phosphor sheet 4 singulated by the singulation process described above is picked up by a pickup process that is the next process of the singulation process.
- a pickup process that is the next process of the singulation process.
- the singulated phosphor layer 7 is in a state of being stuck on the support 3.
- the singulated phosphor layer 7 is peeled off and picked up from the support 3 by a pickup device (not shown) provided with a suction device such as a collet 8 (state S3).
- the individualized phosphor layer 7 (an example of the individualized phosphor sheet 4) picked up by the pickup process described above is attached to the light source by the application process which is the next process of the pickup process.
- the singulated phosphor layer 7 is picked up by a collet 8.
- the collet 8 is transported together with the individualized phosphor layer 7 to the position of the LED chip 9 (an example of a light source) mounted on the substrate 11, thereby the light extraction surface of the LED chip 9 and the individualized phosphor layer 7.
- the adhesive surface (for example, the lower surface) is made to oppose.
- the collet 8 presses and adheres the adhesive surface of the singulated phosphor layer 7 to the light extraction surface of the LED chip 9 (state S4).
- the reflector 10 may be formed around the LED chip 9 on the substrate 11.
- an adhesive (not shown) for attaching the singulated phosphor layer 7 and the LED chip 9 in the attaching step.
- this adhesive a well-known die bond agent and an adhesive agent can be used.
- acrylic resin, epoxy resin, urethane resin, silicone resin, modified silicone resin, phenol resin, polyimide, polyvinyl alcohol, polymethacrylate resin, melamine resin, urea resin adhesive can be used.
- the phosphor layer 2 has adhesiveness
- the individualized phosphor layer 7 and the LED chip 9 may be attached using this adhesiveness.
- the sticking step is a step of heating the individual phosphor layer 7 and sticking it to the LED chip 9
- this sticking step is performed in the atmosphere, the LED chip 9 and the individual phosphor layer 7 are not separated. Air bubbles may be caught in When bubbles are bitten, light is irregularly reflected at the interface between the bubbles and the LED chip 9 and at the interface between the bubbles and the singulated phosphor layer 7. Thereby, the light extraction efficiency from the LED chip 9 is lowered, and as a result, the luminance of the light emitter (for example, the light emitter 13 shown in FIG. 2) manufactured using the phosphor sheet 4 is lowered. From the viewpoint of preventing such bubble entrapment, this sticking step is preferably performed in a vacuum atmosphere.
- the light emitting body manufacturing method described above may further include a connection step of electrically connecting the LED chip 9 and the substrate 11 which is an example of a circuit board as other steps.
- this connection step the electrode of the LED chip 9 and the wiring of the substrate 11 are electrically connected by a known method. Thereby, the light emitter 13 can be obtained.
- the LED chip 9 has an electrode on the light extraction surface side, the electrode on the upper surface of the LED chip 9 and the wiring of the substrate 11 are connected by wire bonding.
- the LED chip 9 is a flip chip type having an electrode pad on the surface opposite to the light emitting surface, the electrode surface of the LED chip 9 is opposed to the wiring of the substrate 11 and these are connected by batch bonding.
- the substrate 11 and the LED chip 9 may be connected before the individualized phosphor sheet 4 (for example, the individualized phosphor layer 7) is attached.
- the individual phosphor layer 7 When the individual phosphor layer 7 is attached to the LED chip 9 in a semi-cured state, the individual phosphor layer 7 can be cured at a suitable timing before or after the connection step described above. For example, when thermocompression bonding is performed so that the flip chip type LED chip 9 is bonded to the substrate 11 at once, the individualized phosphor layer 7 may be simultaneously cured by the heating. In the case where the package in which the LED chip 9 and the substrate 11 are connected is surface-mounted on a larger circuit board, the individualized phosphor layer 7 may be cured simultaneously with soldering by solder reflow. .
- the individual phosphor layer 7 When the LED chip 9 is attached in a state where the individual phosphor layer 7 is cured, after the individual phosphor layer 7 and the LED chip 9 are attached, the individual phosphor layer 7 There is no need to provide a curing process.
- the case where the individualized phosphor layer 7 is affixed to the LED chip 9 in a cured state includes, for example, a case where a separate adhesive layer is formed on the cured individualized phosphor layer 7, or an individualized phosphor layer. This is the case when the body layer 7 has heat-fusibility after curing.
- the manufacturing method of the light emitting body described above may further include a sealing step of sealing the LED chip 9 after the pasting step is performed as another step.
- a sealing step of sealing the LED chip 9 after the pasting step is performed as another step.
- the transparent sealing material 12 is placed on the substrate 11 (in detail, a reflector so as to cover the LED chip 9 after the individualized phosphor layer 7 is attached). 10).
- this LED chip 9 is sealed by the transparent sealing material 12 (state S5).
- the transparent sealing material 12 a silicone resin is suitably used from the viewpoint of transparency and heat resistance.
- the phosphor sheet 4 includes the phosphor layer 2 on the support 3 is illustrated. It is not limited to. That is, the phosphor sheet 4 used in this method for manufacturing a phosphor may be composed of the phosphor layer 2, or the phosphor layer 2 and the transparent resin layer 5 illustrated in FIG. 1B. It may consist of a laminated body, or may further include other layers such as the diffusion layer described above.
- the phosphor sheet 4 includes the phosphor layer 2 and the transparent resin layer 5
- both the phosphor layer 2 and the transparent resin layer 5 on the support 3 are singulated in the individualization step. .
- the pick-up process the laminated body obtained by dividing the phosphor layer 2 and the transparent resin layer 5 is picked up from the support 3. In the sticking step, the picked-up laminate (separated) is stuck on the light extraction surface of the LED chip 9.
- the light emitter according to the embodiment of the present invention includes the phosphor sheet 4 described above.
- the light emitter 13 shown in FIG. 2 includes an individualized phosphor layer 7 as the phosphor sheet 4 on the light extraction surface of the LED chip 9.
- Such a light emitter can be widely applied to an in-vehicle headlight, a backlight of a television or a smartphone, illumination, and the like.
- the phosphor sheet 4 and a phosphor using the phosphor sheet are preferably applied to a light source unit such as a backlight because they are excellent in color reproducibility and have high luminous flux and high durability.
- the light source unit according to the embodiment of the present invention includes the phosphor sheet 4 described above.
- the light source unit includes a light source having a phosphor having the phosphor sheet 4.
- Such a light source unit can be applied to displays for televisions, smartphones, tablet computers, and game machines.
- the display according to the embodiment of the present invention includes a light source unit having the phosphor sheet 4 described above.
- This display includes a display provided with a light source unit having a light emitter (light emitter manufactured using the phosphor sheet 4) in the present invention.
- a display is a liquid crystal display.
- the color reproduction range of a liquid crystal display when a light-emitting body produced using the phosphor sheet 4 is used as a backlight of a liquid crystal display can be evaluated by a DCI ratio.
- the DCI ratio is an area ratio in the chromaticity region when the area of the DCI chromaticity region according to the DCI (Digital Cinema Initiative) standard is used as a reference (100%).
- the DCI ratio can be measured by the following procedure.
- a color filter that transmits red light produced by a known method is placed on the produced illuminant, and 1 W of electric power is applied to the illuminant to turn on the illuminant, and the total luminous flux measurement system (HM) -3000, manufactured by Otsuka Electronics Co., Ltd.) to measure the chromaticity of the emitted light.
- the chromaticity of the emitted light is measured for each of a case where a color filter that transmits green light is placed on the light emitter and a case where a color filter that transmits blue light is placed.
- the DCI ratio can be calculated by dividing the area of the triangle having the obtained three chromaticities as vertices by the area of the DCI chromaticity region.
- Silicone resin T11 is OE-6351A / B (manufactured by Toray Dow Corning). The refractive index of the silicone resin T11 is 1.41. Silicone resin T12 is KER6075LV A / B (made by Shin-Etsu Chemical Co., Ltd.). The refractive index of the silicone resin T12 is 1.45. The silicone resin T13 is XE14-C2860 (manufactured by Momentive Performance Materials). The refractive index of the silicone resin T13 is 1.50. Silicone resin T14 is OE6630 A / B (made by Toray Dow Corning Co., Ltd.). The refractive index of the silicone resin T14 is 1.53.
- Silicone resin T15 contains 75 parts by weight of the following component (E), 10 parts by weight of component (F), 25 parts by weight of component (G), 0.025 parts by weight of reaction inhibitor, and 0.01% of platinum catalyst. It was obtained by mixing parts by weight.
- the transparent resin sheet produced using the silicone resin T15 had a storage elastic modulus at 25 ° C. of 1 Mpa, a storage elastic modulus at 100 ° C. of 0.01 MPa, and exhibited good heat-fusibility.
- the refractive index of the silicone resin T15 is 1.56.
- the component (E) is (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 0.45 (HO 1/2 ) 0.03 .
- the component (F) is ViMe 2 SiO (MePhSiO) 17.5 SiMe 2 Vi.
- the component (G) is (HMe 2 SiO) 2 SiPh 2 .
- Me is a methyl group
- Vi is a vinyl group
- Ph is a phenyl group.
- the reaction inhibitor is 1-ethynylhexanol.
- the platinum catalyst is a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.
- the platinum content of this solution is 5% by weight.
- Silicone resin T16 was obtained by the following preparation method.
- the refractive index of the silicone resin T16 is 1.60.
- silicone resin T16 In the preparation method of silicone resin T16, 1-naphthyltrimethoxysilane (892.8 g) and 1,3-divinyl-1,3-diphenyldimethyldisiloxane (372.0 g) were charged into a reaction vessel and mixed in advance. Thereafter, trifluoromethanesulfonic acid (6.15 g) was added, and water (213.84 g) was added with stirring, followed by heating under reflux for 2 hours. Then, heating and normal pressure distillation were performed until it became 85 degreeC.
- 1-naphthyltrimethoxysilane 50 g was charged into a reaction vessel, heated and melted, and trifluoromethanesulfonic acid (0.06 g) was added. Subsequently, acetic acid (9.3 g) was added dropwise while heating to 45 ° C. to 50 ° C. After completion of dropping, the mixture was heated and stirred at 50 ° C. for 30 minutes. Low boiling point substances were distilled off under normal pressure by heating until the reaction temperature reached 80 ° C. Thereafter, the mixture was cooled to room temperature, 1,3,3-tetramethyldisiloxane (4.4 g) was added dropwise and heated until the reaction temperature reached 45 ° C.
