KR20180090260A - A phosphor sheet, a phosphor, a light source unit, a display, and a manufacturing method of a phosphor using the phosphor sheet - Google Patents

Abstract

A phosphor sheet comprising a red phosphor, a? -Type sialon phosphor and a phosphor layer. This red phosphor is the Mn-activated double fluoride represented by the general formula (1).
(General formula)
A ₂ MF ₆ : Mn (1)
Wherein A is at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs and further comprising at least one of Na and K, M is at least one element selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn.

Description

A phosphor sheet, a phosphor, a light source unit, a display, and a manufacturing method of a phosphor using the phosphor sheet

The present invention relates to a phosphor sheet, a phosphor body using the same, a light source unit, a display, and a method of manufacturing a phosphor.

BACKGROUND ART A light emitting diode (LED) is a backlight of a liquid crystal display (LCD), characterized by low power consumption, long life, Light and other vehicles. LEDs are expected to form a huge market in the field of general lighting in the future because of their low environmental load.

Since the emission spectrum of the LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain white light suitable for the backlight of the LCD or the general illumination using the LED, it is necessary to provide a phosphor suitable for each chip on the LED chip to convert the light emission wavelength. Specifically, there are a method of providing a yellow phosphor on a blue LED chip (hereinafter referred to as a blue LED chip), a method of providing a red phosphor and a green phosphor on a blue LED chip, A method of providing a red phosphor, a green phosphor and a blue phosphor is proposed. Among these methods, a method of installing a yellow phosphor on a blue LED chip and a method of installing a red phosphor and a green phosphor on a blue LED chip are most widely adopted at present from the viewpoint of luminous efficiency and cost of the LED chip.

As a phosphor used for display-purpose LEDs and the like, it is desired that the half-width of the emission peak is narrow from the viewpoint of expanding the color reproduction range. In Patent Document 1, a method of obtaining a white light emission is described the use of a half width of the emission peak in a narrow red phosphor is Mn-activated clothing fluoride phosphor, a yellow phosphor or a green phosphor of Eu ^{2 +} resurrection alkaline-earth silicon nitride phosphor.

Japanese Unexamined Patent Application Publication No. 178574

However, in a light emitting body using a conventional phosphor as described in Patent Document 1, it is difficult to improve the color reproducibility and compatibility with high light. The present invention aims to solve such a problem.

In order to solve the above problems and achieve the object, the phosphor sheet according to the present invention comprises a phosphor layer containing a red phosphor, a? -Sialon phosphor and a resin, wherein the red phosphor is represented by the general formula (1) Is a Mn-activated double fluoride.

(General formula)

A ₂ MF ₆ : Mn (1)

Wherein A is at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs and further comprising at least one of Na and K, M is at least one element selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn.

The phosphor sheet according to the present invention is the phosphor sheet according to the above invention, wherein the phosphor layer comprises a single layer or a plurality of layers comprising the red phosphor, the? -Sialon phosphor and the resin, The? -Sialon phosphor and the resin are included in the same layer.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the refractive index of the resin is 1.45 or more and 1.7 or less.

Further, the phosphor sheet according to the present invention is characterized in that, in the above invention, the resin is a silicone resin.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-mentioned 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.

Further, in the phosphor sheet according to the present invention, in the above-mentioned invention, 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 preferably 50% by weight or more and 90% Or less.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-described invention, the D50 of the red phosphor is 10 m or more and 40 m or less.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-described invention, the D10 of the red phosphor is 3 m or more.

Further, in the phosphor sheet according to the present invention, in the above-described invention, (D90-D10) / D50 of the red phosphor is 0.5 or more and 1.5 or less.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the porosity in the phosphor layer is 0.1% or more and 3% or less.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-described invention, the phosphor layer contains fine particles.

Further, the phosphor sheet according to the present invention is characterized in that, in the above invention, the fine particles are silicon fine particles.

Further, 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.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-mentioned invention, the refractive index of the resin contained in the transparent resin layer is 1.3 to 1.6.

Further, the phosphor sheet according to the present invention is characterized in that, in the above-mentioned 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.

Further, 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 phosphor sheet according to the present invention is characterized in that the fine particles contained in the transparent resin layer are at least one selected from the group consisting of silica fine particles, alumina fine particles and silicon fine particles.

The phosphor sheet according to the present invention is characterized in that the transparent resin layer has a minimum transmittance of 80% or more at a wavelength of 400 to 800 nm.

The phosphor sheet according to the present invention is characterized in that the ratio of the fine particles in the total solid content in the transparent resin layer in the above invention is 0.1 wt% or more and 30 wt% or less.

The phosphor sheet according to the present invention is characterized in that the average particle diameter of the fine particles contained in the transparent resin layer in the above invention is 1 nm or more and 1000 nm or less.

Further, a method of manufacturing a phosphor according to the present invention is a method of manufacturing a phosphor, comprising: a step of separating a phosphor sheet according to any one of the above inventions; a pickup step of picking up the separated phosphor sheet; And attaching the light source to the light source.

Further, the phosphor according to the present invention is characterized by comprising the phosphor sheet according to any one of the above-mentioned inventions.

Further, the light source unit according to the present invention is characterized by including the phosphor sheet described in any one of the above inventions.

Further, the display according to the present invention is characterized by including the light source unit described in the above invention.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an improvement in color reproducibility and a phosphor sheet capable of satisfying a high luminous flux. The light emitting unit, the light source unit, and the display including the phosphor sheet according to the present invention exert the effect of improving the color reproducibility and ensuring high brightness.

1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention.
1B is a side view showing another example of the phosphor sheet according to the embodiment of the present invention.
2 is a process diagram showing an example of a method of manufacturing a phosphor using a phosphor sheet according to an embodiment of the present invention.

Hereinafter, preferred embodiments of a phosphor sheet according to the present invention, a light emitting unit using the same, a light source unit, a display, and a method for manufacturing a light emitting body will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications may be made depending on the purpose and use.

<Phosphor Sheet>

The phosphor sheet according to the embodiment of the present invention contains a phosphor layer containing a red phosphor, a? -Sialon phosphor and a resin. In this phosphor sheet, the red phosphor is a Mn-activated double fluoride represented by the general formula (1).

A ₂ MF ₆ : Mn (1)

In the general formula (1), A is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) At least one alkali metal. 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).

1A is a side view showing an example of a phosphor sheet according to an embodiment of the present invention. 1A, a phosphor sheet 4 according to an embodiment of the present invention includes a phosphor layer 2 containing a phosphor 1 and a resin 14 on a support 3. As shown in Fig. 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. For example, as shown in Fig. 1A, a phosphor layer 2 is formed on a support 3 to constitute a phosphor sheet 4. Fig.

The phosphor layer 2 may be composed of a single layer containing the red phosphor and the? -Sialon phosphor as the phosphor 1 and the resin 14. Alternatively, the phosphor layer 2 may be composed of a plurality of layers containing the phosphor 1 and the resin 14. In the case where the phosphor layer 2 is composed of a plurality of layers, the first phosphor layer containing the red phosphor and the resin 14 as the phosphor 1, the? -Type sialon phosphor as the phosphor 1 and the resin (14) And the second phosphor layer may be stacked one on top of the other to constitute a plurality of layers of the phosphor layer 2. Preferably, the red phosphor and the? -Sialon phosphor as the phosphor 1 and the resin 14 are contained in the same layer in the single layer or the plurality of layers constituting the phosphor layer 2. This is for the reasons given below.

Even if the phosphor layer 2 is a laminate of a layer including a red phosphor (first phosphor layer) and a layer including a? -Type sialon phosphor (second phosphor layer), improvement in color reproducibility and compatibility with high light are possible However, in the phosphor layer 2, it is necessary to separately control the film thickness of each layer. As a result, the resulting chromaticity fluctuation of the phosphor sheet 4 becomes large. By contrast, in the phosphor layer 2, since the red phosphor and the? -Sialon phosphor as the phosphor 1 and the resin 14 are included in the same layer, the chromaticity variation of the phosphor sheet 4 is improved.

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 as shown in Fig. In the phosphor sheet 4 shown in Fig. 1B, the transparent resin layer 5 is formed on the upper surface (the surface opposite to the support 3) of the phosphor layer 2 composed of, for example, a single layer or a plurality of layers have. The presence of the transparent resin layer 5 improves the durability of the phosphor sheet 4.

In the present embodiment, the phosphor sheet 4 is provided with a phosphor layer 2 of a single layer or a plurality of layers, or the phosphor layer 2 and the transparent resin layer 5, From the standpoint of maintenance of shape and ease of handling, it is usually supported by the support 3. That is, in the present embodiment, the phosphor sheet 4 and the support 3 are sometimes referred to as a &quot; phosphor sheet &quot;.

<Phosphor layer>

The phosphor layer 2 is a layer mainly containing the phosphor 1 and the resin 14, for example, as shown in Figs. 1A and 1B. As the phosphor 1, at least a red phosphor represented by the general formula (1) and a? -Type sialon phosphor can be given.

(Red phosphor)

The red phosphor is a phosphor having an emission peak at a wavelength of 590 nm to 750 nm. In order to improve the color reproducibility of the phosphor sheet 4 according to the embodiment of the present invention, the phosphor sheet 2 contains a Mn-activated double fluoride (A ₂ MF ₆ : Mn ). &Lt; / RTI &gt; The red phosphor which is the Mn-activated double fluoride is referred to as &quot; Mn-activated double fluoride complex fluorescent substance &quot;. Hereinafter, the Mn-recovered complex fluorophore complex fluorescent material is appropriately abbreviated as &quot; red fluorescent substance &quot;.

The Mn-activated birefringent complex fluorescent substance is a phosphor which uses manganese (Mn) as an activator and a fluoride complex salt of an alkali metal or an alkaline earth metal as a host crystal. In the Mn-activated birefringent complex fluorescent material, the coordination center of the fluoride complex forming the host crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, or Sn) Is preferably 6. A preferable Mn-activated birefringent complex fluorescent material is K ₂ SiF ₆ : Mn in which A is K (potassium) and M is Si (silicon) in the general formula (1). This is called a KSF phosphor.

The proportion of the red phosphor (i.e., the Mn-activated birefringent complex fluorescent substance) 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, more preferably 60% by weight or less. Since this ratio is equal to or more than the preferable lower limit value, the color reproduction range of the phosphor sheet 4 is further improved. On the other hand, when the ratio is 80% by weight or less, the chromaticity fluctuation of the phosphor sheet 4 is improved. When the 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 (see Fig. 1A) is preferably 5 mu m or more, and more preferably 10 mu m or more. Further, the D50 of the red phosphor is preferably 40 m or less, more preferably 30 m or less. When the D50 of the red phosphor is 5 占 퐉 or more, the phosphor sheet 4 in high light can be obtained. When the D50 of the red phosphor is 40 占 퐉 or less, the chromaticity variation of the phosphor sheet 4 is improved.

Further, D10 of the red phosphor as the phosphor (1) is preferably 3 m or more, and more preferably 5 m or more. Thus, the durability of the phosphor sheet 4 is improved. The upper limit of D10 of the red phosphor is not particularly limited, but is preferably 15 占 퐉 or less, more preferably 12 占 퐉 or less.

Further, in the red phosphor as the phosphor 1, the value x represented by the following formula (11) is preferably 0.5 or more and 1.8 or less, more preferably 1.5 or less. Further, the upper limit value of the value x is preferably 1.50 or less, more preferably 1.4 or less, even more preferably 1.35 or less, still more preferably 1 or less.

x = (D90-D10) / D50 (11)

The value x is an index of the particle size distribution of the red phosphor. The small value x means that a red phosphor (for example, KSF phosphor) having a small particle diameter, which causes a decrease in durability, is few and a red phosphor having a large diameter (for example, KSF phosphor) do. When the value x is 1.5 or less, the durability and chromaticity fluctuation of the phosphor sheet 4 are further improved.

However, if the particle size distribution of the red phosphor in the phosphor layer 2 is too narrow, light is hardly scattered in the phosphor sheet 4. In this case, when the phosphor sheet 4 is used to assemble the phosphor, a problem called a yellow ring occurs. The yellow ring is a phenomenon in which the colors appear different when the light emitting body is viewed from the front and when viewed from the oblique direction. This yellow ring is a phenomenon that is conspicuous when light scattering in the phosphor layer 2 is small. From the viewpoint of suppression of yellowing, the value x is preferably 0.5 or more.

Here, D10, D50 and D90 are particle diameters measured by the following methods. For example, the cross section of the phosphor layer 2 is observed with an SEM, and in the obtained two-dimensional image, the distance between the two intersections of the straight line intersecting the outer edge of the particle of the phosphor 1 at two points becomes the maximum The distance is calculated, and it is defined as the individual particle diameter of the particle. (Particle diameter) of 50% of the passing particle size distribution was taken as D50, the particle diameter of 10% of the passing particle size distribution from the small particle size side was D10, and the particle size distribution The particle size of 90% is D90.