- acetic acid (18 g) was added dropwise at 45 ° C. to 50 ° C. After completion of dropping, the mixture was heated and stirred at 50 ° C. for 30 minutes.
- Acetic anhydride (15.5 g) was added dropwise while keeping the temperature at 60 ° C. or lower by air cooling or water cooling, and after completion of the dropwise addition, the mixture was stirred at 50 ° C. for 30 minutes. Next, toluene and water were added, and stirring, standing, and extraction of the lower layer were repeated, followed by washing with water.
- organopolysiloxane resin P1 52.0 parts by mass of organopolysiloxane resin P1, 30.0 parts by mass of organopolysiloxane P2, 14.0 parts by mass of organotrisiloxane represented by the formula: HMe 2 SiOPh 2 SiOSiMe 2 H, and platinum-1 , 3-Divinyl-1,1,3,3-tetramethyldisiloxane complex 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane solution (0.
- a curable silicone composition was prepared by mixing 0.25 part by mass of a solution containing 1% by mass.
- Silicone resin T17 was obtained by the following preparation method.
- the refractive index of the silicone resin T17 is 1.65.
- silicone resin T17 methyltrimethoxysilane (16.6 g), phenyltrimethoxysilane (56.2 g), “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, Catalyst Kasei Kogyo Co., Ltd.) )
- Composition Titanium oxide particles 20% by weight, methanol 80% by weight (194 g), propylene glycol monomethyl ether acetate (126.9 g) are placed in a reaction vessel, and water (21.9 g) and phosphoric acid ( 0.36 g) was added dropwise with stirring so that the reaction temperature did not exceed 40 ° C.
- silicone resin T14 (8.00 g) was mixed with the obtained titanium oxide particles (50.00 g), and a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries Co., Ltd.) was used. The mixture was stirred and degassed for 20 minutes, thereby producing a silicone resin T17. As a result of measuring the refractive index, the average refractive index of the silicone resin T17 was 1.65.
- Silicone resin T18 was obtained by the following preparation method.
- the refractive index of the silicone resin T18 is 1.70.
- silicone resin T18 In the preparation method of silicone resin T18, silicone resin T14 (3.0 g) is mixed with titanium oxide particles (60.0 g) grafted with polysiloxane in the same manner as the preparation method of silicone resin T17 described above, and planetary type Using a stirring / degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring / degassing was performed at 1000 rpm for 20 minutes. Thereby, silicone resin T18 was produced. As a result of measuring the refractive index, the refractive index of the silicone resin T18 was 1.70.
- the fluororesin T21 is AF2400S (Mitsui / DuPont Fluorochemical).
- the refractive index of the fluororesin T21 is 1.30.
- the fluororesin T22 is CTX-800 (CT-solv 180 solution) (manufactured by Asahi Glass Co., Ltd.).
- the refractive index of the fluororesin T22 is 1.35.
- the green phosphor is a ⁇ -sialon phosphor called GR-MW540K (manufactured by Denka Co., Ltd.).
- the yellow phosphor is a Ce-doped YAG phosphor called NYAG-02 (manufactured by Intematix).
- the red phosphor T1 is KSF phosphor sample A (manufactured by Nemoto Lumi Material Co., Ltd.).
- the red phosphor T2 is KSF phosphor sample B (manufactured by Nemoto Lumi Material Co., Ltd.).
- the red phosphor T3 is a KSF phosphor sample C (manufactured by Nemoto Lumi Material Co., Ltd.).
- the red phosphor T4 is a KSF phosphor sample D (manufactured by Nemoto Lumi Material Co., Ltd.).
- the red phosphor T5 is a KSF phosphor sample E (manufactured by Nemoto Lumi Material Co., Ltd.).
- the red phosphor T6 is a KSF phosphor sample F (manufactured by Nemoto Lumi Material Co., Ltd.).
- the D10, D50 and D90 of the red phosphors T1 to T6 used in this example were measured by the following method. The measurement results are shown in Table 1. Table 1 also shows a value x calculated based on the above equation (11) based on the measured D10, D50, and D90.
- a phosphor sheet (for example, phosphor sheet 4 shown in FIGS. 1A and 1B) is prepared as described later, and the cross section of the phosphor layer is SEM.
- the maximum distance is calculated from the distance between the two intersections of the straight line that intersects the outer edge of the particle at two points, and this is defined as the individual particle size of the particle. did.
- the particle size of 10% of the accumulated portion from the small particle size side is D10
- the particle size of 50% of the accumulated portion is D50
- the accumulated portion was designated as D90.
- a base film is an example of the support body (For example, support body 3 shown to FIG. 1A and 1B) of the fluorescent substance sheet in this invention.
- the base film was a PET film.
- This PET film is “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd.), and its film thickness is 50 ⁇ m.
- Silicone fine particles were obtained by the following production method.
- a 2 L four-necked round bottom flask is equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel, and this flask is 2.5% containing 10,000 ppm of polyether-modified siloxane “BYK333” as a surfactant.
- ammonia water (2 L) was added, and the temperature was raised by an oil bath while stirring at 300 rpm. When the internal temperature reached 50 ° C., a mixture of methyltrimethoxysilane and phenyltrimethoxysilane (22/78 mol%) (200 g) was dropped from the dropping funnel over 30 minutes.
- the obtained silicone fine particles were observed with an SEM and confirmed to be monodispersed spherical fine particles.
- As a result of calculating the average particle diameter of the silicone fine particles from the obtained SEM image it was 50 nm.
- the refractive index of the silicone fine particles was measured by a liquid immersion method and found to be 1.54.
- As a result of observing the silicone fine particles with a cross-sectional TEM it was confirmed that the particles were single-structured fine particles.
- the silica fine particles T31 are Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.). The average particle diameter of the silica fine particles T31 is 12 nm. The refractive index of the silica fine particles T31 is 1.46.
- the silica fine particles T32 are “Admanano” YA050C (manufactured by Admatechs Co., Ltd.). The average particle diameter of the silica fine particles T32 is 50 nm. The refractive index of the silica fine particles T32 is 1.46.
- the silica fine particles T33 are “Admanano” YA100C (manufactured by Admatechs Co., Ltd.).
- the average particle diameter of the silica fine particles T33 is 100 nm.
- the refractive index of the silica fine particles T33 is 1.46.
- Silica fine particles T34 are “Admafine” SO-E1 (manufactured by Admatechs Co., Ltd.).
- the average particle diameter of the silica fine particles T34 is 250 nm.
- the refractive index of the silica fine particles T34 is 1.46.
- Silica fine particles T35 are HPS-1000 (manufactured by Toa Gosei Co., Ltd.).
- the average particle diameter of the silica fine particles T35 is 1000 nm.
- the refractive index of the silica fine particles T35 is 1.46.
- Silica fine particles T36 are “Admafine” SO-E5 (manufactured by Admatechs Co., Ltd.). The average particle diameter of the silica fine particles T36 is 1500 nm. The refractive index of the silica fine particles T36 is 1.46.
- the alumina fine particles are Aeroxide AluC (manufactured by Nippon Aerosil Co., Ltd.).
- the average particle diameter of the alumina fine particles is 12 nm.
- the refractive index of the alumina fine particles is 1.77.
- the titania fine particles are MT-01 (manufactured by Teika Co., Ltd.).
- the average particle diameter of the titania fine particles is 10 nm.
- the refractive index of the titania fine particles is 2.50.
- ⁇ Preparation of phosphor sheet> silicone resin, silicone fine particles, red phosphor, and green phosphor were mixed in a predetermined ratio in a polyethylene container having a volume of 300 mL. Furthermore, 8 wt% of toluene was added as a solvent, and a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries) was used to stir and degas at 1000 rpm to obtain a resin solution for preparing a phosphor layer. . Then, the fluorescent substance layer preparation resin liquid was apply
- ⁇ Measurement of film thickness of phosphor layer In the measurement of the thickness of the phosphor layer in this example, the thickness at a predetermined position of the PET film for producing the phosphor layer was measured in advance with a micrometer and marked. Next, a phosphor layer was formed on this PET film, and then the thickness of the marking portion was measured again with a micrometer. The thickness of the phosphor layer was obtained by subtracting the thickness of the PET film previously measured from the obtained thickness. In this example, the film thickness was measured at 25 points in a grid pattern at intervals of 10 mm, and the average value of these was taken as the film thickness of the phosphor layer.
- a phosphor sheet provided with a transparent resin layer on the phosphor layer was obtained.
- the “phosphor sheet having a transparent resin layer on the phosphor layer” is appropriately referred to as a “phosphor sheet with a transparent resin layer”.
- a transparent resin layer-forming resin solution is applied onto a PET film using a slit die coater and dried at 130 ° C. for 30 minutes, whereby a transparent resin sheet is formed.
- a vacuum laminator V130 manufactured by Nikko Materials Co., Ltd.
- the phosphor layer of the phosphor sheet and the transparent resin layer of the transparent resin sheet are thermocompression bonded at 100 ° C. for 30 seconds in a vacuum atmosphere of 1 hPa. By pasting together.
- the PET film on the transparent resin sheet side was peeled off, thereby forming a transparent resin layer on the phosphor layer.
- a phosphor sheet with a transparent resin layer was obtained.
- ⁇ Porosity measurement> the phosphor sheet was cut by a focused ion beam (FIB) processing method, and the cross section of the phosphor layer was observed by SEM. 20 cross-sections were observed per phosphor sheet, and the total cross-sectional area corresponding to the voids of the 20 obtained two-dimensional images was calculated. By dividing the total cross-sectional area corresponding to the void by the total cross-sectional area of these 20 two-dimensional images, the porosity of the phosphor layer was obtained.
- FIB focused ion beam
- the phosphor sheet or the phosphor sheet with a transparent resin layer (1 cm square) produced as described above was cut with a cutting device (GCUT manufactured by UHT), thereby producing a 1 mm square.
- 100 individual sheets were prepared.
- the individual sheet is obtained by dividing a phosphor sheet or a phosphor sheet with a transparent resin layer.
- a die bonding apparatus manufactured by Toray Engineering
- a 1 mm square piece sheet was vacuum-adsorbed with a collet and peeled from the base film.
- the phosphor layer of this individual sheet was aligned and pasted on the surface of the blue LED chip of the LED package in which the flip chip type blue LED chip was mounted and the reflector was formed around the blue LED chip. .
- an adhesive was applied in advance on the blue LED chip, and a phosphor layer was attached via the adhesive. Silicone resin T15 was used for this adhesive.
- Total luminous flux retention (%) (total luminous flux after 300 hours / total luminous flux immediately after the start of the test) ⁇ 100
- ⁇ Color reproduction range measurement> In the measurement of the color reproduction range in this example, a color filter that transmits red light produced by a known method was placed on the luminous body produced as described above, and the chromaticity of the emitted light was measured. Similarly, the chromaticity of the emitted light was measured for each of the case where a color filter that transmits green light was placed on the light emitter and the case where a color filter that transmitted blue light was placed. The DCI ratio was calculated by dividing the area of the triangle with the three chromaticities obtained as vertices by the area of the DCI chromaticity region. The higher the DCI ratio, the better the color reproducibility.
- the refractive index of the refractive index measurement sample is measured using a refractive index / film thickness measuring device “prism coupler MODEL 2010 / M” (manufactured by Metricon Co., Ltd.). The refractive index of the cured fluororesin was measured.
- ⁇ Preparation of refractive index measurement sample> In the preparation of the refractive index measurement sample in this example, the resin contained in the phosphor sheet was stirred for 10 minutes at 1000 rpm using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), and defoamed. Thus, a dispersion of this resin was produced. After 5 cc of this dispersion was dropped onto a PET film, it was heated in an oven at 150 ° C. for 1 hour, thereby producing an average refractive index measurement sample as a refractive index measurement sample.
- the light transmittance of the transparent resin layer containing fine particles is a basic configuration using an integrating sphere attached to a spectrophotometer (U-4100 Spectrophotometer (manufactured by Hitachi, Ltd.)). It was obtained by measuring the light transmittance of the measurement sample.
- the transmittance measurement sample used in each example was used.
- the slit was 2 nm and the scanning speed was 600 nm / min.
- the smallest value among the light transmittances at wavelengths of 400 nm to 800 nm was defined as the minimum transmittance.
- the silicone resin and fine particles used for the transparent resin layer are mixed in a polyethylene container having a volume of 300 mL, and the planetary stirring deaerator “Mazerustar KK-400” (manufactured by Kurabo Industries Co., Ltd.) Was stirred at 1000 rpm for 10 minutes and defoamed to prepare a dispersion.
- the dispersion is applied onto quartz glass with a blade coater and then heated in an oven at 150 ° C. for 1 hour.
- permeability measurement sample was produced about each Example.
- ⁇ Measurement of film thickness of transmittance measurement sample> In the film thickness measurement of the transmittance measurement sample in this example, the thickness at a predetermined position of the quartz glass was previously measured with a micrometer, and the measured position was marked. Next, after forming a transmittance measurement sample of the transparent resin layer on the quartz glass, the thickness of the marking portion was again measured with a micrometer. The film thickness of this transmittance measurement sample was obtained by subtracting the thickness of the quartz glass previously measured from the obtained thickness. The film thickness was measured at 25 points in a grid pattern at intervals of 10 mm, and the average value of these was taken as the film thickness of the transmittance measurement sample.
- Examples 1 to 6 (Examples 1 to 6) -Effect of phosphor particle size- In Examples 1 to 6, a phosphor sheet having a phosphor layer having the composition shown in Table 2 was prepared, and the porosity was measured by the method described above. Also, a phosphor (light emitting device) was prepared using the phosphor sheets obtained in each of Examples 1 to 6, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. did. These measurement results are shown in Table 3. As can be seen with reference to Tables 2 and 3, when the phosphor sheet according to the present invention was used, all of Examples 1 to 6 were able to obtain a light emitter with excellent color reproducibility and high luminous flux. .
- the D50 of the red phosphor is 10 ⁇ m or more like the D50 of the red phosphors T2 to T6 shown in Table 1, the total luminous flux is further improved, and the D10 of the red phosphors T3 to T6 shown in Table 1 is improved.
- the D10 of the red phosphor is 5 ⁇ m or more, the total luminous flux retention rate is further improved.
- the porosity of the phosphor sheet tended to decrease as the D10 and D50 of the red phosphor increased.
- Example 7 to 13 Effect of phosphor concentration-
- a phosphor sheet having a phosphor layer having the composition shown in Table 4 was prepared, and the porosity was measured by the method described above.
- a phosphor was prepared using the phosphor sheet obtained in each of Examples 7 to 13, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 5.
- Table 4 shows the composition of Example 6 again, and Table 5 shows the result of Example 6 again. From Tables 4 and 5, it was found that the higher the concentration of the phosphors such as the red phosphor T6 and the green phosphor, the higher the total luminous flux retention rate.
- Examples 14 to 17 Effect of silicone fine particles
- a phosphor sheet having a phosphor layer having the composition shown in Table 6 was produced, and the porosity was measured by the method described above.
- a phosphor was prepared using the phosphor sheets obtained in each of Examples 14 to 17, and the chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 7. From Tables 6 and 7, it was found that the chromaticity variation ( ⁇ (Cx)) was further improved by containing the silicone fine particles.
- a phosphor sheet was produced with a composition in which the silicone resin T15 was 50 wt% and the red phosphor T6 was 50 wt%.
- a phosphor sheet was produced with a composition in which the silicone resin T15 was 50 wt% and the green phosphor was 50 wt%.
- Example 19 to 25 Effect of refractive index of phosphor layer resin-
- phosphor sheets having phosphor layers having the compositions shown in Table 9 were produced. Further, the film thickness of the phosphor layer of the phosphor sheet produced in each of Examples 19 to 25 was measured by the method described above. Moreover, also about the fluorescent substance sheet of Example 10, the film thickness of the fluorescent substance layer was measured. Further, a phosphor was produced using the phosphor sheet produced in each of Examples 19 to 25, and chromaticity, total luminous flux, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 10. Table 9 shows the composition of Example 10 again, and Table 10 shows the measurement result of Example 10 again.
- Example 26 to 36 Effect of refractive index of transparent resin layer-
- a resin solution for preparing a transparent resin layer was applied onto the phosphor sheet prepared in Example 6 using a slit die coater, and this resin solution for preparing a transparent resin layer was applied.
- a phosphor resin sheet having a transparent resin layer on a phosphor layer is prepared by preparing a transparent resin sheet by the above-described method using silicone resin T15 and bonding the phosphor layer and the transparent resin layer. Produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 26 to 36 was measured by the method described above.
- the phosphor layer side of the phosphor sheet with the transparent resin layer produced in each of Examples 26 to 36 is attached on the LED chip to produce a light emitter, and the chromaticity, total luminous flux is obtained by the above-described method.
- the total luminous flux retention and the color reproduction range were measured.
- Table 11 shows the types of resins used in the production of the resin liquid for producing the transparent resin layer in each of Examples 26 to 36 and the measurement results in Examples 26 to 36.
- Examples 37 to 42-Refractive index of fine particles- resin solutions for preparing a transparent resin layer having the compositions shown in Table 12 were prepared. Next, the transparent resin layer preparation resin solution prepared in each of Examples 37 to 42 was applied on the phosphor sheet prepared in Example 10, and the transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 37 to 42 was measured by the method described above. Next, the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 37 to 42 is attached on the LED chip to produce a light emitter. The luminous flux, total luminous flux retention, and color reproduction range were measured. Further, a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing the transparent resin layer prepared in each of Examples 37 to 42, and the light transmittance of the transparent resin layer was measured by the above-described method. . Table 13 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 37 to 42 and the measurement results thereof.
- Example 43 to 47 Additional amount of silica fine particles-
- resin solutions for preparing a transparent resin layer having the compositions shown in Table 14 were prepared.
- the transparent resin layer preparation resin solution prepared in each of Examples 43 to 47 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 43 to 47 was measured by the method described above.
- the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 43 to 47 is attached on the LED chip to produce a light emitter.
- the luminous flux, total luminous flux retention, and color reproduction range were measured.
- a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 43 to 47, and the light transmittance of the transparent resin layer was measured by the method described above.
- Table 15 shows the refractive index difference between the resin and fine particles of the transparent resin layer in each of Examples 43 to 47, and the measurement results thereof.
- Table 14 shows the compositions of Examples 38 and 39 again, and Table 15 shows the results of Examples 38 and 39 again.
- the content of the silica fine particles T31 is preferably 30% by weight or less and more preferably 10% by weight or less from the viewpoint of the minimum transmittance. Further, it was found that the content of the silica fine particles T31 is preferably 0.1% by weight or more and more preferably 1% by weight or more from the viewpoint of suppressing variation in the thickness of the transparent resin layer. .
- Example 48 to 52 Alumina fine particle addition amount-
- resin solutions for preparing a transparent resin layer having the compositions shown in Table 16 were prepared.
- the transparent resin layer preparation resin solution prepared in each of Examples 48 to 52 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 48 to 52 was measured by the method described above.
- the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 48 to 52 is attached on the LED chip to produce a light emitter.
- the luminous flux, total luminous flux retention, and color reproduction range were measured.
- a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing the transparent resin layer prepared in each of Examples 48 to 52, and the light transmittance of the transparent resin layer was measured by the method described above.
- Table 17 shows the difference in refractive index between the resin and fine particles of the transparent resin layer in each of Examples 48 to 52 and the measurement results thereof.
- Table 16 shows the compositions of Examples 38 and 41 again, and Table 17 shows the results of Examples 38 and 41 again.
- the content of the alumina fine particles is preferably 30% by weight or less, and more preferably 10% by weight or less from the viewpoint of the minimum transmittance.
- the content of the alumina fine particles is preferably 0.1% by weight or more, and more preferably 1% by weight or more, from the viewpoint of suppressing variation in the thickness of the transparent resin layer.
- Example 53 to 57 -Addition amount of silicone fine particles-
- a resin liquid for preparing a transparent resin layer having the composition shown in Table 18 was prepared.
- the transparent resin layer preparation resin solution prepared in each of Examples 53 to 57 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 53 to 57 was measured by the method described above.
- the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 53 to 57 is attached on the LED chip to produce a light emitter.
- the luminous flux, total luminous flux retention, and color reproduction range were measured.
- a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 53 to 57, and the light transmittance of the transparent resin layer was measured by the method described above.
- Table 19 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 53 to 57 and the measurement results thereof.
- Table 18 shows the compositions of Examples 38 and 40 again, and Table 19 shows the results of Examples 38 and 40 again.
- Example 58 to 62 Particle size of fine particles-
- resin solutions for preparing a transparent resin layer having the compositions shown in Table 20 were prepared.
- the transparent resin layer preparation resin solution prepared in each of Examples 58 to 62 was applied on the phosphor sheet prepared in Example 10, and this transparent resin layer preparation resin solution was applied at 130 ° C. for 30 minutes. By drying, a phosphor sheet having a transparent resin layer on the phosphor layer was produced.