In the case of the LED light source on which the phosphor sheet 4 is mounted, the fluorescent sheet 4 (4) may be formed by any of a mechanical polishing method, a microtome method, a CP method (Cross-section Polisher), and a focused ion beam ) Is polished so that the cross section of the phosphor layer 2 is observed, and then the above-mentioned grain size can be calculated from a two-dimensional image obtained by observing the obtained cross section with an SEM.

(? -type sialon phosphors)

The? -type sialon phosphor is a solid solution of? -type silicon nitride, in which aluminum (Al) is solid-solved at the Si position of the? -type silicon nitride crystal and oxygen (O) is substituted at the nitrogen (N) position. Si _{6 - z} Al _z O _z N _{8 -z} is used as a general formula of β-type sialon since there are two food atoms in the unit cell (unit lattice) of β-type sialon used for β-type sialon phosphors . In this general formula, z is a value of more than 0 and less than 4.2. In the? -Type sialon phosphors of the present embodiment, the solubility range of? -Sialon is very wide and the molar ratio of (Si, Al) / (N, O) needs to be maintained at 3/4. The general method for producing β-type sialon is to add silicon oxide and aluminum nitride in addition to silicon nitride, or to add aluminum oxide and aluminum nitride.

The β-type sialon is a β-type sialon phosphor which is excited by ultraviolet to blue light and exhibits green light emission with a wavelength of 520 nm to 560 nm by introducing a light emitting element (Eu, Sr, Mn, Ce or the like) . This is preferably used as a green light emission component of a light emitting body such as a white LED. Specifically, europium (Eu ^{2 +)} having β-type sialon phosphor is Eu ^{2 +} phosphor between the resurrection β-type sialon is, since the emission spectrum is very sharp, blue, green, and image processing is required of the red narrow band emission containing It is a material suitable for a display device or a backlight source of a liquid crystal display panel.

The D50 of the? -Sialon phosphor as the phosphor 1 (see FIG. 1A) is preferably 1 占 퐉 or more, and more preferably 10 占 퐉 or more. The D50 of the? -Sialon phosphor is preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less. The shape of the β-type sialon phosphor is not particularly limited and various spheres such as spheres and columns can be used. Here, D50 is the particle diameter measured in the same manner as in the case of the above-mentioned red phosphor.

The content of the? -Sialon phosphor as the phosphor 1 in the phosphor layer 2 is preferably not less than 3% by weight of the entire phosphor layer 2 from the viewpoint of enlarging the color reproduction range, 2) is more preferably 5% by weight or more. The content of the? -Sialon phosphor is preferably not more than 50% by weight of the entire phosphor layer (2), more preferably not more than 40% by weight of the entire phosphor layer (2).

The sum 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 wt% or more and 90 wt% or less. The lower limit of the total of these proportions is more preferably 65% by weight or more, and still more preferably 70% by weight or more. The total upper limit of these proportions is more preferably 85% by weight or less, and even more preferably 80% by weight or less. Since the total of both of these ratios is 50% by weight or more, the heat radiation of the phosphor layer 2 is improved, so that the heat storage of the phosphor 1 contained in the phosphor layer 2 can be suppressed. As a result, the high luminous flux of the phosphor sheet 4 can be maintained. Further, when the sum of both of these ratios is 90 wt% or less, the chromaticity variation of the phosphor sheet 4 is improved.

The porosity of the phosphor layer 2 in the phosphor sheet 4 having the phosphor 1 and the phosphor 2 in the present invention is preferably 3% More preferably 2% or less, still more preferably 1% or less, still more preferably 0.5% or less. This is because the smaller the porosity of the phosphor layer 2 is, the higher the extraction efficiency of the light from the phosphor layer 2 is, and hence the phosphor sheet 4 that gives a light emitter in high light can be obtained. The porosity in the phosphor layer 2 is not particularly limited to a lower limit, but is preferably 0.1% or more.

Here, the porosity is the ratio of the voids in the phosphor layer 2. This porosity can be measured by the following method. For example, the phosphor sheet 4 may be formed by a method such as mechanical polishing, microtome method, CP method (cross-section polisher), and focused ion beam (FIB) do. Thereafter, the area corresponding to the voids of the phosphor layer 2 is calculated from the two-dimensional image obtained by observing the obtained cross section with an SEM, and the area of the calculated voids is calculated by dividing the area of the whole of the phosphor layer 2 Divide by area. Thereby, the porosity of the phosphor layer 2 is obtained.

By setting the D10 and D50 of the red phosphor contained in the phosphor layer 2 within the above preferable range and by making the above value x (see Expression (11)), which is an index of the particle size distribution of the red phosphor, smaller, The porosity of the substrate 2 tends to decrease.

(Other phosphors)

The phosphor layer 2 may further contain a phosphor other than the above-mentioned phosphor (1). Examples of the fluorescent substance other than the above-mentioned fluorescent substance 1 include other red fluorescent substance, other green fluorescent substance, yellow fluorescent substance, and blue fluorescent substance. In the present embodiment, 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 to 500 nm.

The other red phosphor is other than the red phosphor represented by the general formula (1) (Mn activated polyfluoride complex fluorescent material). Examples of 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.

Other green phosphors are other than? -Type sialon phosphors. As other green phosphors, for example, SrAl ₂ O ₄ : Eu, Y ₂ SiO ₅ : Ce, Tb, MgAl ₁₁ O ₁₉ : Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ : Eu, Ba) Ga ₂ S ₄ : Eu, and the like.

Examples of the yellow phosphor include a yttrium-aluminum oxide phosphor activated with at least cerium, a yttrium-gadolinium-aluminum oxide phosphor activated with at least cerium, and a yttrium-gallium aluminum oxide phosphor activated with at least cerium.

As a blue phosphor, such as _{Sr 5 (PO 4) 3 Cl} : Eu, (SrCaBa) 5 (PO 4) 3 Cl: Eu, (BaCa) 5 (PO 4) 3 Cl: Eu, (Mg, Ca, Sr And Ba) ₂ B ₅ O ₉ Cl: Eu, Mn, (PO ₄ ) ₆ Cl ₂ : Eu, Mn and the like (at least one element among Mg, Ca, Sr and Ba)

Examples of fluorescent materials that emit light in response to 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 O _{12 : Ce, Y 3 Al 5 O} 12: YAG -based phosphor, such as _{Ce, Tb 3 Al 5 O 12} : TAG -based phosphors, such as _{Ce, (Ba, Sr) 2} SiO 4: Eu -based phosphors or Ca ₃ Sc ₂ Si ₃ O _12: Ce based phosphor, (Sr, Ba, Mg) 2 SiO 4: silicate-based phosphor such as _{Eu, (Ca, Sr) 2} Si 5 N 8: Eu, (Ca, Sr) AlSiN 3: Eu, CaSiAlN 3 : nitro, such as Eu nitride-based _{phosphor, Ca y (Si, Al)} 12 (O, N) 16: Eu , etc. of the oxynitride-based fluorescent material, and further (Ba, Sr, Ca) Si 2 O 2 N 2: Eu -based Phosphors, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu-based phosphors, and SrAl ₂ O ₄ : Eu and Sr ₄ Al ₁₄ O ₂₅ : Eu phosphors.

(Suzy)

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. When the refractive index of the resin 14 is 1.45 or more, the refractive index difference with the Mn-activated birefringent complex fluorescent material having the average refractive index of about 1.4 (the red fluorescent material as the fluorescent substance 1) becomes large and light is easily scattered in the fluorescent substance layer 2 Loses. As a result, the length of the optical path from when the light enters the phosphor layer 2 to when it emerges 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 the phosphor for expressing the desired chromaticity can be reduced.

On the other hand, when the refractive index of the resin 14 exceeds 1.7, the light in the phosphor layer 2 is excessively scattered and the optical path length becomes longer than necessary. As a result, the luminescent light emitted from the phosphor 1 in the phosphor layer 2 is likely to be absorbed by the phosphor 1, and as a result, the intensity of the light emitted from the phosphor is lowered.

The material of the resin 14 is not particularly limited as long as it can uniformly disperse the fluorescent substance (such as the fluorescent substance 1 shown in Fig. 1A) therein and can form the fluorescent substance layer 2. Fig. As the resin 14, for example, a silicone resin, an epoxy resin, a polyarylate resin, a PET modified polyarylate resin, a polycarbonate resin, a cyclic olefin resin, a polyethylene terephthalate resin, a polymethyl methacrylate resin, A polypropylene resin, a modified acrylic resin, a polystyrene resin, and an acrylonitrile-styrene copolymer resin. Of these, silicone resins and epoxy resins are preferable from the viewpoint of transparency. In view of heat resistance, a silicone resin is particularly preferable.

As the silicone resin which is an example of the resin (14) used in the present invention, a curable silicone resin is preferable. The curable silicone resin used as the resin (14) may be any one of a one-liquid type and a two-liquid type (three-liquid type). The curable silicone resin is a type which causes a condensation reaction by moisture or catalyst in the air, such as a dealcohol type, a defoaming type, a deacetyl type, a dehydroxylamine type and the like. Further, the curable silicone resin has a side reaction type which causes a hydrosilylation reaction by a catalyst. As the resin 14, any of these types of curable silicone resins may be used. Particularly, the addition reaction type silicone resin is more preferable because it has no byproducts accompanied by the curing reaction, has a small curing shrinkage, and is easy to accelerate curing by heating.

The addition reaction type silicone resin as an example of the resin (14) is formed by, for example, a hydrosilylation reaction of 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 vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, Octenyltrimethoxysilane, and the like. Examples of the "compound having a hydrogen atom bonded to a silicon atom" include methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane and methylhydrogenpolysiloxane-CO-methylphenylpolysiloxane . Examples of the addition reaction type silicone resin include those formed by the hydrosilylation reaction of such a material. As the resin 14, other known resins such as those described in, for example, JP-A-2010-159411 can be used.

As the resin 14, for example, a commercially available silicone sealant for general LED applications can be used. Specific examples thereof include OE-6630A / B and OE-6336A / B manufactured by Toray Dow Coming Co., Ltd. and SCR-1012A / B and SCR-1016A / B manufactured by Shinetsu Chemical Industry Co., .

Further, the silicone resin as the resin 14 may be one having heat-sealability. This is because when the resin 14 of the phosphor layer 2 is a silicone resin having heat sealability, the phosphor sheet 4 having the phosphor layer 2 has heat-sealability, Can be heated and attached to the LED chip. The heat fusion property referred to herein is a property of being softened by heating. When the phosphor sheet 4 has heat-sealability, 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-emitting body and the like can be simplified. In the phosphor layer 2 of the heat-sealable phosphor sheet 4, 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.

As an example of the silicone resin having heat sealability, it is particularly preferable to be a crosslinked product obtained by a hydrosilylation reaction of a crosslinkable silicone composition containing the following components (A) to (D). The crosslinked product can be preferably used as a matrix resin for a phosphor sheet 4 which does not require an adhesive since the storage elastic modulus at 60 ° C to 250 ° C is reduced and a high adhesive force is obtained by heating.

(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)

In the average unit formula (21), R ¹ 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. However, 65 mol% to 75 mol% of R ¹ is a phenyl group, and 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. a, b and c are numbers satisfying 0.5? a? 0.6, 0.4? b? 0.5, 0? c? 0.1 and a + b =

The component (B) is an organopolysiloxane represented by the following general formula (2). This organopolysiloxane has a content within a range of 5 to 15 parts by weight based on 100 parts by weight of the component (A).

R ³ ₃ SiO (R ³ ₂ SiO) _m SiR ³ ₃ (2)

In the general formula (2), 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. However, 40 mol% to 70 mol% of R ³ is a phenyl group, at least one of R ³ is an alkenyl group. m is an integer within the range of 5 to 50;

The component (C) is an organotrisiloxane represented by the following general formula (3). The organotrisiloxane is an amount such that the molar ratio of the silicon atom-bonded hydrogen atoms in the component (C) to the sum of the alkenyl groups in the component (A) and the alkenyl groups in the component (B) is within the range of 0.5 to 2.

^{_{(HR 4 2 SiO) 2 SiR}} 4 2 ··· (3)

In the general formula (3), R ⁴ is a phenyl group or an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms. Provided that 30 to 70 mol% of R ⁴ is a phenyl group.

Component (D) is a catalyst for hydrosilylation reaction. The catalyst for hydrosilylation reaction is an amount sufficient to promote the hydrosilylation reaction of the alkenyl group in the component (A) and the silicon atom-binding hydrogen atom in the component (B).