- the film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 58 to 62 was measured by the method described above.
- the phosphor layer side of the phosphor sheet with a transparent resin layer produced in each of Examples 58 to 62 is attached on the LED chip to produce a light emitter.
- the luminous flux, total luminous flux retention, and color reproduction range were measured.
- a transmittance measurement sample having a thickness of 100 ⁇ m was prepared using the resin liquid for preparing a transparent resin layer prepared in each of Examples 58 to 62, and the light transmittance of the transparent resin layer was measured by the method described above. .
- Table 21 shows the refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 58 to 62 and the measurement results thereof.
- Table 20 shows the compositions of Examples 38 and 39 again, and Table 21 shows the results of Examples 38 and 39 again. From Tables 20 and 21, it was found that the smaller the particle size of the fine particles, the higher the minimum transmittance and the smaller the variation in the thickness of the transparent resin layer.
- a phosphor sheet was prepared with a composition in which the silicone resin T15 was 40 wt% and the yellow phosphor (YAG yellow phosphor) was 60 wt%, and the porosity was obtained by the method described above. Was measured. Further, a phosphor was prepared using the obtained phosphor sheet, and chromaticity, total luminous flux, total luminous flux retention, and color reproduction range were measured by the above-described methods. These measurement results are shown in Table 22. From Table 22, it was found that when a YAG yellow phosphor was used, the color reproduction range was 70%, which was not suitable for a backlight for a liquid crystal display.
- the phosphor sheet according to the present invention, the light emitter using the phosphor sheet, the light source unit, the display, and the method for producing the light emitter are a phosphor sheet that achieves both improved color reproducibility and high luminous flux, and Is suitable for a manufacturing method of a light emitter, a light source unit, a display, and a light emitter.
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Abstract
Description
(一般式)
A2MF6:Mn ・・・(1)
(一般式(1)において、Aは、Li、Na、K、RbおよびCsからなる群より選ばれ、かつNaおよびKの少なくとも1つを含む1種以上のアルカリ金属であり、Mは、Si、Ti、Zr、Hf、GeおよびSnからなる群より選ばれる1種以上の4価元素である。)
本発明の実施の形態に係る蛍光体シートは、赤色蛍光体、β型サイアロン蛍光体および樹脂を含む蛍光体層を含有するものである。この蛍光体シートにおいて、赤色蛍光体は、一般式(1)で表されるMn賦活複フッ化物である。
A2MF6:Mn ・・・(1)
一般式(1)において、Aは、リチウム(Li)、ナトリウム(Na)、カリウム(K)、ルビジウム(Rb)およびセシウム(Cs)からなる群より選ばれ、かつNaおよびKの少なくとも1つを含む1種以上のアルカリ金属である。Mは、ケイ素(Si)、チタン(Ti)、ジルコニウム(Zr)、ハフニウム(Hf)、ゲルマニウム(Ge)およびスズ(Sn)からなる群より選ばれる1種以上の4価元素である。
蛍光体層2は、例えば図1A、1Bに示すように、主として蛍光体1と樹脂14とを含む層である。蛍光体1としては、少なくとも、一般式(1)で表される赤色蛍光体と、β型サイアロン蛍光体とが挙げられる。
赤色蛍光体とは、波長590nm~750nmに発光ピークを有する蛍光体のことである。本発明の実施の形態に係る蛍光体シート4は、その色再現性を向上させるために、蛍光体層2中に、上述した一般式(1)で表されるMn賦活複フッ化物(A2MF6:Mn)である赤色蛍光体を含む必要がある。このMn賦活複フッ化物である赤色蛍光体は、「Mn賦活複フッ化物錯体蛍光体」と称される。以下、Mn賦活複フッ化物錯体蛍光体は、「赤色蛍光体」と適宜略記される。
x=(D90-D10)/D50 ・・・(11)
値xは、赤色蛍光体の粒度分布の指標である。値xが小さいということは、耐久性低下の原因となる小粒径の赤色蛍光体(例えばKSF蛍光体)が少なく、かつ、色度ばらつきの原因となる大粒径の赤色蛍光体(例えばKSF蛍光体)が少ないことを意味する。値xが1.5以下であることによって、蛍光体シート4の耐久性および色度ばらつきがさらに改善する。
β型サイアロン蛍光体とは、β型窒化ケイ素の固溶体であり、β型窒化ケイ素結晶のSi位置にアルミニウム(Al)が置換固溶し、窒素(N)位置に酸素(O)が置換固溶したものである。β型サイアロン蛍光体に用いられるβ型サイアロンの単位胞(単位格子)に2式量の原子があるので、β型サイアロンの一般式として、Si6-zAlzOzN8-zが用いられる。この一般式において、zは、0超、4.2未満の値である。本実施の形態におけるβ型サイアロン蛍光体において、β型サイアロンの固溶範囲は非常に広く、また、(Si、Al)/(N、O)のモル比は、3/4を維持する必要がある。β型サイアロンの一般的な製法は、窒化ケイ素の他に、酸化ケイ素と窒化アルミニウムとを、あるいは酸化アルミニウムと窒化アルミニウムとを加えて加熱する方法である。
蛍光体層2は、上記した蛍光体1以外の蛍光体をさらに含有していてもよい。上記した蛍光体1以外の蛍光体としては、例えば、他の赤色蛍光体、他の緑色蛍光体、黄色蛍光体、青色蛍光体等が挙げられる。本実施の形態において、緑色蛍光体とは、波長500nm~560nmに発光ピークを有する蛍光体のことである。黄色蛍光体とは、波長560nm~590nmに発光ピークを有する蛍光体のことである。青色蛍光体とは、波長430nm~500nmに発光ピークを有する蛍光体のことである。
蛍光体層2に含まれる樹脂14の屈折率は、1.45以上、1.7以下である。この樹脂14の屈折率は、1.5以上であることがより好ましく、また、1.65以下であることがより好ましい。この樹脂14の屈折率が1.45以上であることで、平均的な屈折率が1.4前後であるMn賦活複フッ化物錯体蛍光体(蛍光体1としての赤色蛍光体)との屈折率差が大きくなり、蛍光体層2中で光が散乱しやすくなる。そのため、光が蛍光体層2に入ってから出るまでの光路長が長くなる。光路長が長くなることで、LEDチップから放射される青色光が蛍光体層2中の蛍光体1により色変換されやすくなるため、所望の色度を発現するための蛍光体量を少なくすることができる。
(R1 2SiO2/2)a(R1SiO3/2)b(R2O1/2)c ・・・(21)
平均単位式(21)において、R1は、フェニル基、炭素原子数1~6のアルキル基もしくはシクロアルキル基、または炭素原子数2~6のアルケニル基である。ただし、R1の65モル%~75モル%はフェニル基であり、R1の10モル%~20モル%はアルケニル基である。R2は、水素原子または炭素原子数1~6のアルキル基である。a、b、およびcは、0.5≦a≦0.6、0.4≦b≦0.5、0≦c≦0.1、かつa+b=1を満たす数である。
R3 3SiO(R3 2SiO)mSiR3 3 ・・・(2)
一般式(2)において、R3は、フェニル基、炭素原子数1~6のアルキル基もしくはシクロアルキル基、または炭素原子数2~6のアルケニル基である。ただし、R3の40モル%~70モル%はフェニル基であり、R3の少なくとも1個はアルケニル基である。mは、5~50の範囲内の整数である。
(HR4 2SiO)2SiR4 2 ・・・(3)
一般式(3)において、R4は、フェニル基、または炭素原子数1~6のアルキル基もしくはシクロアルキル基である。ただし、R4の30モル%~70モル%は、フェニル基である。
本発明の実施の形態に係る蛍光体シート4は、蛍光体層2中の蛍光体1の樹脂14への分散安定性を向上させることを目的として、蛍光体層2中に微粒子を含有してもよい。この微粒子の例としては、チタニア、シリカ、アルミナ、シリコーン、ジルコニア、セリア、窒化アルミニウム、炭化ケイ素、窒化ケイ素、チタン酸バリウム等で構成される微粒子が挙げられる。これらは、単独で用いられてもよく、2種類以上併用されてもよい。蛍光体層2中に含有する微粒子としては、入手しやすいという観点から、シリカ微粒子、アルミナ微粒子、シリコーン微粒子が好ましく、硬度が低いという観点から、シリコーン微粒子が特に好ましい。この微粒子の硬度が低いことにより、蛍光体1の分散工程にて赤色蛍光体の破砕を抑制する効果があり、この結果、より発光強度の高い蛍光体シート4を得ることが可能である。
蛍光体層2には、その他の成分として、常温での硬化を抑制してポットライフを長くするために、ヒドロシリル化反応遅延剤を配合することが好ましい。ヒドロシリル化反応遅延剤としては、例えば、3-メチル-1-ブチン-3-オール、3,5-ジメチル-1-ヘキシン-3-オール、フェニルブチノール、1-エチニル-1-シクロヘキサノール等の炭素-炭素三重結合を有するアルコール誘導体、3-メチル-3-ペンテン-1-イン、3,5-ジメチル-3-ヘキセン-1-イン等のエンイン化合物、テトラメチルテトラビニルシクロテトラシロキサン、テトラメチルテトラヘキセニルシクロテトラシロキサン等のアルケニル基含有低分子量シロキサン、メチル-トリス(3-メチル-1-ブチン-3-オキシ)シラン、ビニル-トリス(3-メチル-1-ブチン-3-オキシ)シラン等のアルキン含有シラン等が挙げられる。