When the values of a, b and c in the average unit formula (21) of the component (A) satisfy the above conditions, a sufficient hardness at room temperature of the obtained crosslinked product is obtained, and softening at a high temperature of the crosslinked product is obtained Loses. When the content of the phenyl group in the general formula (2) of the component (B) is less than the lower limit of the above range, softening at a high temperature of the resulting crosslinked product is insufficient. On the other hand, if the content of the phenyl group exceeds the upper limit of the above range, the transparency of the resultant crosslinked product is lost and the mechanical strength thereof is lowered. In the general formula (2), at least one of R ³ is an alkenyl group. This is because, when the component (B) does not have an alkenyl group, the component (B) is not introduced into the crosslinking reaction, and the component (B) may bleed out from the resulting crosslinked product. Further, in the general formula (2), m is an integer within a range of 5 to 50. The numerical value of m is a range in which the handling workability can be maintained while maintaining the mechanical strength of the resulting crosslinked product.

The content of the component (B) is an amount that falls within a range of 5 to 15 parts by weight based on 100 parts by weight of the component (A). The range of the content is a range for obtaining sufficient softening at a high temperature of the resulting crosslinked product.

In the general formula (3) of the component (C), R ⁴ is a phenyl group or an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms. Examples of the 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. Examples of the cycloalkyl group as R ⁴ include a cyclopentyl group and a cycloheptyl group. The content of the phenyl group in R ⁴ is within a range of 30 mol% to 70 mol%. This content range is a range in which sufficient softening can be obtained at a high temperature of the obtained crosslinked product 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 the silicon atom-bonded hydrogen atoms in the component (C) is in the range of 0.5 to 2, relative to the total of the alkenyl groups in the component (A) and the alkenyl groups in the component . This content range is a range in which sufficient hardness at room temperature of the obtained crosslinked product can be obtained.

The component (D) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the silicon atom-binding hydrogen atom in the component (C). Examples of the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Of these, platinum-based catalysts are preferable in that the curing of the silicone composition can be remarkably accelerated. Examples of the platinum catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex. In particular, the platinum-based catalyst is preferably a platinum-alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane , Alkenylsiloxanes obtained by substituting a part of methyl groups in these alkenylsiloxanes with ethyl groups or phenyl groups, and alkenylsiloxanes in which vinyl groups of these alkenylsiloxanes are substituted with allyl groups or hexenyl groups. Particularly, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable in view of good stability of the platinum-alkenylsiloxane complex.

In order to improve the stability of the platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl- 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl- Tetraphenyldisiloxane, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, or an organosiloxane oligomer such as a dimethylsiloxane oligomer is preferably added . Particularly, it is preferable to add an alkenylsiloxane to the complex.

The content of the component (D) is not particularly limited as far as it is sufficient to accelerate the hydrosilylation reaction of the silicon atom-bonded hydrogen atoms in the component (A) and the alkenyl groups in the component (B) and the component (C). Preferably, 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 by mass in the silicone composition. Furthermore, the content of the component (D) is preferably such that the metal atom is within the range of 0.01 ppm to 100 ppm, particularly preferably the metal atom is within the range of 0.01 ppm to 50 ppm. The range of the content is such that the resulting silicone composition is sufficiently crosslinked, and problems such as coloring do not occur.

On the other hand, the ratio of the resin (14) in the total solid content in the phosphor layer (2) is preferably 10 wt% or more and 60 wt% or less. This is because, by setting the ratio of the resin 14 within the above range, it is possible to improve both the color reproducibility of the phosphor sheet 4 and high durability.

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 and film thickness measuring apparatus "prism coupler MODEL 2010 / M" (manufactured by Metricon). The refractive index measurement sample was prepared by preparing a dispersion of the resin 14 by stirring and defoaming the resin 14 at 1000 rpm for 10 minutes using a planetary stirring defoaming apparatus "Mazerstar KK-400" (manufactured by Gurabo) , Dropping 5 cc of the dispersion liquid onto the PET film, and then heating in an oven at 150 캜 for 1 hour.

(Fine particles)

The phosphor sheet 4 according to the embodiment of the present invention is intended to improve dispersion stability of the phosphor 1 in the phosphor layer 2 with respect to the resin 14 even when the phosphor sheet 2 contains fine particles do. Examples of the fine particles include fine particles composed of titania, silica, alumina, silicon, 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 fine particles of silica, fine particles of alumina or fine particles of silicon and fine particles of silicon in view of low hardness from the viewpoint that they are easy to obtain. As the hardness of the fine particles is low, there is an effect of suppressing the breakage of the red phosphor in the dispersing step of the phosphor 1, and as a result, it is possible to obtain the phosphor sheet 4 having higher luminescence intensity.

As examples of the silicon fine particles, hydrolysis of organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organanediacetoxysilane, organotrioxime silane and organosiloxymesilane, Followed by condensation. Examples of the silicon fine particles include silicon fine particles.

Examples of the organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, propyltrimethoxysilane, i-propyltrimethoxysilane, n-butyltriethoxysilane, i-propyltrimethoxysilane, i-propyltrimethoxysilane, Butyltriethoxysilane, t-butyltributoxysilane, N-beta (aminoethyl) gamma -aminopropyltrimethoxysilane, gamma -glycidoxypropylsilane, Trimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and the like.

Examples of the organodialkoxysilane include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropylmethyldiethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (Phenylaminomethyl) methyldimethoxysilane, vinylmethyldiethoxysilane, and the like.

Examples of the organotriacetoxysilane include methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, and the like. Examples of the organanediacetoxysilane include dimethyldiacetoxysilane, methylethyldiacetoxysilane, vinylmethyldiacetoxysilane, vinylethyldiacetoxysilane, and the like. Examples of the organotrioxime silane include methyltrismethylethylketooxime silane, vinyltrismethylethylketooxime silane, and the like. Examples of the organosiloxane silane include methylethylbismethylethylketooxime silane and the like.

Such fine particles (fine particles contained in the phosphor layer 2) are specifically disclosed in Japanese Laid-Open Patent Application No. 63-77940, Japanese Laid-Open Patent Publication No. 6-248081, A method reported in JP-A-2003-342370, a method reported in JP-A-4-88022, and the like. It is also possible to use at least one organosilane such as organotrialkoxy silane, organodialkoxysilane, organotriacetoxysilane, organotriacetoxysilane, organotrioxime silane, organosiloxane silane, and the like, and partial hydrolyzate thereof To an aqueous alkali solution to obtain fine particles by hydrolysis and condensation; or by adding at least one of organosilane and partial hydrolyzate thereof to water or an acidic solution and adding at least one of the organosilane and its partial hydrolyzate A method in which a hydrolyzed partial condensate is obtained and then an alkali is added to proceed the condensation reaction to obtain fine particles; a method in which at least one of organosilane and its hydrolyzate is used as an upper layer and a mixed solution of alkali or alkali and an organic solvent is used as a lower layer At their interface, at least one of the organosilane and its hydrolyzate By total hydrolysis-condensation is known also how to obtain the fine particles. In either of these methods, fine particles contained in the phosphor layer 2 in the present invention can be obtained.

In the preparation of spherical organopolysilsesquioxane fine particles by hydrolysis and condensation of at least one of organosilane and partial hydrolyzate thereof among them, as disclosed in Japanese Patent Application Laid-Open No. 2003-342370 It is preferable to use the silicon fine particles obtained by the method of adding the polymer dispersant into the reaction solution.

In the present invention, the average particle diameter of the silicon fine particles is represented by D50. The lower limit of the average particle diameter is preferably 0.05 탆 or more, more preferably 0.1 탆 or more. The upper limit of the average particle diameter is preferably 2.0 탆 or less, and more preferably 1.0 탆 or less. By using such silicon fine particles, it is possible to obtain a phosphor layer (2) having excellent discharging property and excellent film thickness uniformity when a slit die coater is used. It is also preferable to use spherical silicon fine particles as the monodisperse. The average particle diameter (D50) of the silicon fine particles can be obtained by the same method as the average particle diameter of the red phosphor as the above-mentioned phosphor (1).

The proportion of the fine particles in the total solid content in the phosphor layer 2 is preferably 0.1 wt% or more and 10 wt% or less. The dispersion stability of the phosphor 1 in the phosphor layer 2 (among the resin 14) can be improved, and as a result, the color reproducibility of the phosphor sheet 4 And high light flux and high durability can both be achieved.

The respective contents of the phosphor 1, the resin 14 and the silicon fine particles in the phosphor layer 2 in the present invention can be obtained from the phosphor layer 2 that has been produced and the LED light source on which the phosphor layer 2 is mounted. For example, a phosphor layer 2 is embedded and cut with a predetermined resin, and a sample having a section polished is prepared. The exposed cross section is observed with a scanning electron microscope (SEM) It is possible to clearly distinguish the particle portion of the phosphor 1, the silicon fine particle portion and the resin 14 portion of the phosphor 1. It is possible to accurately measure the respective volume ratios of the phosphor 1 (phosphor particles), the silicon fine particles and the resin 14 in the entire phosphor layer 2 from the area ratio on the cross section. When the specific gravity of each component forming the phosphor layer 2 is clear, the weight ratio of the phosphor 1 to the phosphor layer 2 can be calculated by dividing the respective volume ratios by the respective specific gravity. When the composition of each component forming the phosphor layer 2 is not clear, the composition of each of these components can be determined by analyzing the cross-section of the phosphor layer 2 by high-resolution spectroscopic infrared spectroscopy or IPC emission analysis . If the composition of each of these components is known, the specific gravity inherent to the material of the resin 14 and the phosphor 1 can be estimated to be considerably accurate, and the weight ratio can be obtained by using this.

(Other components)

In the phosphor layer 2, a hydrosilylation reaction retarder is preferably added as another component in order to suppress curing at room temperature and to increase the usable time. As the hydrosilylation reaction retarder, for example, 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexane 3-pentene-1-yne and 3,5-dimethyl-3-hexene-1-yne and the like, and organic compounds such as tetramethyltetravinylcyclotetra Methyl-1-butyne-3-oxy) silane, vinyl-tris (3-methyl-1-butyne-3 -Oxy) silane, and the like.

In the phosphor layer 2, fine particles such as fumed silica, glass powder, quartz powder and the like, an inorganic filler such as zinc oxide, a pigment, a flame retardant, a heat resistant agent, an oxidizing agent A dispersant, a solvent, an adhesion-imparting agent such as a silane coupling agent or a titanium coupling agent, or the like.

&Lt; Transparent resin layer >

The transparent resin layer 5 (see Fig. 1B) is a resin layer having a total light transmittance at a wavelength of 450 nm of 90% or more and not containing the phosphor 1. The transparent resin layer 5 is laminated on the phosphor layer 2, for example, as shown in Fig. 1B. The minimum transmittance of the transparent resin layer 5 at a wavelength of 400 to 800 nm is preferably 80% or more. The minimum transmittance referred to here is the smallest value among the light transmittances at wavelengths of 400 nm to 800 nm. With the minimum transmittance of 80% or more, the phosphor sheet 4 is easily compatible with high light-fastness 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 or the like) in the phosphor layer 2 and as a result, Durability is improved.

The transparent resin layer 5 may further contain fine particles. Since the transparent resin layer 5 contains fine particles, the uniformity of the film thickness of the transparent resin layer 5 is improved. Therefore, the phosphor sheet 4 is picked up with high accuracy in the pickup process of the phosphor sheet 4 It is possible. One reason for the non-uniformity of the thickness of the transparent resin layer 5 is the flow of the resin in the drying step when the transparent resin layer 5 is formed. In this drying step, since the resin contained in the transparent resin layer 5 is reduced in viscosity by heating, the resin easily flows. Particularly, in the case where the resin contained in the transparent resin layer 5 is a silicone resin having heat-sealability, since the viscosity of the resin is remarkably lowered, the film thickness of the transparent resin layer 5 tends to become uneven. It is particularly important that the transparent resin layer 5 contains fine particles in order to maintain the uniformity of the thickness of the transparent resin layer 5 when a silicone resin having thermal fusion bonding is used for the transparent resin layer 5 Do.

The improvement in the uniformity of the film thickness of the transparent resin layer 5 also has the effect of enhancing the function of the transparent resin layer 5 as a protective layer. If there is a thin portion of the transparent resin layer 5 locally, this thin portion does not sufficiently function as a protective layer, and therefore the durability of the resulting light emitting body is low. According to the present invention, such a situation can be suppressed.

(Suzy)

Examples of the resin used for the transparent resin layer 5 include silicone resins, fluororesins, epoxy resins, polyarylate resins, PET modified polyarylate resins, polycarbonate resins, cyclic olefin resins, polyethylene terephthalate resins, It is preferable that the resin is at least one resin selected from acrylate resin, polypropylene resin, modified acrylic resin, polystyrene resin and acrylonitrile / styrene copolymer resin. Of these, at least one resin selected from a silicone resin, a fluororesin and an epoxy resin is more preferable, and a silicone resin is particularly preferable from the viewpoint of heat resistance.

When the resin used for the transparent resin layer 5 is a silicone resin, the silicone resin may be one having heat-sealability. When the transparent resin layer 5 is formed by the transparent resin sheet method described later because the silicone resin has thermal fusion property, the phosphor layer 2 and the transparent resin layer 5 can be firmly adhered to each other.

(Fine particles)

It is preferable that the fine particles used for the transparent resin layer 5 have small absorption and light emission in visible light. Examples of the fine particles include fine particles such as titania, silica, alumina, silicon, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate. Of these, at least one fine particle selected from silica fine particles, alumina fine particles and silicon fine particles is more preferable from the viewpoint of availability, and from the viewpoint that the refractive index and the particle diameter can be easily controlled, the fine silicon particles are particularly preferable.

The minimum transmittance of the transparent resin layer 5 at a wavelength of 400 to 800 nm is reduced to 80% by decreasing the particle diameter of the fine particles in the transparent resin layer 5 and further reducing the difference in refractive index between the resin and the fine particles in the transparent resin layer 5. [ Or more.

The average particle diameter of the fine particles contained in the transparent resin layer 5 is preferably 1 nm or more, more preferably 3 nm or more. The average particle diameter of the fine particles is preferably 1000 nm or less, more preferably 300 nm or less. By setting the average particle diameter of the fine particles to a preferable lower limit value or more, the fine particles can be stably dispersed in the transparent resin layer 5. When the average particle diameter of the fine particles is 1000 nm or less, scattering of light in the transparent resin layer 5 can be suppressed, so that the transparent resin layer 5 can maintain a high light transmittance.

The average particle diameter of the fine particles (fine particles contained in the transparent resin layer 5) referred to herein is the 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 above-described phosphor 1.

The proportion of the fine particles in the total solid content in the transparent resin layer 5 is preferably 0.1% by weight or more, more preferably 1% by weight or more. The proportion of the fine particles is preferably 30% by weight or less, and more preferably 10% by weight or more. By controlling the ratio of the fine particles to a preferable lower limit value or more, the film thickness variation of the transparent resin layer 5 can be suppressed. When the ratio of the fine particles is not more than the preferable upper limit value, the high light transmittance of the transparent resin layer 5 can be maintained.

(Other features)

The light transmittance of the transparent resin layer 5 containing fine particles can be measured using a spectrophotometer. For example, when using a U-4100 spectrophotometer manufactured by Hitachi Seisakusho Co., Ltd., the sample light transmittance of the transparent resin layer 5 can be measured with the basic configuration using an integrating sphere attached to this measuring apparatus. As for the measurement conditions of the light transmittance, the slit is 2 nm and the scanning speed is 600 nm / min.

A sample for measuring the light transmittance of the transparent resin layer 5 (hereinafter referred to as &quot; transmittance measurement sample &quot;) can be produced by the following method. For example, the resin and fine particles used in the transparent resin layer 5 are stirred and defoamed to prepare a dispersion. The dispersion is coated on a quartz glass with a blade coater, and then heated in an oven at 150 DEG C for 1 hour Heat it. In this way, a sample for measuring the transmittance can be produced.

Measurement of Transmittance The film thickness of the sample can be measured by the following method. For example, the predetermined position of the quartz glass is measured in advance in the micrometer, and the measured position is marked. Subsequently, a sample for measuring the transmittance of the transparent resin layer 5 is formed on the quartz glass by the above-described method, and then the thickness of the marking portion is measured again by micrometer. The film thickness of this transmittance measurement sample can be obtained by subtracting the thickness of the quartz glass measured first from the thickness thus obtained.

The difference in refractive index 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 is preferably 1.6 or less. Since the refractive index of the resin is 1.3 or more, the refractive index difference between the transparent resin layer 5 and the phosphor layer 2 becomes relatively small, so that the light extraction efficiency from the phosphor layer 2 to the transparent resin layer 5 can be improved have. In addition, since the refractive index of this resin is 1.6 or less, the refractive index difference between the transparent resin layer 5 and the air layer becomes relatively small, and thus the light extraction efficiency from the transparent resin layer 5 to the air layer can be improved. The refractive index of the resin contained in the transparent resin layer 5 is preferably not more than the refractive index of the resin contained in the phosphor layer 2 from the viewpoint of further improving the light extraction efficiency.

The refractive index of the resin contained in the transparent resin layer 5 can be measured by measuring the refractive index of the refractive index measurement sample using a refractive index / film thickness measuring apparatus "prism coupler MODEL 2010 / M" (Metric Corporation). The refractive index measurement sample was prepared by dispersing the resin by stirring and defoaming at 1000 rpm for 10 minutes using a planetary stirring type defoaming device "Mazerstar KK-400 ", and then dispersing the dispersion by 5 cc onto the PET film , And heating it at 150 占 폚 for 1 hour in an oven.

&Lt; Other layer >

The phosphor sheet 4 according to the embodiment of the present invention may have a phosphor layer or a diffusion layer separate from the phosphor layer 2 on at least one of the phosphor layer 2 and the phosphor layer 2. In this case, the transparent resin layer formed under the phosphor layer 2 or a separate phosphor layer (for example, between any phosphor layer and the surface of the LED chip) can be attached to the LED chip without using an adhesive, It is preferable to have heat-sealability. When the above-mentioned transparent resin layer is attached to the surface of an LED chip such as GaN or sapphire having a high refractive index, the smaller the difference between the refractive index of the surface of the LED chip and the refractive index difference of the transparent resin layer positioned below the phosphor layer, The light extraction efficiency for the transparent resin layer can be improved from the surface. 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 the emitted light can be weakened and more uniform light emitted can be obtained. Therefore, it is preferable that the diffusion layer is formed on the upper layer of the phosphor layer 2.

<Production method of phosphor sheet>

Next, a method of manufacturing the phosphor sheet 4 according to the embodiment of the present invention will be described in detail. The manufacturing method described below is an example, and the manufacturing method of the phosphor sheet 4 is not limited to this.

One method of manufacturing the phosphor sheet 4 is to directly coat the phosphor layer 2 on the support 3. [ In this method, first, a solution in which the phosphor 1 is dispersed in the resin 14 (hereinafter referred to as a &quot; resin solution for forming a phosphor layer &quot;) is prepared as a coating solution for forming the phosphor layer 2. The resin liquid for preparing the phosphor layer is obtained by mixing the phosphor (1) and the resin (14) in a solvent.

When it is necessary to add a solvent to adjust the viscosity, the kind of the solvent is not particularly limited as long as it can adjust the viscosity of the resin 14 in a flowing state. Examples of 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.

The components necessary for constituting the phosphor layer 2 and the components such as a solvent to be added as required are combined so as to have a predetermined composition, and then the combination of these components is mixed with a homogenizer, a self-ball type stirrer, , A planetary ball mill, a bead mill or the like to obtain a resin solution for producing a phosphor layer. It is also preferable to perform defoaming under the condition of vacuum or reduced pressure after this mixed dispersion or in the course of this mixed dispersion.

However, the Mn-activated birefringent complex fluorescent substance as the fluorescent substance 1 has a property of being low in hardness and tough as compared with a fluorescent substance produced by baking at a high temperature such as a? -Sialon selenium fluorescent substance. Therefore, when dispersing the Mn-recovered complex fluorophore complex fluorescent substance by a stirring / kneading machine or the like, the dispersion condition is set so that the impact applied to the Mn-activated birefringent complex fluorescent substance becomes as small as possible, . By suppressing the fracture of the Mn-activated birefringent complex fluorescent substance, it is possible to obtain the fluorescent substance sheet 4 having high light emission intensity.

Next, the resin solution for fabricating the phosphor layer prepared as described above is coated on the support 3 and dried. Thus, the phosphor layer (2) obtained on the support (3) is produced by heating and curing. The application of the resin solution for forming the phosphor layer onto the support 3 can be carried out by using a reverse roll coater, a blade coater, a slit die coater, a direct gravure coater, an offset gravure coater, a kiss coater, a screen printing, a natural roll coater, Roll coater, roll coater, roll coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater and the like. In order to obtain the uniformity of the film thickness of the phosphor layer 2, it is preferable to coat the phosphor layer 2 with a slit die coater. The phosphor layer 2 can also be formed by a printing method such as screen printing, gravure printing, or flat printing. In particular, screen printing is preferably used.

Drying of the resin solution for forming the phosphor layer can be performed using a general heating apparatus such as a hot-air drier or an infrared drier. For heating and curing the phosphor layer 2, a general heating apparatus such as a hot-air dryer or an infrared dryer is used. In this case, the heat curing conditions are usually 40 ° C to 250 ° C for 1 minute to 5 hours, preferably 100 ° C to 200 ° C for 2 minutes to 3 hours.

By the above-described method, the phosphor sheet 4 including at least the phosphor layer 2 can be manufactured. As shown in Fig. 1A, the phosphor sheet 4 is supported by the support 3 in 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. Of these, glass or a resin film is preferably used because of ease of production of the phosphor sheet 4 and ease of fragmentation of the phosphor sheet 4. Particularly, from the viewpoint of adhesion when the phosphor sheet 4 is attached to the LED chip, the support 3 is preferably a flexible film. Further, a film having high strength is preferable as the support 3, as there is no fear of breaking or the like when handling the support 3 in film form. In view of their required characteristics and economical efficiency, a resin film is preferable as the support 3. Of the resin films used as the support 3, plastic films selected from the group consisting of polyethylene terephthalate, polyphenylene sulfide, polypropylene and polyimide are preferable from the viewpoint of economy and handleability. Further, in the case of drying the resin solution for forming the phosphor layer or when a high temperature of 200 DEG C or more is required for attaching the phosphor sheet 4 to the LED chip, a polyimide film is preferable in terms of heat resistance. In order to facilitate the peeling of the phosphor sheet 4 from the support 3, the surface of the support 3 may be subjected to release treatment in advance.

When the transparent resin layer 5 is formed on the phosphor layer 2 in the method of manufacturing the phosphor sheet 4, the transparent resin layer 5 may be formed by a direct coating method, a transparent resin sheet method . The direct coating method is a method in which a resin solution (hereinafter referred to as &quot; resin solution for producing a transparent resin layer &quot;) viscosity-adjusted by a transparent resin solvent for the production of a transparent resin layer 5, , Followed by drying and heat curing treatment.

In the direct coating method, the resin solution for forming the transparent resin layer may be applied by the same method as the preparation of the phosphor layer 2 (application of the resin solution for forming the phosphor layer) In order to obtain thickness uniformity, it is preferable to apply a resin liquid for forming a transparent resin layer with a slit die coater. The resin liquid for forming the transparent resin layer can be dried by using a general heating apparatus such as a hot air drier or an infrared drier. For heating and curing the transparent resin layer 5 formed by the drying, a general heating apparatus such as a hot air drier or an infrared drier is used. In this case, the heat curing is usually carried out at 40 ° C to 250 ° C for 1 minute to 5 hours, preferably at 100 ° C to 200 ° C for 2 minutes to 3 hours.

The transparent resin sheet method is a method in which 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 prepared transparent resin sheet are bonded to each other, And a transparent resin layer 5 is formed on the transparent resin layer 5. The transparent resin sheet can be produced by the same method as the phosphor sheet 4 having the above-described phosphor layer 2. That is, the same method as the above-mentioned method for producing the phosphor sheet 4 is carried out using the "resin liquid for preparing a transparent resin layer" instead of the "resin liquid for phosphor layer preparation", and a predetermined support (for example, ), A transparent resin sheet 5 can be formed.

When the transparent resin layer 5 is formed on the phosphor layer 2 by the transparent resin sheet method, the resin of at least one of the phosphor layer 2 and the transparent resin layer 5 is in the semi-cured state There is a need. The phosphor layer 2 and the transparent resin layer 5 can be adhered to each other when the resin of at least one of the layers is in a semi-cured state. In this transparent resin sheet method, it is more preferable that at least the resin of the transparent resin layer 5 is semi-cured, and both of the resin of the resin 14 and the transparent resin layer 5 of the phosphor layer 2 are in a semi-cured state Is particularly preferable.