透明樹脂層5(図1B参照)は、波長450nmにおける全光線透過率が90%以上であり、蛍光体1を含まない樹脂層である。透明樹脂層5は、例えば図1Bに示すように、蛍光体層2の上に積層される。また、透明樹脂層5の波長400nm~800nmにおける最小透過率は、80%以上であることが好ましい。ここでいう最小透過率とは、波長400nm~800nmにおける光透過率のうち最も小さい値のことである。この最小透過率が80%以上であることによって、蛍光体シート4は、高光束化と高耐久性とを両立しやすくなる。蛍光体層2の上に透明樹脂層5があることにより、蛍光体層2中の蛍光体1(例えば赤色蛍光体等)の耐久性が向上し、この結果、蛍光体シート4としての耐久性が向上する。
透明樹脂層5に用いられる樹脂としては、シリコーン樹脂、フッ素樹脂、エポキシ樹脂、ポリアリレート樹脂、PET変性ポリアリレート樹脂、ポリカーボネート樹脂、環状オレフィン樹脂、ポリエチレンテレフタレート樹脂、ポリメチルメタアクリレート樹脂、ポリプロピレン樹脂、変性アクリル樹脂、ポリスチレン樹脂およびアクリルニトリル・スチレン共重合体樹脂から選択される1種類以上の樹脂であることが好ましい。中でも、シリコーン樹脂、フッ素樹脂、エポキシ樹脂から選択される1種類以上の樹脂がより好ましく、耐熱性の面から、シリコーン樹脂が特に好ましい。
透明樹脂層5に用いられる微粒子は、可視光における吸収や発光が小さいものが好ましい。この微粒子としては、例えば、チタニア、シリカ、アルミナ、シリコーン、ジルコニア、セリア、窒化アルミニウム、炭化ケイ素、窒化ケイ素、チタン酸バリウム等の微粒子が挙げられる。これらのうち、入手しやすいという観点から、シリカ微粒子、アルミナ微粒子、シリコーン微粒子から選択される1種類以上の微粒子がより好ましく、屈折率や粒径を制御しやすいという観点から、シリコーン微粒子が特に好ましい。
微粒子を含有する透明樹脂層5の光透過率は、分光光度計を用いて測定することができる。例えば、日立製作所製:U-4100 Spectrophotomaterを用いる場合は、この測定装置に付属の積分球を用いた基本構成で透明樹脂層5のサンプルの光透過率を測定することができる。この光透過率の測定条件については、スリットは2nmとし、走査速度は600nm/分とする。
本発明の実施の形態に係る蛍光体シート4は、蛍光体層2の上および下の少なくとも一方に、蛍光体層2とは異なる別の蛍光体層や拡散層を備えていてもよい。この場合、蛍光体層2または別の蛍光体層の下(例えば、いずれかの蛍光体層とLEDチップ表面との間)に形成される透明樹脂層は、LEDチップに接着剤を使用せずに貼り付けできるように、熱融着性を備えることが好ましい。屈折率の高いGaNやサファイア等のLEDチップ表面に上記の透明樹脂層が貼り付けられた場合、このLEDチップ表面の屈折率と、いずれかの蛍光体層の下に位置する透明樹脂層との屈折率差が小さいほど、このLEDチップ表面からこの透明樹脂層への光取り出し効率を向上させることができる。それ故、この場合は、この透明樹脂層の屈折率が1.56以上であることが好ましい。
つぎに、本発明の実施の形態に係る蛍光体シート4の作製方法について、詳細に説明する。なお、以下に説明する作製方法は一例であり、蛍光体シート4の作製方法は、これに限定されない。
本発明の実施の形態に係る発光体の製造方法(蛍光体シート4を用いた発光体の製造方法)について説明する。図2は、本発明の実施の形態に係る蛍光体シートを用いた発光体の製造方法の一例を示す工程図である。なお、以下の説明は一例であり、本発明の実施の形態に係る発光体の製造方法は、以下に説明するものに限定されない。
個片化工程において、蛍光体シート4の個片化は、金型によるパンチング、レーザーによる加工、ダイシングやカッティング等の方法により、行うことができる。このとき、蛍光体シート4としての蛍光体層2は、半硬化状態でもよいし、予め硬化されていてもよい。レーザーによる加工は、蛍光体層2に高エネルギーが付与されるので、蛍光体層2の樹脂(例えば図1Aに示す樹脂14)の焼け焦げや蛍光体(例えば図1Aに示す蛍光体1)の劣化を回避することが非常に難しい。したがって、蛍光体シート4の個片化の方法としては、刃物による切削または切断が望ましい。
上述した個片化工程によって個片化された蛍光体シート4は、個片化工程の次工程であるピックアップ工程によってピックアップされる。例えば、図2に示すように、個片化蛍光体層7は、支持体3上に貼り付けられた状態にある。ピックアップ工程において、個片化蛍光体層7は、コレット8等の吸引装置を備えたピックアップ装置(図示せず)により、支持体3から剥離されてピックアップされる(状態S3)。
上述したピックアップ工程によってピックアップされた個片化蛍光体層7(個片化された蛍光体シート4の一例)は、ピックアップ工程の次工程である貼付工程によって光源に貼り付けられる。例えば、図2に示すように、個片化蛍光体層7は、コレット8によってピックアップされた状態にある。コレット8は、基板11に実装されたLEDチップ9(光源の一例)の位置へ個片化蛍光体層7とともに搬送され、これにより、LEDチップ9の光取り出し面と個片化蛍光体層7の接着面(例えば下面)とを対向させる。ついで、コレット8は、LEDチップ9の光取り出し面に、個片化蛍光体層7の接着面を押し付けて貼り付ける(状態S4)。このとき、基板11上のLEDチップ9の周囲には、リフレクター10が形成されていてもよい。
上述した発光体の製造方法には、その他の工程として、LEDチップ9と回路基板の一例である基板11とを電気的に接続する接続工程がさらに含まれてもよい。この接続工程において、LEDチップ9の電極と基板11の配線とが、公知の方法で電気的に接続される。これにより、発光体13を得ることができる。LEDチップ9が光取り出し面側に電極を有する場合には、LEDチップ9の上面の電極と基板11の配線とが、ワイヤーボンディングによって接続される。また、LEDチップ9が発光面の反対面に電極パッドを有するフリップチップタイプである場合には、LEDチップ9の電極面を基板11の配線と対向させ、これらが一括接合によって接続される。この場合、基板11とLEDチップ9との接続は、個片化された蛍光体シート4(例えば個片化蛍光体層7)の貼り付け前に行ってもよい。
本発明の実施の形態に係る発光体は、上述した蛍光体シート4を備える。例えば、図2に示される発光体13は、蛍光体シート4としての個片化蛍光体層7をLEDチップ9の光取り出し面上に備える。このような発光体は、車載のヘッドライト、テレビやスマートフォンのバックライト、照明等に幅広く適用することができる。本発明において、蛍光体シート4およびこれを用いた発光体は、色再現性の向上に優れ、高光束、高耐久性を有するため、バックライト等の光源ユニットに適用することが好ましい。
蛍光体シート4を用いて作製した発光体を液晶ディスプレイのバックライトとして使用したときの液晶ディプレイの色再現範囲は、DCI比で評価することができる。DCI比とは、DCI(Digital Cinema Initiative)規格に係るDCI色度領域の面積を基準(100%)としたときの、色度領域における面積比のことである。DCI比は、下記の手順で測定することができる。
シリコーン樹脂T11は、OE-6351A/B(東レ・ダウコーニング社製)である。シリコーン樹脂T11の屈折率は、1.41である。シリコーン樹脂T12は、KER6075LV A/B(信越化学工業社製)である。シリコーン樹脂T12の屈折率は、1.45である。シリコーン樹脂T13は、XE14-C2860(モメンティブ・パフォーマンス・マテリアル社製)である。シリコーン樹脂T13の屈折率は、1.50である。シリコーン樹脂T14は、OE6630 A/B(東レ・ダウコーニング株式会社製)である。シリコーン樹脂T14の屈折率は、1.53である。
フッ素樹脂T21は、AF2400S(三井・デュポンフロロケミカル社製)である。フッ素樹脂T21の屈折率は、1.30である。フッ素樹脂T22は、CTX-800(CT-solv180溶液)(旭硝子社製)である。フッ素樹脂T22の屈折率は、1.35である。
緑色蛍光体は、GR-MW540K(デンカ株式会社製)というβ型サイアロン蛍光体である。黄色蛍光体は、NYAG-02(Intematix社製)というCeドープYAG蛍光体である。赤色蛍光体T1は、KSF蛍光体サンプルA(株式会社ネモト・ルミマテリアル製)である。赤色蛍光体T2は、KSF蛍光体サンプルB(株式会社ネモト・ルミマテリアル製)である。赤色蛍光体T3は、KSF蛍光体サンプルC(株式会社ネモト・ルミマテリアル製)である。赤色蛍光体T4は、KSF蛍光体サンプルD(株式会社ネモト・ルミマテリアル製)である。赤色蛍光体T5は、KSF蛍光体サンプルE(株式会社ネモト・ルミマテリアル製)である。赤色蛍光体T6は、KSF蛍光体サンプルF(株式会社ネモト・ルミマテリアル製)である。
基材フィルムは、本発明における蛍光体シートの支持体(例えば図1A、1Bに示す支持体3)の一例である。本実施例において、基材フィルムは、PETフィルムとした。このPETフィルムは、“セラピール”BX9(東レフィルム加工(株)製)であり、その膜厚は、50μmである。
シリコーン微粒子は、以下の製造方法によって得た。
シリカ微粒子T31は、Aerosil200(日本アエロジル(株)製)である。シリカ微粒子T31の平均粒径は、12nmである。シリカ微粒子T31の屈折率は、1.46である。シリカ微粒子T32は、“アドマナノ”YA050C(アドマテックス(株)製)である。シリカ微粒子T32の平均粒径は、50nmである。シリカ微粒子T32の屈折率は、1.46である。シリカ微粒子T33は、“アドマナノ”YA100C(アドマテックス(株)製)である。シリカ微粒子T33の平均粒径は、100nmである。シリカ微粒子T33の屈折率は、1.46である。シリカ微粒子T34は、“アドマファイン”SO-E1(アドマテックス(株)製)である。シリカ微粒子T34の平均粒径は、250nmである。シリカ微粒子T34の屈折率は、1.46である。シリカ微粒子T35は、HPS-1000(東亜合成(株)製)である。シリカ微粒子T35の平均粒径は、1000nmである。シリカ微粒子T35の屈折率は、1.46である。シリカ微粒子T36は、“アドマファイン”SO-E5(アドマテックス(株)製)である。シリカ微粒子T36の平均粒径は、1500nmである。シリカ微粒子T36の屈折率は、1.46である。
アルミナ微粒子は、Aeroxide AluC(日本アエロジル(株)製)である。このアルミナ微粒子の平均粒径は、12nmである。このアルミナ微粒子の屈折率は、1.77である。
チタニア微粒子は、MT-01(テイカ株式会社製)である。このチタニア微粒子の平均粒径は、10nmである。このチタニア微粒子の屈折率は、2.50である。
本実施例における蛍光体シートの作製では、容積300mLのポリエチレン製容器にシリコーン樹脂、シリコーン微粒子、赤色蛍光体、緑色蛍光体を所定の比率で混合した。さらに、溶媒としてトルエンを8wt%添加し、遊星式撹拌・脱泡装置“マゼルスターKK-400”(クラボウ製)を用い、1000rpmで撹拌・脱泡して、蛍光体層作製用樹脂液を得た。その後、スリットダイコーターを用いて蛍光体層作製用樹脂液をPETフィルム上に塗布し、130℃で30分乾燥させることにより、蛍光体層を作製して、蛍光体シートを得た。
本実施例における蛍光体層の膜厚測定では、蛍光体層を作製するPETフィルムの所定位置の厚さを予めマイクロメーターで測定し、マーキングした。ついで、蛍光体層をこのPETフィルム上に作製し、その後、マーキング部分の厚さを再びマイクロメーターで測定した。得られた厚さから、先に測定しておいたPETフィルムの厚さを差し引くことで、この蛍光体層の膜厚を得た。本実施例において、膜厚は10mm間隔で碁盤目状に25点測定し、これらの平均値を蛍光体層の膜厚とした。