The bonding of the phosphor layer 2 and the transparent resin layer 5 is preferably performed by heating. The viscosity of each resin of the phosphor layer 2 and the transparent resin layer 5 is lowered by heating so that the phosphor layer 2 and the transparent resin layer 5 can be firmly bonded. In order to sufficiently lower the viscosity of each resin at the time of bonding, the heating conditions are preferably 40 ° C or higher, more preferably 60 ° C or higher, and particularly preferably 80 ° C or higher. If the temperature of each resin at the time of bonding is too high, the semi-cured resin (for example, the resin of the transparent resin layer 5) is cured before the fluorescent layer 2 and the transparent resin layer 5 are bonded It is difficult for the phosphor layer 2 and the transparent resin layer 5 to adhere to each other. From the viewpoint of suppressing thermal curing at the time of bonding, the heating conditions are preferably 200 ° C or lower, more preferably 170 ° C or lower, and particularly preferably 150 ° C or lower.

When bubbles are mixed at the time of bonding the phosphor layer 2 and the transparent resin layer 5, light is diffused from the interface between the bubbles and the phosphor layer 2 and the interface between the bubbles and the transparent resin layer 5, do. As a result, the light extraction efficiency from the phosphor sheet 4 is lowered, and as a result, the luminance of the light emitting body manufactured using the phosphor sheet 4 is lowered. It is preferable that the bonding of the phosphor layer 2 and the transparent resin layer 5 be performed in a vacuum atmosphere from the viewpoint of preventing the incorporation of such bubbles. In an atmosphere of vacuum, the pressure is not higher than a predetermined value. The pressure in this vacuum atmosphere is 100 hPa or less, more preferably 10 hPa or less, further preferably 5 hPa or less, particularly preferably 1 hPa or less.

(Method for manufacturing phosphor with phosphor sheet)

A method of manufacturing a phosphor according to an embodiment of the present invention (a method of manufacturing a phosphor using the phosphor sheet 4) will be described. 2 is a process diagram showing an example of a method of manufacturing a phosphor using a phosphor sheet according to an embodiment of the present invention. The following description is only an example, and the method of manufacturing the light emitting device according to the embodiment of the present invention is not limited to the following description.

The manufacturing method of the phosphor using the phosphor sheet 4 includes three processes in a largely divided manner. The first step is a step of separating the phosphor sheet 4 into individual pieces. The second step is a pick-up step of picking up the individualized phosphor sheet 4. The third step is an adhering step of adhering the picked-up phosphor sheet 4 (separated by the individualizing step) to the light source. In addition, the method for manufacturing the light-emitting body may include other steps as necessary.

Hereinafter, the phosphor sheet 4 includes the phosphor layer 2 formed on the support 3, and the phosphor layer 2 as the phosphor sheet 4 is discretized to form an LED chip A method of manufacturing a light emitting device according to an embodiment of the present invention will be described with reference to FIG.

(Discretization process)

In the disassembling step, the disassembling of the phosphor sheet 4 can be performed by a method such as punching using a metal mold, laser processing, dicing or cutting. At this time, the phosphor layer 2 as the phosphor sheet 4 may be semi-cured or cured in advance. Since the high energy is applied to the phosphor layer 2, it is possible to prevent the resin (e.g., the resin 14 shown in Fig. 1A) of the phosphor layer 2 from being rubbed off and the phosphor (for example, It is very difficult to avoid deterioration of the phosphor (1). Therefore, as a method of separating the phosphor sheet 4, cutting or cutting with a blade is preferable.

For example, as shown in Fig. 2, the phosphor layer 2 as the phosphor sheet 4 is supported by the support 3. In the disassembling step, the phosphor layer 2 on the support 3 is cut by the blade 6 (state S1). As a result, the phosphor layer 2 is divided into a plurality of segments and processed into the discrete phosphor layer 7 (state S2). At this time, the discrete fluorescent substance layer 7 remains attached to the support 3.

The blade 6 is, for example, a rotary blade. As a device for cutting the phosphor layer 2 by a rotary blade, an apparatus used for cutting (dicing) a semiconductor substrate called a dicer into individual chips can be suitably used. By using the dicer, the width of the divided line of the phosphor layer 2 can be precisely controlled by setting the thickness and condition of the rotary blade. Therefore, the cutting of the phosphor layer 2 by simply pressing the blade can be performed Precision is obtained. In the case of any of these cutting methods, the phosphor layer 2 may be individualized for each support 3. Alternatively, the phosphor layer 2 may be separated and the support 3 may not be cut. At this time, with respect to the support 3, it is preferable to perform a so-called half cut in which an infeed line which does not penetrate is inserted.

In the discretization process, it is preferable that the phosphor layer 2 is cut by dry cutting. A dry cut is a cutting method that does not use a liquid such as water at the time of cutting. The cutting of the phosphor layer 2 in the individualizing step is not limited to this, and for example, cutting by the Thomson blade can be mentioned. The dry cut is particularly effective when the phosphor layer 2 contains a phosphor such as K ₂ SiF ₆ : Mn, etc., whose luminous efficiency is lowered by reacting with water.

The phosphor sheet 4 may be subjected to punching processing before, after, or simultaneously with the discretization step. As the punching processing, known methods such as laser processing and punching using a metal mold can be suitably used. However, since laser processing causes the resin of the phosphor layer 2 to be crushed or deteriorated, the punching process Is more preferable.

(Pickup process)

The phosphor sheet 4 separated by the above-described fragmentation process is picked up by a pick-up process which is the next step of the fragmentation process. For example, as shown in Fig. 2, the discrete fluorescent substance layer 7 is attached on the support 3. Fig. In the pickup process, the discrete phosphor layer 7 is peeled from the support 3 and picked up (state S3) by a pick-up device (not shown) provided with a suction device such as a collet 8 or the like.

(Attaching step)

The discrete fluorescent substance layer 7 (an example of the discrete fluorescent substance sheet 4) picked up by the pick-up process described above is attached to the light source by an attaching step which is the next step of the pickup process. For example, as shown in Fig. 2, the individualized fluorescent substance layer 7 is picked up by the collet 8. The collet 8 is transported together with the individual fluorescent material layer 7 to the position of the LED chip 9 (an example of the light source) mounted on the substrate 11, (For example, the lower surface) of the discrete fluorescent material layer 7 are opposed to each other. Subsequently, the collet 8 presses the adhesion surface of the individualized fluorescent substance layer 7 on the light extraction surface of the LED chip 9 (S4). At this time, the reflector 10 may be formed around the LED chip 9 on the substrate 11.

It is preferable to use an adhesive (not shown) for attaching the discrete fluorescent substance layer 7 and the LED chip 9 in the attaching step. As the adhesive, known die bonding agents or adhesives can be used. For example, an adhesive of acrylic resin type, epoxy resin type, urethane resin type, silicone resin type, modified silicone resin type, phenol resin type, polyimide type, polyvinyl alcohol type, polymethacrylate resin type, melamine resin type and urea resin type can be used. When the phosphor layer 2 has adhesiveness, the individualized phosphor layer 7 and the LED chip 9 may be adhered using the stickiness.

In the case where the attaching step is a step of heating the discrete fluorescent substance layer 7 and attaching the discrete fluorescent substance layer 7 to the LED chip 9, . &Lt; / RTI &gt; When bubbles are mixed, light diffuses irregularly at the interface between the bubbles and the LED chip 9 and at the interface between the bubbles and the individual fluorescent material layer 7. As a result, the light extraction efficiency from the LED chip 9 is lowered, and as a result, the luminance of the light emitting body (for example, the light emitting body 13 shown in Fig. 2) produced using the phosphor sheet 4 is lowered Throw away. From the viewpoint of preventing the incorporation of such bubbles, it is preferable that the attachment step is performed in a vacuum atmosphere.

(Other processes)

The above-described manufacturing method of the light-emitting body may further include a connection step for electrically connecting the LED chip 9 and the substrate 11, which is an example of a circuit substrate, as another process. In 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 emitting body 13 can be obtained. When the LED chip 9 has an electrode on the light extraction surface side, the upper surface electrode of the LED chip 9 and the wiring of the substrate 11 are connected by wire bonding. When the LED chip 9 is a flip-chip type having an electrode pad on the opposite surface of the light emitting surface, the electrode surface of the LED chip 9 is made to face the wiring of the substrate 11, do. In this case, the connection between the substrate 11 and the LED chip 9 may be performed before attachment of the individualized phosphor sheet 4 (for example, the individual fluorescent material layer 7).

In the case where the modified phosphor layer 7 is adhered to the LED chip 9 in a semi-cured state, the individual-modified phosphor layer 7 can be cured at a suitable timing before or after the above-described connection step. For example, when joining thermocompression bonding to bond the flip chip type LED chip 9 to the substrate 11 in a lump, it is also possible to cure the discrete fluorescent material layer 7 simultaneously with the heating. When the package in which the LED chip 9 and the substrate 11 are connected to each other is surface-mounted on a larger circuit board, soldering may be performed in the solder reflow and the singulated phosphor layer 7 may be cured .

In the case where the discrete fluorescent substance layer 7 adheres to the LED chip 9 in a cured state, after the discrete fluorescent substance layer 7 and the LED chip 9 are attached, the curing of the discrete fluorescent substance layer 7 There is no need to install the course. The case where the discrete fluorescent substance layer 7 is adhered to the LED chip 9 in a cured state is a case where an adhesive layer is separately formed on the cured discrete fluorescent substance layer 7 or the discrete fluorescent substance layer 7 ) Has heat-sealability after curing, and the like.

Further, in the above-described manufacturing method of the light emitting body, as a further step, a sealing step for sealing the LED chip 9 after the attachment step is performed may be further included. 2, the transparent sealing material 12 is formed on the substrate 11 so as to cover the LED chip 9 after the individualized fluorescent substance layer 7 is adhered The inside of the reflector 10). Thus, the LED chip 9 is sealed by the transparent sealing material 12 (state S5). In this manner, the light emitting body 13 as shown in Fig. 2 is manufactured. As the transparent sealing material 12, a silicone resin is suitably used from the viewpoints of transparency and heat resistance.

2, the case where the phosphor sheet 4 includes the phosphor layer 2 on the support member 3 is exemplified. However, the method of manufacturing the phosphor member is not limited thereto It is not. That is, the phosphor sheet 4 used in the method for manufacturing the phosphor may include the phosphor layer 2, or may be a laminate of the phosphor layer 2 and the transparent resin layer 5, Or may include another layer such as the diffusion layer described above. For example, in the case where the phosphor sheet 4 includes the phosphor layer 2 and the transparent resin layer 5, the phosphor layer 2 and the transparent resin layer 5 on the support 3 ) Are all reorganized. In the pick-up step, the individualized laminate of the phosphor layer 2 and the transparent resin layer 5 is picked up from the support 3. In the attaching step, the picked-up laminate (individual piece) is attached to the light extraction surface of the LED chip 9.

<Light Emitting Device, Light Source Unit, Display>

The phosphor according to the embodiment of the present invention comprises the phosphor sheet 4 described above. For example, the light emitting body 13 shown in Fig. 2 is provided with a discrete fluorescent substance layer 7 as a phosphor sheet 4 on the light extraction surface of the LED chip 9. Such a light emitting body can be widely applied to a headlight mounted on a vehicle, a backlight of a television or a smart phone, illumination, and the like. In the present invention, the phosphor sheet 4 and the light emitting body using the phosphor sheet 4 are preferably applied to a light source unit such as a backlight, because the phosphor sheet 4 is excellent in improvement of color reproducibility and has high light flux and high durability.

The light source unit according to the embodiment of the present invention includes the phosphor sheet 4 described above. This light source unit also includes a light emitting body having a phosphor sheet 4. Such a light source unit can be applied to a display for a television, a smart phone, a tablet computer, or a game machine.

The display according to the embodiment of the present invention includes the light source unit having the above-described phosphor sheet 4. [ This display also includes a light source unit having a light emitting body (a light emitting body manufactured using the phosphor sheet 4) in the present invention. Examples of such a display include a liquid crystal display and the like.

<Color reproduction range measurement>

The color reproduction range of the liquid crystal display when the phosphor prepared using the phosphor sheet 4 is used as the backlight of the liquid crystal display can be evaluated by the DCI ratio. DCI is the area ratio in the chromaticity region when the area of the DCI chromaticity region concerning the DCI (Digital Cinema Initiative) standard is set as a reference (100%). The DCI ratio can be measured by the following procedure.

First, a color filter for transmitting red light produced by a known method was placed on a manufactured luminous body, power of 1 W was applied to the luminous body, the luminous body was turned on, and the whole luminous flux measurement system (HM-3000, The chromaticity of the emitted light is measured. Likewise, the chromaticity of emitted light is measured for each of a case where a color filter transmitting green light is placed on this light emitting body and a case where a color filter transmitting blue light is put on. The DCI ratio can be calculated by dividing the area of the obtained triangle having the three chromaticities as apexes by the area of the DCI chromaticity region.

Example

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited thereto.

<Silicone Resin>

The silicone resin T11 is OE-6351A / B (manufactured by Dow Corning Toray Co., Ltd.). The refractive index of the silicone resin T11 is 1.41. The silicone resin T12 is KER6075LV A / B (manufactured 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. The silicone resin T14 is OE6630 A / B (manufactured by Dow Corning Toray Co., Ltd.). The refractive index of the silicone resin T14 is 1.53.

Silicone resin T15 was obtained by mixing 75 parts by weight of the following component (E), 10 parts by weight of the component (F), 25 parts by weight of the component (G), 0.025 part by weight of the reaction inhibitor and 0.01 part by weight of the platinum catalyst . The transparent resin sheet produced using the silicone resin T15 had a storage elastic modulus at 25 占 폚 of 1 Mpa and a storage elastic modulus at 100 占 폚 of 0.01 MPa and exhibited good heat-sealability. The refractive index of the silicone resin T15 is 1.56.

In the silicone resin T15, 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 . (F) is ViMe ₂ SiO (MePhSiO) _17.5 SiMe ₂ Vi. (G) component is (HMe ₂ SiO) ₂ SiPh ₂ . Provided that Me is a methyl group, Vi is a vinyl group, and 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 a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex. The platinum content of this solution was 5 wt%.

The silicone resin T16 was obtained by the following production method. The refractive index of silicone resin T16 is 1.60.

In the production 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 Then, trifluoromethanesulfonic acid (6.15 g) was added thereto, and water (213.84 g) was added thereto while stirring, and the mixture was heated under reflux for 2 hours. Thereafter, heating and atmospheric pressure distillation was carried out until the temperature reached 85 ° C. Subsequently, toluene (435.6 g) and potassium hydroxide (3.28 g) were charged, and the mixture was distilled off under reduced pressure and heated at 120 캜 until reaction was carried out at this temperature for 6 hours. Thereafter, the reaction mixture was cooled to room temperature, and acetic acid (3.524 g) was added to neutralize. One was separated by filtration and then the resulting salt, by removing heat from the reduced pressure distillation of the low boiling point of water a clear solution is obtained, the average unit _{formula: (MePhViSiO 1/2) 0.40} (NaphSiO 3/2) organopolysiloxane resin represented by P1 _{0 .60} Was obtained.

Further, 1-naphtyltrimethoxysilane (50 g) was added to the reaction vessel, and after heating and melting, trifluoromethanesulfonic acid (0.06 g) was added. Subsequently, acetic acid (9.3 g) was added dropwise while heating to 45 캜 to 50 캜. After completion of dropwise addition, the mixture was heated and stirred at 50 占 폚 for 30 minutes. The low boiling point product was distilled off under reduced pressure until the reaction temperature became 80 ° C. Thereafter, the mixture was cooled to room temperature, 1,3,3-tetramethyldisiloxane (4.4 g) was added dropwise, and the mixture was heated until the reaction temperature reached 45 ° C. Subsequently, acetic acid (18 g) was added dropwise at 45 캜 to 50 캜. After completion of dropwise addition, the mixture was heated and stirred at 50 占 폚 for 30 minutes. Acetic anhydride (15.5 g) was added dropwise by air cooling or water cooling while keeping the temperature at 60 캜 or lower, and the mixture was heated and stirred at 50 캜 for 30 minutes. Then, toluene and water were added, and the mixture was stirred, left standing, and lower layer were repeatedly washed with water. After confirming that the pH of the lower layer 7, to remove heat from the upper layer was evaporated under reduced pressure to a low-boiling water in the toluene layer, and the average unit _{formula: (HMe 2 SiO 1/2} ) 0.60 (NaphSiO 3/2) represented by _{0, 0.40,} 43 g of colorless transparent liquid organopolysiloxane P2 was obtained.

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- , A solution of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane of 1,3,3-tetramethyldisiloxane complex (a solution containing 0.1% by mass of platinum) 0.25 parts by mass were mixed to prepare a curable silicone composition.

The silicone resin T17 was obtained by the following production method. The refractive index of the silicone resin T17 is 1.65.

In the process for producing the silicone resin T17, methyltrimethoxysilane (16.6 g), phenyltrimethoxysilane (56.2 g), "Optraque TR-527" (trade name, manufactured by Shokubai Kasei Kogyo Co., (19.9 g) and propylene glycol monomethyl ether acetate (126.9 g) were charged in a reaction vessel and to the solution were added water (21.9 g) and phosphoric acid (0.36 g) While stirring, the reaction temperature was dropped so as not to exceed 40 캜. After the dropwise addition, a distillation apparatus was provided in the flask, and the obtained solution was heated and stirred at a bath temperature of 105 DEG C for 2.5 hours to carry out a reaction while distilling off methanol produced by hydrolysis. Thereafter, this solution was further heated and stirred at a bath temperature of 115 캜 for 2 hours, and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

Next, silicone resin T14 (8.00 g) was mixed with the resulting titanium oxide particles (50.00 g) and stirred at 1000 rpm for 20 minutes using a planetary stirring and defoaming device "Mazerstar KK-400" . By defoaming, a silicone resin T17 was produced. As a result of measuring the refractive index, the average refractive index of the silicone resin T17 was 1.65.

The silicone resin T18 was obtained by the following production method. The refractive index of the silicone resin T18 is 1.70.

In the production method of the silicone resin T18, silicone resin T14 (3.0 g) was mixed with 60.0 g of the titanium oxide grains grafted with polysiloxane in the same manner as in the above-mentioned production of the silicone resin T17, Star KK-400 "(Kurabo Industries, Ltd.) for 20 minutes at 1000 rpm. Thus, a silicone resin T18 was produced. As a result of measuring the refractive index, the refractive index of the silicone resin T18 was 1.70.

<Fluorine Resin>

The fluororesin T21 is AF2400S (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.). The refractive index of the fluororesin T21 is 1.30. The fluororesin T22 is CTX-800 (CT-solv 180 solution) (manufactured by Asahi Glass). The refractive index of the fluororesin T22 is 1.35.

<Phosphor>

The green phosphor is a β-type sialon phosphor called GR-MW540K (manufactured by Denka Kogyo Co., Ltd.). The yellow phosphor is a Ce-doped YAG phosphor called NYAG-02 (manufactured by Intematix). The red phosphor T1 is a KSF phosphor sample A (manufactured by NEMOTO RUMI MATERIALS CO., LTD.). And the red phosphor T2 is a KSF phosphor sample B (manufactured by Nippon Kayaku Co., Ltd., Rumi Material Co., Ltd.). The red phosphor T3 is a KSF phosphor sample C (manufactured by Nemoto, Rumi Material Co., Ltd.). The red phosphor T4 is a KSF phosphor sample D (manufactured by Nemoto, Rumi Material Co., Ltd.). The red phosphor T5 is a KSF phosphor sample E (manufactured by Nemoto, Rumi Material Co., Ltd.). The red phosphor T6 is a KSF phosphor sample F (manufactured by Nemoto, Rumi Material Co., Ltd.).

D10, D50 and D90 of the red phosphors T1 to T6 used in this example were measured by the following methods. The measurement results are shown in Table 1. Table 1 also shows the value x calculated on the basis of the above-described formula (11) based on the measured D10, D50 and D90.

In the method of measuring D10, D50 and D90 of the red phosphors T1 to T6, a phosphor sheet (for example, a phosphor sheet 4 shown in Figs. 1A and 1B) is prepared as described below and the cross section of the phosphor layer is measured by SEM From the obtained two-dimensional image, the maximum distance among the two intersections of the straight line intersecting with the outer edge of the particle at two points was calculated and defined as individual particle diameters of the particles. The particle size of 10% of the passing particle size distribution from the small particle size side was D10, the particle size of the passing particle size distribution 50% was D50, and the particle size of the passing particle size distribution 90% To D90.

<Base film>

The base film is an example of a support (for example, the support 3 shown in Figs. 1A and 1B) of the phosphor sheet in the present invention. In the present embodiment, the base film was a PET film. This PET film is "Cerafil" BX9 (manufactured by Toray Film Processing Co., Ltd.), and its film thickness is 50 μm.

&Lt; Silicon fine particles &

The silicon fine particles were obtained by the following production methods.

In the method for producing silicon fine particles, a stirrer, a thermometer, a reflux tube, and a dropping funnel were placed in a 2 L four-necked round bottom flask, and 2.5% ammonia water containing 10000 ppm of polyether modified siloxane "BYK333" as a surfactant 2L) was added, and the mixture was heated with an oil bath while stirring at 300 rpm. When the internal temperature reached 50 캜, a mixture (22/78 mol%) of methyltrimethoxysilane and phenyltrimethoxysilane (200 g) was added dropwise from the dropping funnel over 30 minutes. Stirring was further continued at the same temperature for 60 minutes, acetic acid (reagent grade) (about 5 g) was added, stirred and mixed, and filtration was carried out. Water (600 mL) was added to the resulting particles on the filter twice, and methanol (200 mL) was added once, followed by filtration and washing. The cake on the filter was taken out and freeze-dried for 10 hours after being crushed to obtain a white powder (40 g) as silicon fine particles.

As a result of observation by SEM, it was confirmed that the obtained silicon fine particles were monodispersed spherical fine particles. From the obtained SEM image, the average particle diameter of the silicon fine particles was calculated and found to be 50 nm. The refractive index of the silicon fine particles was measured by an immersion method and found to be 1.54. As a result of observing the silicon microparticles in cross section TEM, it was confirmed that the particles were fine particles having a single structure.

&Lt; Silica fine particles &

The fine silica particles T31 are Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.). The average particle diameter of the fine silica particles T31 is 12 nm. The refractive index of the fine silica particles T31 is 1.46. The silica fine particle T32 is "Adamanano" YA050C (manufactured by Admatechs Co., Ltd.). The average particle diameter of the fine silica particles T32 is 50 nm. The refractive index of the silica fine particle T32 is 1.46. The fine silica particles T33 are "Adamanano" 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 particle T33 is 1.46. The fine silica particles T34 are "Admafine" SO-E1 (manufactured by Admatechs Co., Ltd.). The average particle diameter of the fine silica particles T34 is 250 nm. The refractive index of the fine silica particles T34 is 1.46. The silica fine particle T35 is HPS-1000 (manufactured by Dojo Kasei Corporation). The average particle diameter of the fine silica particles T35 is 1000 nm. The refractive index of the silica fine particle T35 is 1.46. The fine silica particles T36 are "ADMAPINE" 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 particle T36 is 1.46.

<Alumina fine particles>

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.

<Titania fine particles>

The titania fine particle is MT-01 (manufactured by Teika K.K.). The average particle diameter of the titania fine particles is 10 nm. The refractive index of the titania fine particles is 2.50.

<Fabrication of phosphor sheet>

In the production of the phosphor sheet in the present embodiment, a silicone resin, a silicon fine particle, a red phosphor and a green phosphor were mixed at a predetermined ratio in a polyethylene container having a volume of 300 mL. Further, toluene was added as a solvent in an amount of 8 wt% and stirred and defoamed at 1000 rpm using a planetary stirring and defoaming device "Mazerstar KK-400" (Kurabo) to obtain a resin solution for producing a phosphor layer. Thereafter, a resin solution for forming a phosphor layer was coated on a PET film using a slit die coater and dried at 130 DEG C for 30 minutes to obtain a phosphor layer, and a phosphor sheet was obtained.

<Measurement of Film Thickness of Phosphor Layer>

In the film thickness measurement of the phosphor layer in the present embodiment, the predetermined position thickness of the PET film for fabricating the phosphor layer was measured in advance in micrometers and marked. Subsequently, a phosphor layer was formed on the PET film, and then the thickness of the marking portion was measured again by micrometer. The film thickness of the phosphor layer was obtained by subtracting the thickness of the PET film measured first from the obtained thickness. In the present embodiment, the film thickness was measured at 25 points on a checkerboard eye at intervals of 10 mm, and the average value thereof was defined as the film thickness of the phosphor layer.

<Formation of Transparent Resin Layer by Direct Coating Method>

In the formation of the transparent resin layer by the direct coating method in the present embodiment, a silicone resin, a fluororesin, and fine particles were mixed at a predetermined ratio in a polyethylene container having a volume of 300 mL. Further, 5 wt% of toluene was added as a solvent, and then stirred and defoamed at 1000 rpm for 20 minutes using a planetary stirring and defoaming device "Mazerusta KK-400" (Kurabo) Solution. Subsequently, a resin solution for forming a transparent resin layer was coated on the phosphor layer using a slit die coater and dried at 130 캜 for 30 minutes to form a transparent resin layer on the phosphor layer. As a result, a phosphor sheet having a transparent resin layer on the phosphor layer was obtained. Hereinafter, the &quot; phosphor sheet having a transparent resin layer on the phosphor layer &quot; is appropriately referred to as &quot; phosphor sheet with transparent resin layer &quot;.