本実施例における直接塗布法による透明樹脂層の形成では、容積300mLのポリエチレン製容器にシリコーン樹脂またはフッ素樹脂、微粒子を所定の比率で混合した。さらに、溶媒としてトルエンを5wt%添加し、その後、遊星式撹拌・脱泡装置“マゼルスターKK-400”(クラボウ製)を用い、1000rpmで20分間撹拌・脱泡して、透明樹脂層作製用樹脂液を得た。ついで、スリットダイコーターを用いて透明樹脂層作製用樹脂液を蛍光体層上に塗布し、130℃で30分乾燥させることにより、この蛍光体層上に透明樹脂層を形成した。この結果、蛍光体層上に透明樹脂層を備える蛍光体シートを得た。以下、「蛍光体層上に透明樹脂層を備える蛍光体シート」は、「透明樹脂層付き蛍光体シート」と適宜称される。
本実施例における透明樹脂シート法による透明樹脂層の形成では、スリットダイコーターを用いて透明樹脂層作製用樹脂液をPETフィルム上に塗布し、130℃で30分乾燥させることにより、透明樹脂シートを得た。ついで、ニッコー・マテリアルズ株式会社製の真空ラミネーターV130を用いて、蛍光体シートの蛍光体層と透明樹脂シートの透明樹脂層とを、1hPaの真空雰囲気下において100℃で30秒加熱圧着することにより、貼り合わせた。その後、透明樹脂シート側のPETフィルムを剥離し、これにより、この蛍光体層上に透明樹脂層を形成した。この結果、透明樹脂層付き蛍光体シートを得た。
本実施例における透明樹脂層の膜厚測定では、透明樹脂層を作製する蛍光体シートの所定位置の厚さを予めマイクロメーターで測定し、マーキングした。ついで、透明樹脂層をこの蛍光体シート上に形成し、その後、マーキング部分の厚さを再びマイクロメーターで測定した。得られた厚さから、先に測定しておいた厚さを差し引くことで、この透明樹脂層の膜厚を得た。本実施例において、膜厚は10mm間隔で碁盤目状に25点測定した。この測定結果から、それぞれのサンプルの平均値および膜厚ばらつき(=最大膜厚-最小膜厚)を算出した。
本実施例における空隙率測定では、蛍光体シートを集束イオンビーム(FIB)加工法により切断し、蛍光体層の断面をSEMにより観察した。1つの蛍光体シートにつき20ヶ所の断面を観察し、得られた20枚の2次元画像の空隙に相当する断面積の合計を算出した。この空隙に相当する断面積の合計を、これら20枚の2次元画像の断面積の合計で除することにより、この蛍光体層の空隙率を得た。
本実施例における発光体の製造方法では、上述したように作製した蛍光体シートまたは透明樹脂層付き蛍光体シート(1cm角)をカッティング装置(UHT社製GCUT)によりカットし、これにより、1mm角の個片シートを100個、作製した。本実施例において、個片シートは、蛍光体シートまたは透明樹脂層付き蛍光体シートを個片化したものである。ついで、ダイボンディング装置(東レエンジニアリング製)を用いて、1mm角の個片シート(蛍光体層等)を、コレットで真空吸着して基材フィルムから剥離した。この個片シートの蛍光体層を、フリップチップ型の青色LEDチップが実装され、かつこの青色LEDチップの周囲にリフレクターが形成されたLEDパッケージの青色LEDチップ表面に、位置合わせして貼り付けた。このとき、この青色LEDチップ上に、予め接着剤を塗布し、この接着剤を介して蛍光体層を貼り付けた。この接着剤には、シリコーン樹脂T15を使用した。このようにして、蛍光体シートまたは透明樹脂層付き蛍光体シートを備えた発光体を作製した。
本実施例における色度および全光束の測定では、上述したように作製した発光体に1Wの電力を投入して、この発光体のLEDチップを点灯させ、全光束測定システム(HM-3000、大塚電子社製)を用いて、CIE1931 XYZ表色系の色度(Cx,Cy)および全光束(lm)を測定した。本実施例では、各蛍光体シートにつき、それぞれ10個の発光体(LEDチップを備えたもの)を作製し、これら10個の発光体の色度の平均値と、色度ばらつきの指標である色度Cxの標準偏差(σ)とを求めた。
本実施例における全光束保持率の測定では、各蛍光体シートを青色LEDチップに搭載した発光体に、1Wの電力を投入して、この青色LEDチップを点灯させ、この点灯状態の発光体(青色LEDチップ)を温度85℃、湿度85%の条件下で放置し、300時間経過後の全光束を測定した。下記の式に基づき全光束保持率を算出することによって、発光体およびその蛍光体シートの耐久性を評価した。全光束保持率が高いほど、耐久性に優れていることを示す。
全光束保持率(%)=(300時間経過後の全光束/試験開始直後の全光束)×100
本実施例における色再現範囲の測定では、上述したように作製した発光体上に、公知の方法で作製した赤色光を透過するカラーフィルターを載せて、発光光の色度を測定した。同様に、この発光体上に緑色光を透過するカラーフィルターを載せた場合と青色光を透過するカラーフィルターを載せた場合とのそれぞれについて、発光光の色度を測定した。得られた3つの色度を頂点とした三角形の面積をDCI色度領域の面積で除することにより、DCI比を算出した。DCI比が高いほど、色再現性が良好である。
本実施例における屈折率の測定では、屈折率・膜厚測定装置“プリズムカプラMODEL2010/M”(メトリコン社製)を使用して、屈折率測定サンプルの屈折率を測定し、これにより、シリコーン樹脂およびフッ素樹脂硬化物の屈折率を測定した。
本実施例における屈折率測定サンプルの作製では、蛍光体シートに含有する樹脂を、遊星式攪拌脱泡装置“マゼルスターKK-400”(クラボウ社製)を用い、1000rpmで10分間攪拌し、脱泡して、この樹脂の分散液を作製した。この分散液を、PETフィルム上に5cc滴下した後、オーブンによって150℃で1時間加熱し、これにより、屈折率測定サンプルとして平均屈折率測定サンプルを作製した。
本実施例における透過率測定において、微粒子を含有する透明樹脂層の光透過率は、分光光度計(U-4100 Spectrophotomater(日立製作所製))に付属の積分球を用いた基本構成で、透過率測定サンプルの光透過率を測定することによって得た。透過率測定サンプルは、各実施例で作製したものを用いた。この光透過率の測定条件については、スリットは2nmとし、走査速度は600nm/分とした。また、得られた測定結果において、波長400nm~800nmにおける光透過率のうち最も小さい値は、最小透過率とした。
本実施例における透過率測定サンプルの作製では、透明樹脂層に用いるシリコーン樹脂および微粒子を、容積300mLのポリエチレン製容器に混合し、遊星式攪拌脱泡装置“マゼルスターKK-400”(クラボウ社製)を用い、1000rpmで10分間攪拌し、脱泡して、分散液を作製した。この分散液を、石英ガラス上にブレードコーターによって塗布した後、オーブンによって150℃で1時間加熱する。このようにして、透過率測定サンプルは、各実施例について作製した。
本実施例における透過率測定サンプルの膜厚測定では、石英ガラスの所定位置の厚さを予めマイクロメーターで測定し、この測定した位置をマーキングした。ついで、この石英ガラス上に透明樹脂層の透過率測定サンプルを形成した後、マーキング部分の厚さを再びマイクロメーターで測定した。得られた厚さから、先に測定しておいた石英ガラスの厚さを差し引くことで、この透過率測定サンプルの膜厚を得た。膜厚は10mm間隔で碁盤目状に25点測定し、これらの平均値を透過率測定サンプルの膜厚とした。
実施例1~6では、表2に示した組成の蛍光体層を備えた蛍光体シートを作製し、上述の方法により空隙率を測定した。また、実施例1~6の各々で得られた蛍光体シートを用いて発光体(発光装置)を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。これらの測定結果は、表3に示す。表2、3を参照してわかるように、本発明に係る蛍光体シートを用いた場合、実施例1~6のいずれも、色再現性に優れ、高光束な発光体を得ることができた。また、表1に示す赤色蛍光体T2~T6のD50のように、赤色蛍光体のD50が10μm以上であれば、全光束がより向上し、表1に示す赤色蛍光体T3~T6のD10のように、赤色蛍光体のD10が5μm以上であれば、全光束保持率がより向上することがわかった。また、表1に示す赤色蛍光体T1~T6のD10およびD50のように、赤色蛍光体のD10およびD50が大きいほど、蛍光体シートの空隙率は小さくなる傾向が見られた。
実施例7~13では、表4に示した組成の蛍光体層を備えた蛍光体シートを作製し、上述の方法により空隙率を測定した。また、実施例7~13の各々で得られた蛍光体シートを用いて発光体を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。これらの測定結果は、表5に示す。なお、表4は実施例6の組成を再掲し、表5は実施例6の結果を再掲する。表4、5から、赤色蛍光体T6および緑色蛍光体等の蛍光体の濃度が高いほど、全光束保持率がより向上することがわかった。
実施例14~17では、表6に示した組成の蛍光体層を備えた蛍光体シートを作製し、上述の方法により空隙率を測定した。また、実施例14~17の各々で得られた蛍光体シートを用いて発光体を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。これらの測定結果は、表7に示す。表6、7から、シリコーン微粒子を含有することにより、色度ばらつき(σ(Cx))はさらに改善することがわかった。
実施例18では、シリコーン樹脂T15が50wt%であり、赤色蛍光体T6が50wt%である組成で、蛍光体シートを作製した。同様に、シリコーン樹脂T15が50wt%であり、緑色蛍光体が50wt%である組成で、蛍光体シートを作製した。これらの得られた2枚の蛍光体シートの蛍光体層側を、真空ラミネーターV130(ニッコー・マテリアルズ株式会社製)を用いて貼り合わせ、これにより、赤色蛍光体を含む蛍光体層と緑色蛍光体を含む層とが積層された蛍光体シートを作製し、上述の方法により空隙率を測定した。また、この得られた蛍光体シートを用いて発光体を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。これらの測定結果は、表8に示す。表8から、実施例18では、色再現性の向上と高光束とを両立できるが、色度ばらつきは大きくなることがわかった。
実施例19~25では、表9に示した組成の蛍光体層を備えた蛍光体シートを作製した。また、実施例19~25の各々で作製した蛍光体シートの蛍光体層の膜厚は、上述の方法により測定した。また、実施例10の蛍光体シートについても、蛍光体層の膜厚を測定した。さらに、実施例19~25の各々で作製した蛍光体シートを用いて発光体を作製し、上述の方法により、色度、全光束、色再現範囲を測定した。これらの測定結果は、表10に示す。なお、表9は実施例10の組成を再掲し、表10は実施例10の測定結果を再掲する。
実施例26~32および実施例34~36では、実施例6で作製した蛍光体シート上に、スリットダイコーターを用いて透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることで、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。実施例33では、シリコーン樹脂T15を用いて上述の方法により透明樹脂シートを作製し、蛍光体層と透明樹脂層とを貼り合わせることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。実施例26~36の各々で作製した蛍光体シートの透明樹脂層の膜厚を、上述の方法で測定した。また、実施例26~36の各々で作製した透明樹脂層付き蛍光体シートの蛍光体層側をLEDチップ上に貼り付けることにより、発光体を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。実施例26~36の各々で透明樹脂層作製用樹脂液の作製に使用した樹脂の種類および実施例26~36での測定結果は、表11に示す。
実施例37~42では、表12に示した組成の透明樹脂層作製用樹脂液を作製した。つぎに、実施例10で作製した蛍光体シート上に、実施例37~42の各々で作製した透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。
実施例43~47では、表14に示した組成の透明樹脂層作製用樹脂液を作製した。つぎに、実施例10で作製した蛍光体シート上に、実施例43~47の各々で作製した透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。
実施例48~52では、表16に示した組成の透明樹脂層作製用樹脂液を作製した。つぎに、実施例10で作製した蛍光体シート上に、実施例48~52の各々で作製した透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。
実施例53~57では、表18に示した組成の透明樹脂層作製用樹脂液を作製した。つぎに、実施例10で作製した蛍光体シート上に、実施例53~57の各々で作製した透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。
実施例58~62では、表20に示した組成の透明樹脂層作製用樹脂液を作製した。つぎに、実施例10で作製した蛍光体シート上に、実施例58~62の各々で作製した透明樹脂層作製用樹脂液を塗布し、この透明樹脂層作製用樹脂液を130℃で30分乾燥させることにより、蛍光体層上に透明樹脂層を有する蛍光体シートを作製した。
実施例1~62に対する比較例では、シリコーン樹脂T15が40wt%であり、黄色蛍光体(YAG系黄色蛍光体)が60wt%である組成で、蛍光体シートを作製し、上述の方法により空隙率を測定した。また、得られた蛍光体シートを用いて発光体を作製し、上述の方法により、色度、全光束、全光束保持率、色再現範囲を測定した。これらの測定結果は、表22に示す。表22から、YAG系黄色蛍光体を用いた場合、色再現範囲は70%であり、液晶ディスプレイ用バックライトとしては不向きなものであることがわかった。
2 蛍光体層
3 支持体
4 蛍光体シート
5 透明樹脂層
6 刃物
7 個片化蛍光体層
8 コレット
9 LEDチップ
10 リフレクター
11 基板
12 透明封止材
13 発光体
14 樹脂
Claims (24)
- 赤色蛍光体とβ型サイアロン蛍光体と樹脂とを含む蛍光体層を備え、
前記赤色蛍光体は、一般式(1)で表されるMn賦活複フッ化物である、
ことを特徴とする蛍光体シート。
(一般式)
A2MF6:Mn ・・・(1)
(一般式(1)において、Aは、Li、Na、K、RbおよびCsからなる群より選ばれ、かつNaおよびKの少なくとも1つを含む1種以上のアルカリ金属であり、Mは、Si、Ti、Zr、Hf、GeおよびSnからなる群より選ばれる1種以上の4価元素である。) - 前記蛍光体層は、前記赤色蛍光体と前記β型サイアロン蛍光体と前記樹脂とを含む単一層または複数層からなり、
前記赤色蛍光体、前記β型サイアロン蛍光体および前記樹脂は、同一層に含まれる、
ことを特徴とする請求項1に記載の蛍光体シート。 - 前記樹脂の屈折率は、1.45以上、1.7以下である、ことを特徴とする請求項1または2に記載の蛍光体シート。
- 前記樹脂は、シリコーン樹脂である、ことを特徴とする請求項1~3のいずれか一つに記載の蛍光体シート。
- 前記蛍光体層における全固形分に占める前記赤色蛍光体の割合は、20重量%以上、60重量%以下である、ことを特徴とする請求項1~4のいずれか一つに記載の蛍光体シート。
- 前記蛍光体層における全固形分に占める前記赤色蛍光体の割合と前記β型サイアロン蛍光体の割合との合計は、50重量%以上、90重量%以下である、ことを特徴とする請求項1~5のいずれか一つに記載の蛍光体シート。
- 前記赤色蛍光体のD50は、10μm以上、40μm以下である、ことを特徴とする請求項1~6のいずれか一つに記載の蛍光体シート。
- 前記赤色蛍光体のD10は、3μm以上である、ことを特徴とする請求項1~7のいずれか一つに記載の蛍光体シート。
- 前記赤色蛍光体の(D90-D10)/D50は、0.5以上、1.5以下である、ことを特徴とする請求項1~8のいずれか一つに記載の蛍光体シート。
- 前記蛍光体層中の空隙率は、0.1%以上、3%以下である、ことを特徴とする請求項1~9のいずれか一つに記載の蛍光体シート。
- 前記蛍光体層に微粒子を含有する、ことを特徴とする請求項1~10のいずれか一つに記載の蛍光体シート。
- 前記微粒子は、シリコーン微粒子である、ことを特徴とする請求項11に記載の蛍光体シート。
- 前記蛍光体層上にさらに透明樹脂層が積層される、ことを特徴とする請求項1~12のいずれか一つに記載の蛍光体シート。
- 前記透明樹脂層に含まれる樹脂の屈折率は、1.3以上、1.6以下である、ことを特徴とする請求項13に記載の蛍光体シート。
- 前記透明樹脂層に含まれる樹脂の屈折率は、前記蛍光体層に含まれる樹脂の屈折率以下である、ことを特徴とする請求項14に記載の蛍光体シート。
- 前記透明樹脂層は、微粒子を含有する、ことを特徴とする請求項13~15のいずれか一つに記載の蛍光体シート。
- 前記透明樹脂層に含まれる微粒子は、シリカ微粒子、アルミナ微粒子、シリコーン微粒子から選択される1種類以上である、ことを特徴とする請求項16に記載の蛍光体シート。
- 前記透明樹脂層の波長400nm~800nmにおける最小透過率は、80%以上である、ことを特徴とする請求項13~17のいずれか一つに記載の蛍光体シート。
- 前記透明樹脂層における全固形分に占める微粒子の割合は、0.1重量%以上、30重量%以下である、ことを特徴とする請求項16、17、請求項16を引用する請求項18のいずれか一つに記載の蛍光体シート。
- 前記透明樹脂層に含まれる微粒子の平均粒径は、1nm以上、1000nm以下である、ことを特徴とする請求項16、17、請求項16を引用する請求項18、請求項19のいずれか一つに記載の蛍光体シート。
- 請求項1~20のいずれか一つに記載の蛍光体シートを個片化する個片化工程と、
個片化された前記蛍光体シートをピックアップするピックアップ工程と、
個片化された前記蛍光体シートを光源に貼り付ける貼付工程と、
を含むことを特徴とする発光体の製造方法。 - 請求項1~20のいずれか一つに記載の蛍光体シートを備える、ことを特徴とする発光体。
- 請求項1~20のいずれか一つに記載の蛍光体シートを備える、ことを特徴とする光源ユニット。
- 請求項23に記載の光源ユニットを備える、ことを特徴とするディスプレイ。
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107731996A (zh) * | 2017-09-28 | 2018-02-23 | 惠州市华瑞光源科技有限公司 | Led灯珠及其制备方法 |
JP2019001985A (ja) * | 2017-06-14 | 2019-01-10 | デンカ株式会社 | フッ化物蛍光体とそれを用いた発光装置 |
JP2019001986A (ja) * | 2017-06-14 | 2019-01-10 | デンカ株式会社 | フッ化物蛍光体とそれを用いた発光装置 |
JP2019064136A (ja) * | 2017-09-29 | 2019-04-25 | 日亜化学工業株式会社 | 透光性シートの製造方法 |
WO2019181478A1 (ja) * | 2018-03-20 | 2019-09-26 | 株式会社タムラ製作所 | 波長変換部材及び波長変換素子 |
JP2019186537A (ja) * | 2018-03-30 | 2019-10-24 | 日亜化学工業株式会社 | 波長変換部材及び発光装置 |
WO2019218337A1 (en) * | 2018-05-18 | 2019-11-21 | Rohm And Haas Electronic Materials Llc | Two-layer phosphor film for led |
CN110753735A (zh) * | 2017-06-14 | 2020-02-04 | 电化株式会社 | 氟化物荧光体和使用其的发光装置 |
JPWO2019021926A1 (ja) * | 2017-07-28 | 2020-07-30 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法 |
US11114589B2 (en) | 2017-06-14 | 2021-09-07 | Denka Company Limited | Fluoride phosphor and light-emitting device using same |
WO2022044860A1 (ja) * | 2020-08-25 | 2022-03-03 | デンカ株式会社 | フッ化物蛍光体、複合体および発光装置 |
WO2022075293A1 (ja) * | 2020-10-06 | 2022-04-14 | シャープ株式会社 | 波長変換素子、光学機器及び波長変換素子の製造方法 |
WO2022255173A1 (ja) * | 2021-06-02 | 2022-12-08 | 東レ株式会社 | 色変換組成物、色変換シート、それを含む光源ユニット、ディスプレイおよび照明装置 |
WO2023037831A1 (ja) * | 2021-09-09 | 2023-03-16 | 信越化学工業株式会社 | 被覆ksf蛍光体、該蛍光体の製造方法、該蛍光体を含有する硬化性シリコーン組成物及び光半導体装置 |
JP7530019B2 (ja) | 2020-08-31 | 2024-08-07 | 日亜化学工業株式会社 | 発光装置の製造方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110945389B (zh) * | 2017-07-28 | 2021-08-03 | 东丽株式会社 | 颜色转换组合物、颜色转换膜以及包含其的装置 |
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US11239213B2 (en) | 2019-05-17 | 2022-02-01 | Applied Materials, Inc. | In-situ curing of color conversion layer in recess |
DE102022131065A1 (de) * | 2022-11-23 | 2024-05-23 | Ams-Osram International Gmbh | Modifizierung von silikonen mit polysilsesquioxanpartikeln |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010093132A (ja) * | 2008-10-09 | 2010-04-22 | Sharp Corp | 半導体発光装置およびそれを用いた画像表示装置、液晶表示装置 |
JP2012178574A (ja) * | 2010-10-15 | 2012-09-13 | Mitsubishi Chemicals Corp | 白色発光装置及び照明器具 |
JP2013168480A (ja) * | 2012-02-15 | 2013-08-29 | Konica Minolta Inc | Led装置の製造方法 |
JP2014022704A (ja) * | 2012-07-24 | 2014-02-03 | Toray Ind Inc | 蛍光体含有樹脂シートと発光装置及びその製造方法 |
WO2014077240A1 (ja) * | 2012-11-13 | 2014-05-22 | 電気化学工業株式会社 | 蛍光体、発光素子及び照明装置 |
JP2015052648A (ja) * | 2013-09-05 | 2015-03-19 | 日亜化学工業株式会社 | カラーフィルター及び発光装置の組合せの選択方法並びに画像表示装置の製造方法 |
WO2015056590A1 (ja) * | 2013-10-15 | 2015-04-23 | シャープ株式会社 | 発光装置及びその製造方法 |
JP2015091915A (ja) * | 2013-10-04 | 2015-05-14 | 三菱化学株式会社 | 発光装置、及び波長変換部材 |