&Lt; Formation of transparent resin layer by transparent resin sheet method >

In the formation of the transparent resin layer by the transparent resin sheet method in the present embodiment, a resin solution for forming a transparent resin layer was applied on a PET film using a slit die coater and dried at 130 DEG C for 30 minutes, A sheet was obtained. Subsequently, the phosphor layer of the phosphor sheet and the transparent resin layer of the transparent resin sheet were heated and pressed at 100 캜 for 30 seconds in a vacuum atmosphere of 1 hPa by using a vacuum laminator V130 manufactured by Nikko-Materials, Ltd. . Thereafter, the PET film on the transparent resin sheet side was peeled off, thereby forming a transparent resin layer on the phosphor layer. As a result, a phosphor sheet with a transparent resin layer was obtained.

<Measurement of Film Thickness of Transparent Resin Layer>

In the film thickness measurement of the transparent resin layer in the present embodiment, the predetermined position thickness of the phosphor sheet for producing the transparent resin layer was measured in advance by micrometer and marked. Subsequently, a transparent resin layer was formed on the phosphor sheet, and then the thickness of the marking portion was measured again with a micrometer. The film thickness of the transparent resin layer was obtained by subtracting the thickness measured first from the obtained thickness. In the present embodiment, the film thickness was measured at 25 points on a checkerboard at intervals of 10 mm. From this measurement result, the average value and film thickness variation (= maximum film thickness - minimum film thickness) of each sample were calculated.

&Lt; Measurement of porosity &

In the porosity measurement in the present embodiment, 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 with respect to one phosphor sheet and the sum of the cross sectional areas corresponding to the voids of the 20 two-dimensional images obtained was calculated. The porosity of this phosphor layer was obtained by dividing the total cross-sectional area corresponding to this gap by the cross-sectional sum of these 20 two-dimensional images.

&Lt; Method of producing luminous body &

In the method of manufacturing the light emitting body in this embodiment, the phosphor sheet prepared as described above or the phosphor sheet (1 cm square) having the transparent resin layer is cut with a cutting device (GCUT manufactured by UHT) 100 pieces of 1 mm-square pieces of the prepared sheets were produced. In the present embodiment, the textured sheet is a piece of a phosphor sheet or a phosphor sheet having a transparent resin layer. Subsequently, using a die bonding apparatus (manufactured by TORAY ENGINEERING CO., LTD.), A 1 mm square piece of a release sheet (phosphor layer or the like) was vacuum-adsorbed by a collet to peel off from the base film. The phosphor layers of the redistributed sheets were aligned and attached to the surface of the blue LED chip of the LED package having the flip chip type blue LED chip mounted thereon and the reflector formed around the blue LED chip. At this time, an adhesive was applied on the blue LED chip in advance, and the phosphor layer was attached via the adhesive. Silicone resin T15 was used for this adhesive. Thus, a phosphor sheet or a phosphor sheet with a transparent resin layer was produced.

<Chromaticity, Total luminous flux measurement>

In the measurement of the chromaticity and the total flux of light in the present embodiment, electric power of 1 W was applied to the luminous body prepared as described above, and the LED chip of the luminous body was turned on to measure the total luminous flux measurement system (HM- 3000, (Cx, Cy) and the total luminous flux (lm) of the CIE 1931 XYZ color coordinate system were measured using a spectrophotometer. In this embodiment, ten light emitting bodies (including LED chips) are fabricated for each phosphor sheet, and the average of chromaticity values of these ten light emitting bodies and the standard deviation (?) Of the chromaticity Cx, which is an index of chromaticity fluctuation, Respectively.

&Lt; Measurement of total lumen maintenance ratio &

In the measurement of the total luminous flux retention ratio in the present embodiment, power of 1 W is supplied to a light emitting body on which each phosphor sheet is mounted on the blue LED chip, and the blue LED chip is lit, and the light emitting body ) Was left under the conditions of a temperature of 85 DEG C and a humidity of 85%, and the total luminous flux after 300 hours passed was measured. The durability of the phosphor and the phosphor sheet was evaluated by calculating the total luminous flux retention ratio based on the following formula. The higher the total luminous flux maintenance ratio, the better the durability.

Total luminous flux maintenance rate (%) = (total luminous flux after 300 hours / total luminous flux immediately after start of test) × 100

<Color reproduction range measurement>

In the measurement of the color reproduction range in the present embodiment, a color filter transmitting red light produced by a known method on a luminous body prepared as described above was placed, and the chromaticity of the emitted light was measured. Likewise, the chromaticity of the emitted light was measured for each of a case where a color filter transmitting green light was placed on this light emitting body and a case where a color filter transmitting blue light was placed. The DCI ratio was calculated by dividing the area of the triangle having the obtained three chromaticities as apexes by the area of the DCI chromaticity region. The higher the DCI ratio, the better the color reproducibility.

&Lt; Measurement of refractive index &

In the measurement of the refractive index in the present embodiment, the refractive index of the refractive index measurement sample was measured using a refractive index / film thickness measuring apparatus "prism coupler MODEL2010 / M" (manufactured by Metricon) The refractive index of the cured product was measured.

&Lt; Preparation of refractive index measurement sample &

In the production 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 defoaming device "Mazerstar KK-400" (manufactured by Gurabo) , And a dispersion of this resin was prepared. 5 cc of this dispersion was dropped onto the PET film, and then heated in an oven at 150 占 폚 for 1 hour, thereby obtaining an average refractive index measurement sample as a refractive index measurement sample.

<Measurement of transmittance>

In the transmittance measurement in the present embodiment, the light transmittance of the transparent resin layer containing fine particles was measured using a spectrophotometer (U-4100 Spectrophotomater (Hitachi Sekisui Co., Ltd.) And measuring the light transmittance of the measurement sample. The transmittance measurement samples used in the examples were used. Regarding the measurement conditions of the light transmittance, the slit was 2 nm and the scanning speed was 600 nm / min. Further, in the obtained measurement results, the smallest value among the light transmittances at wavelengths of 400 nm to 800 nm was set to the minimum transmittance.

&Lt; Preparation of transmittance measurement sample >

In the production of the transmittance measurement sample in the present embodiment, the silicone resin and the fine particles used for the transparent resin layer were mixed in a polyethylene container having a volume of 300 mL, and a planetary stirring defoaming apparatus "Mazerstar KK-400" ) At 1000 rpm for 10 minutes and defoamed to prepare a dispersion. This dispersion is coated on quartz glass by a blade coater and then heated in an oven at 150 DEG C for 1 hour. Thus, the transmittance measurement sample was prepared for each example.

<Measurement of Film Thickness of Transmittance Measurement Sample>

In the measurement of the film thickness of the transmittance measuring sample in the present embodiment, the predetermined position thickness of the quartz glass was measured in micrometers in advance, and the measured position was marked. Subsequently, a sample for measuring the transmittance of the transparent resin layer was formed on the quartz glass, and then the thickness of the marking portion was measured again by micrometer. The film thickness of this transmittance measurement sample was obtained by subtracting the thickness of the quartz glass which was measured from the obtained thickness first. The film thickness was measured at 25 points on a checkerboard at intervals of 10 mm, and the average value thereof was defined as the film thickness of the transmittance measurement sample.

(Examples 1 to 6) - Influence by particle size of phosphor -

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 above-described method. Further, a phosphor (light-emitting device) was produced using the phosphor sheet obtained in each of Examples 1 to 6, and the chromaticity, total luminous flux, total luminous flux maintenance ratio and color reproduction range were measured by the above-described method. The results of these measurements are shown in Table 3. As can be seen from Tables 2 and 3, when the phosphor sheet according to the present invention was used, in all of Examples 1 to 6, a luminous body with high color reproducibility and high brightness was obtained. Further, as in the D50 of the red phosphors T2 to T6 shown in Table 1, if the D50 of the red phosphor is 10 m or more, the total luminous flux is further improved, and as in D10 of the red phosphors T3 to T6 shown in Table 1, It was found that when the D10 was 5 占 퐉 or more, the total luminous flux retention ratio was further improved. In addition, as D10 and D50 of the red phosphors T1 to T6 shown in Table 1, the larger the D10 and D50 of the red phosphor, the smaller the porosity of the phosphor sheet was.

(Examples 7 to 13) Influence of phosphor concentration -

In Examples 7 to 13, a phosphor sheet having a phosphor layer of the composition shown in Table 4 was prepared, and the porosity was measured by the above-mentioned method. In addition, a phosphor was produced using the phosphor sheet obtained in each of Examples 7 to 13, and the chromaticity, total luminous flux, total luminous flux maintenance ratio, and color reproduction range were measured by the above-described method. The results of these measurements are shown in Table 5. Table 4 shows the composition of Example 6, and Table 5 shows the results of Example 6. From Tables 4 and 5, it can be seen that the higher the concentration of the phosphor such as the red phosphor T6 and the green phosphor is, the more the total luminous flux retention rate is improved.

(Examples 14 to 17) - Effect of silicon fine particles -

In Examples 14 to 17, a phosphor sheet having a phosphor layer having the composition shown in Table 6 was prepared, and the porosity was measured by the above-described method. Further, a phosphor was produced using the phosphor sheets obtained in Examples 14 to 17, and the chromaticity, total luminous flux, total luminous flux maintenance ratio, and color reproduction range were measured by the above-described method. The results of these measurements are shown in Table 7. From Tables 6 and 7, it was found that the chromaticity variation (? (Cx)) was further improved by containing silicon fine particles.

(Example 18) - A two-layer product of a red phosphor layer and a green phosphor layer -

In Example 18, a phosphor sheet was produced with a composition of 50 wt% of silicone resin T15 and 50 wt% of red phosphor T6. Similarly, a phosphor sheet was prepared with a composition of 50 wt% silicone resin T15 and 50 wt% green phosphor. The phosphor layer side of the obtained two phosphor sheets was bonded by using a vacuum laminator V130 (manufactured by Nikko Material Products Co., Ltd.), whereby a layer including a red phosphor and a layer containing a green phosphor A laminated phosphor sheet was prepared, and the porosity was measured by the above-mentioned method. Further, a phosphor was produced by using the obtained phosphor sheet, and chromaticity, total luminous flux, total luminous flux maintenance ratio and color reproduction range were measured by the above-mentioned method. The results of these measurements are shown in Table 8. From Table 8, it can be seen that although the color reproducibility can be improved and the high luminous flux can be compatible in Example 18, the chromaticity fluctuation becomes large.

(Examples 19 to 25) Influence of Refractive Index of Phosphor Layer Resin -

In Examples 19 to 25, a phosphor sheet having a phosphor layer of the composition shown in Table 9 was produced. The film thickness of the phosphor layer of the phosphor sheet produced in each of Examples 19 to 25 was measured by the above-mentioned method. The film thickness of the phosphor layer was also measured for the phosphor sheet of Example 10. In addition, a phosphor was produced by using the phosphor sheets prepared in each of Examples 19 to 25, and chromaticity, total luminous flux and color reproduction range were measured by the above-mentioned method. The results of these measurements are shown in Table 10. Table 9 shows the composition of Example 10, and Table 10 shows the results of measurement of Example 10.

As can be seen from Tables 9 and 10, a phosphor having the same chromaticity was obtained as the refractive index of the resin of the phosphor layer was higher and the filling rate of the red phosphor T6 and the green phosphor was lower. Further, when the refractive index of this resin was 1.56, the total luminous flux became a maximum value. It is considered that this is because the difference in refractive index between the resin of the phosphor layer and the air layer is increased and the light extraction efficiency is lowered.

(Examples 26 to 36) - Influence of refractive index of transparent resin layer -

In Examples 26 to 32 and Examples 34 to 36, a resin solution for forming a transparent resin layer was applied on the phosphor sheet prepared in Example 6 using a slit die coater, and the resin solution for making the transparent resin layer was applied And dried at 130 DEG C for 30 minutes to prepare a phosphor sheet having a transparent resin layer on the phosphor layer. In Example 33, a transparent resin sheet was produced by the above-described method using the silicone resin T15, and the phosphor layer and the transparent resin layer were bonded to each other to produce a phosphor sheet having a transparent resin layer on the phosphor layer. The film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 26 to 36 was measured by the above-described method. Further, by attaching the phosphor layer side of the phosphor sheet with transparent resin layer prepared in each of Examples 26 to 36 to the LED chip, a light emitting body was manufactured, and the chromaticity, total light flux, total light flux retention, The reproducibility range was measured. The types of resins used in the production of the resin solution for making the transparent resin layer in each of Examples 26 to 36 and the measurement results in Examples 26 to 36 are shown in Table 11. [

From Table 11, it was found that the total luminous flux retention ratio was improved by forming the transparent resin layer. It was also found that when the refractive index of the resin contained in the transparent resin layer is lower than or equal to the refractive index of the resin contained in the phosphor layer, the total light flux is improved.