JP2015212360A (ja) * | 2014-04-17 | 2015-11-26 | パナソニックIpマネジメント株式会社 | 樹脂組成物およびその製造方法並びに半導体装置 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8491816B2 (en) * | 2008-02-07 | 2013-07-23 | Mitsubishi Chemical Corporation | Semiconductor light emitting device, backlight, color image display device and phosphor to be used for them |
JP5332673B2 (ja) * | 2008-02-07 | 2013-11-06 | 三菱化学株式会社 | 半導体発光装置、バックライトおよびカラー画像表示装置 |
US8237348B2 (en) * | 2008-03-03 | 2012-08-07 | Sharp Kabushiki Kaisha | Light-emitting device |
JP5682104B2 (ja) * | 2008-09-05 | 2015-03-11 | 三菱化学株式会社 | 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置 |
JP5391946B2 (ja) * | 2009-09-07 | 2014-01-15 | 日亜化学工業株式会社 | 蛍光体及びそれを用いた発光装置並びに蛍光体の製造方法 |
JP5953797B2 (ja) * | 2012-02-17 | 2016-07-20 | 東レ株式会社 | 半導体発光装置の製造方法 |
JP2013252637A (ja) * | 2012-06-06 | 2013-12-19 | Toray Ind Inc | 蛍光体シート積層体 |
WO2014065358A1 (ja) * | 2012-10-25 | 2014-05-01 | 東レ株式会社 | 蛍光体含有樹脂シートおよび発光装置 |
JP5804149B2 (ja) * | 2014-01-30 | 2015-11-04 | 信越化学工業株式会社 | 複フッ化物蛍光体の製造方法及び処理方法 |
JP6119623B2 (ja) * | 2014-01-30 | 2017-04-26 | 信越化学工業株式会社 | 複フッ化物蛍光体の製造方法 |
JP6008017B2 (ja) * | 2015-06-12 | 2016-10-19 | 日亜化学工業株式会社 | 蛍光体及びこれを用いた発光装置 |
-
2016
- 2016-12-01 CN CN201680066389.7A patent/CN108351444B/zh active Active
- 2016-12-01 KR KR1020187014115A patent/KR102419336B1/ko active IP Right Grant
- 2016-12-01 JP JP2016571440A patent/JP6852401B2/ja active Active
- 2016-12-01 WO PCT/JP2016/085710 patent/WO2017094832A1/ja active Application Filing
- 2016-12-02 TW TW105139781A patent/TWI728011B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010093132A (ja) * | 2008-10-09 | 2010-04-22 | Sharp Corp | 半導体発光装置およびそれを用いた画像表示装置、液晶表示装置 |
JP2012178574A (ja) * | 2010-10-15 | 2012-09-13 | Mitsubishi Chemicals Corp | 白色発光装置及び照明器具 |
JP2013168480A (ja) * | 2012-02-15 | 2013-08-29 | Konica Minolta Inc | Led装置の製造方法 |
JP2014022704A (ja) * | 2012-07-24 | 2014-02-03 | Toray Ind Inc | 蛍光体含有樹脂シートと発光装置及びその製造方法 |
WO2014077240A1 (ja) * | 2012-11-13 | 2014-05-22 | 電気化学工業株式会社 | 蛍光体、発光素子及び照明装置 |
JP2015052648A (ja) * | 2013-09-05 | 2015-03-19 | 日亜化学工業株式会社 | カラーフィルター及び発光装置の組合せの選択方法並びに画像表示装置の製造方法 |
JP2015091915A (ja) * | 2013-10-04 | 2015-05-14 | 三菱化学株式会社 | 発光装置、及び波長変換部材 |
WO2015056590A1 (ja) * | 2013-10-15 | 2015-04-23 | シャープ株式会社 | 発光装置及びその製造方法 |
JP2015212360A (ja) * | 2014-04-17 | 2015-11-26 | パナソニックIpマネジメント株式会社 | 樹脂組成物およびその製造方法並びに半導体装置 |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110753735A (zh) * | 2017-06-14 | 2020-02-04 | 电化株式会社 | 氟化物荧光体和使用其的发光装置 |
JP2019001985A (ja) * | 2017-06-14 | 2019-01-10 | デンカ株式会社 | フッ化物蛍光体とそれを用いた発光装置 |
JP2019001986A (ja) * | 2017-06-14 | 2019-01-10 | デンカ株式会社 | フッ化物蛍光体とそれを用いた発光装置 |
CN110753735B (zh) * | 2017-06-14 | 2023-01-06 | 电化株式会社 | 氟化物荧光体和使用其的发光装置 |
US11114589B2 (en) | 2017-06-14 | 2021-09-07 | Denka Company Limited | Fluoride phosphor and light-emitting device using same |
US10982139B2 (en) | 2017-06-14 | 2021-04-20 | Denka Company Limited | Fluoride phosphor and light-emitting device using same |
JP7004721B2 (ja) | 2017-07-28 | 2022-01-21 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法 |
US12060472B2 (en) | 2017-07-28 | 2024-08-13 | Dupont Toray Specialty Materials Kabushiki Kaisha | Optical member resin sheet, optical member, layered body, or light-emitting device comprising optical member resin sheet, and method for manufacturing optical member resin sheet |
JPWO2019021926A1 (ja) * | 2017-07-28 | 2020-07-30 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | 光学部材用樹脂シート、それを備える光学部材、積層体又は発光デバイス、及び光学部材用樹脂シートの製造方法 |
CN107731996A (zh) * | 2017-09-28 | 2018-02-23 | 惠州市华瑞光源科技有限公司 | Led灯珠及其制备方法 |
JP2019064136A (ja) * | 2017-09-29 | 2019-04-25 | 日亜化学工業株式会社 | 透光性シートの製造方法 |
US11398587B2 (en) | 2017-09-29 | 2022-07-26 | Nichia Corporation | Method of manufacturing light-transmissive sheet |
WO2019181478A1 (ja) * | 2018-03-20 | 2019-09-26 | 株式会社タムラ製作所 | 波長変換部材及び波長変換素子 |
JP7178074B2 (ja) | 2018-03-20 | 2022-11-25 | 国立研究開発法人物質・材料研究機構 | 波長変換部材及び波長変換素子、並びに波長変換部材の製造方法 |
JP2019164302A (ja) * | 2018-03-20 | 2019-09-26 | 株式会社タムラ製作所 | 波長変換部材及び波長変換素子 |
JP2019186537A (ja) * | 2018-03-30 | 2019-10-24 | 日亜化学工業株式会社 | 波長変換部材及び発光装置 |
WO2019218337A1 (en) * | 2018-05-18 | 2019-11-21 | Rohm And Haas Electronic Materials Llc | Two-layer phosphor film for led |
WO2022044860A1 (ja) * | 2020-08-25 | 2022-03-03 | デンカ株式会社 | フッ化物蛍光体、複合体および発光装置 |
JP7554833B2 (ja) | 2020-08-25 | 2024-09-20 | デンカ株式会社 | フッ化物蛍光体、複合体および発光装置 |
JP7530019B2 (ja) | 2020-08-31 | 2024-08-07 | 日亜化学工業株式会社 | 発光装置の製造方法 |
US12117691B2 (en) | 2020-08-31 | 2024-10-15 | Nichia Corporation | Method of producing light-emitting device and planar light source |
WO2022075293A1 (ja) * | 2020-10-06 | 2022-04-14 | シャープ株式会社 | 波長変換素子、光学機器及び波長変換素子の製造方法 |
WO2022255173A1 (ja) * | 2021-06-02 | 2022-12-08 | 東レ株式会社 | 色変換組成物、色変換シート、それを含む光源ユニット、ディスプレイおよび照明装置 |
WO2023037831A1 (ja) * | 2021-09-09 | 2023-03-16 | 信越化学工業株式会社 | 被覆ksf蛍光体、該蛍光体の製造方法、該蛍光体を含有する硬化性シリコーン組成物及び光半導体装置 |
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KR102419336B1 (ko) | 2022-07-12 |
CN108351444A (zh) | 2018-07-31 |
TW201728744A (zh) | 2017-08-16 |
JPWO2017094832A1 (ja) | 2018-09-20 |
TWI728011B (zh) | 2021-05-21 |
CN108351444B (zh) | 2021-10-26 |
KR20180090260A (ko) | 2018-08-10 |
JP6852401B2 (ja) | 2021-03-31 |
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