(Examples 37 to 42) - Refractive index of fine particles -

In Examples 37 to 42, a resin solution for producing a transparent resin layer having the composition shown in Table 12 was prepared. Next, the resin liquid for preparing a transparent resin layer prepared in each of Examples 37 to 42 was applied onto the phosphor sheet prepared in Example 10, and the resin liquid for preparing the transparent resin layer was dried at 130 DEG C for 30 minutes Thereby preparing a phosphor sheet having a transparent resin layer on the phosphor layer.

The film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 37 to 42 was measured by the above-mentioned method. Next, by attaching the phosphor layer side of the phosphor sheet with a transparent resin layer prepared in each of Examples 37 to 42 to the LED chip, a light emitting body was manufactured, and the chromaticity, total light flux, total light flux retention, The color reproduction range was measured. Further, transmittance measurement samples each having a thickness of 100 占 퐉 were prepared using the resin liquid for transparent resin layer fabrication prepared in each of Examples 37 to 42, and the light transmittance of the transparent resin layer was measured by the above-described method. 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 are shown in Table 13.

As can be seen from Tables 12 and 13, the smaller the difference between the refractive index of the resin and the refractive index of the fine particles in the transparent resin layer, the higher the minimum transmittance of the transparent resin layer and the higher the total light flux. It was also found that the addition of the fine particles to the transparent resin layer suppressed the film thickness variation of the transparent resin layer. Further, from the results of Examples 37 and 38, it was found that when the silicone resin T15 exhibiting good heat-sealability was used, the film thickness variation of the transparent resin layer was particularly large.

(Examples 43 to 47) - Addition amount of fine silica particles -

In Examples 43 to 47, a resin solution for producing a transparent resin layer having the composition shown in Table 14 was prepared. Next, the resin liquid for forming the transparent resin layer prepared in each of Examples 43 to 47 was applied onto the phosphor sheet prepared in Example 10, and the resin liquid for forming the transparent resin layer was dried at 130 DEG C for 30 minutes Thereby preparing a phosphor sheet having a transparent resin layer on the phosphor layer.

The film thickness of the transparent resin layer of the phosphor sheet prepared in each of Examples 43 to 47 was measured by the above-mentioned method. Next, by attaching the phosphor layer side of the phosphor sheet with a transparent resin layer prepared in each of Examples 43 to 47 on the LED chip, a phosphor was manufactured, and the chromaticity, total luminous flux, total luminous flux retention, The color reproduction range was measured. Further, transmittance measurement samples each having a thickness of 100 占 퐉 were prepared using the resin liquid for transparent resin layer fabrication prepared in each of Examples 43 to 47, and the light transmittance of the transparent resin layer was measured by the above-described method. The refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 43 to 47 and the measurement results thereof are shown in Table 15. Table 14 shows the compositions of Examples 38 and 39, and Table 15 shows the results of Examples 38 and 39.

With reference to Tables 14 and 15, it was found that the content of the silica fine particles T31 is preferably 30% by weight or less, more preferably 10% by weight or less, from the viewpoint of the minimum transmittance. From the viewpoint of suppressing the film thickness variation of the transparent resin layer, the content of the fine silica particles T31 is preferably 0.1 wt% or more, more preferably 1 wt% or more.

(Examples 48 to 52) - Addition amount of alumina fine particles -

In Examples 48 to 52, a resin solution for producing a transparent resin layer having the composition shown in Table 16 was prepared. Next, on the phosphor sheet prepared in Example 10, the resin liquid for forming the transparent resin layer prepared in each of Examples 48 to 52 was applied, and the resin liquid for forming the transparent resin layer was dried at 130 DEG C for 30 minutes Thereby preparing a phosphor sheet having a transparent resin layer on the phosphor layer.

The film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 48 to 52 was measured by the above-mentioned method. Next, by attaching the phosphor layer side of the phosphor sheet with transparent resin layer prepared in each of Examples 48 to 52 to the LED chip, a phosphor was manufactured, and the chromaticity, total luminous flux, total luminous flux retention, The color reproduction range was measured. Further, transmittance measurement samples each having a thickness of 100 占 퐉 were prepared using the resin liquid for transparent resin layer fabrication prepared in each of Examples 48 to 52, and the light transmittance of the transparent resin layer was measured by the above-described method. The refractive index difference between the resin and the fine particles of the transparent resin layer in each of Examples 48 to 52 and the measurement results thereof are shown in Table 17. Table 16 shows the compositions of Examples 38 and 41, and Table 17 shows the results of Examples 38 and 41.

With reference to Tables 16 and 17, it was found that the content of the alumina fine particles is preferably 30% by weight or less, more preferably 10% by weight or less, from the viewpoint of the minimum transmittance. From the viewpoint of suppressing the film thickness variation of the transparent resin layer, the content of the alumina fine particles is preferably 0.1 wt% or more, more preferably 1 wt% or more.

(Examples 53 to 57) - Addition amount of silicon fine particles -

In Examples 53 to 57, a resin solution for producing a transparent resin layer having the composition shown in Table 18 was prepared. Next, the resin liquid for forming the transparent resin layer prepared in each of Examples 53 to 57 was applied onto the phosphor sheet prepared in Example 10, and the resin liquid for preparing the transparent resin layer was dried at 130 DEG C for 30 minutes Thereby preparing a phosphor sheet having a transparent resin layer on the phosphor layer.

The film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 53 to 57 was measured by the above-described method. Next, by attaching the phosphor layer side of the phosphor sheet with a transparent resin layer prepared in each of Examples 53 to 57 to the LED chip, a phosphor was produced, and the chromaticity, total luminous flux, total luminous flux retention, The color reproduction range was measured. The transmittance of the transparent resin layer was measured by the above-mentioned method by using the resin liquid for transparent resin layer production prepared in each of Examples 53 to 57 and measuring the transmittance of 100 탆 in thickness. 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 are shown in Table 19. Table 18 shows the compositions of Examples 38 and 40, and Table 19 shows the results of Examples 38 and 40.

It can be seen from Tables 18 and 19 that even if the content of silicon fine particles is 50% by weight, the minimum transmittance can be maintained at 80% or more. From the viewpoint of suppressing the film thickness variation of the transparent resin layer, the content of the silicon fine particles is preferably 0.1 wt% or more, more preferably 1 wt% or more.

(Examples 58 to 62) - Particle size of fine particles -

In Examples 58 to 62, a resin solution for producing a transparent resin layer having the composition shown in Table 20 was prepared. Next, on the phosphor sheet produced in Example 10, the resin liquid for making the transparent resin layer prepared in each of Examples 58 to 62 was applied, and the resin liquid for making the transparent resin layer was dried at 130 DEG C for 30 minutes Thereby preparing a phosphor sheet having a transparent resin layer on the phosphor layer.

The film thickness of the transparent resin layer of the phosphor sheet produced in each of Examples 58 to 62 was measured by the above-described method. Next, by attaching the phosphor layer side of the phosphor sheet with a transparent resin layer prepared in each of Examples 58 to 62 to the LED chip, a light emitting body was manufactured, and the chromaticity, total light flux, total light flux retention, The color reproduction range was measured. Further, transmittance measurement samples each having a thickness of 100 占 퐉 were prepared by using the resin liquid for transparent resin layer fabrication prepared in each of Examples 58 to 62, and the light transmittance of the transparent resin layer was measured by the above-described method. 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 are shown in Table 21. Table 20 shows the compositions of Examples 38 and 39, and Table 21 shows the results of Examples 38 and 39. It can be seen from Tables 20 and 21 that the smaller the particle size of the fine particles is, the higher the minimum transmittance is, and the film thickness variation of the transparent resin layer is also suppressed.

(Comparative Example)

In the comparative examples of Examples 1 to 62, a phosphor sheet was prepared with a composition in which the silicone resin T15 was 40 wt% and the yellow fluorescent material (YAG yellow fluorescent material) was 60 wt%, and the porosity was measured by the above-mentioned method. Further, a phosphor was produced using the obtained phosphor sheet, and chromaticity, total luminous flux, total luminous flux maintenance ratio and color reproduction range were measured by the above-described method. The results of these measurements are shown in Table 22. From Table 22, it was found that when the YAG yellow phosphor was used, the color reproduction range was 70%, which was unsuitable as a backlight for a liquid crystal display.

INDUSTRIAL APPLICABILITY As described above, the phosphor sheet according to the present invention, the light emitting unit, the light source unit, the display, and the method for manufacturing the light emitting body are improved in color reproducibility and the phosphor sheet capable of achieving high light fluxes, It is suitable for the manufacturing method.

1: Phosphor
2: phosphor layer
3: Support
4: phosphor sheet
5: Transparent resin layer
6: blade
7: Scattered phosphor layer
8: Collet
9: LED chip
10: Reflector
11: substrate
12: Transparent seal material
13:
14: Resin

Claims (24)

A phosphor layer comprising a red phosphor, a? -Type sialon phosphor and a resin,
The red phosphor is a Mn-activated fluorophosphate represented by the general formula (1)
And the phosphor sheet.
(General formula)
A ₂ MF ₆ : Mn (1)
Wherein A is at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs and further comprising at least one of Na and K, M is at least one element selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn. 2. The phosphor according to claim 1, wherein the phosphor layer comprises a single layer or a plurality of layers including the red phosphor, the? -Sialon phosphor and the resin,
The red phosphor, the? -Sialon phosphor and the resin are contained in the same layer
And the phosphor sheet. The phosphor sheet according to claim 1 or 2, wherein the refractive index of the resin is 1.45 or more and 1.7 or less. The phosphor sheet according to any one of claims 1 to 3, wherein the resin is a silicone resin. The phosphor sheet according to any one of claims 1 to 4, wherein 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. The phosphor according to any one of claims 1 to 5, wherein the total of the ratio of the red phosphor and the? -Sialon phosphor in the total solid content of the phosphor layer is 50 wt% or more and 90 wt% or less Features a phosphor sheet. The phosphor sheet according to any one of claims 1 to 6, wherein the red phosphor has a D50 of 10 mu m or more and 40 mu m or less. The phosphor sheet according to any one of claims 1 to 7, wherein D10 of the red phosphor is 3 m or more. 9. The phosphor sheet according to any one of claims 1 to 8, wherein (D90-D10) / D50 of the red phosphor is 0.5 or more and 1.5 or less. 10. The phosphor sheet according to any one of claims 1 to 9, wherein the porosity of the phosphor layer is 0.1% or more and 3% or less. 11. The phosphor sheet according to any one of claims 1 to 10, wherein the phosphor layer contains fine particles. The phosphor sheet according to claim 11, wherein the fine particles are silicon fine particles. The phosphor sheet according to any one of claims 1 to 12, further comprising a transparent resin layer laminated on the phosphor layer. 14. The phosphor sheet according to claim 13, wherein the refractive index of the resin contained in the transparent resin layer is from 1.3 to 1.6. 15. The phosphor sheet according to claim 14, wherein the refractive index of the resin contained in the transparent resin layer is lower than or equal to the refractive index of the resin contained in the phosphor layer. 16. The phosphor sheet according to any one of claims 13 to 15, wherein the transparent resin layer contains fine particles. The phosphor sheet according to claim 16, wherein the fine particles contained in the transparent resin layer are at least one selected from fine silica particles, fine alumina particles, and fine silicon particles. The phosphor sheet according to any one of claims 13 to 17, wherein the transparent resin layer has a minimum transmittance of 80% or more at a wavelength of 400 to 800 nm. The transparent resin layer according to any one of claims 16, 17 and 16, wherein the ratio of the fine particles in the total solid content in the transparent resin layer is 0.1 wt% to 30 wt% Lt; / RTI &gt; 20. The phosphor sheet according to any one of claims 18 to 19, wherein the average particle diameter of the fine particles contained in the transparent resin layer is 1 nm or more and 1000 nm or less, . 20. A method of manufacturing a phosphor sheet, comprising the steps of: disposing a phosphor sheet according to any one of claims 1 to 20 into individual pieces;
A pick-up step of picking up the fragmented phosphor sheet,
Attaching step of attaching the fragmented phosphor sheet to a light source
Wherein the light emitting device comprises a light emitting diode. A light emitting body comprising the phosphor sheet according to any one of claims 1 to 20. A light source unit comprising the phosphor sheet according to any one of claims 1 to 20. A display comprising the light source unit according to claim 23.

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