JP6541638B2 - Phosphor-containing multilayer film sheet and light emitting device - Google Patents

Description

  The present invention relates to a wavelength conversion member for remote phosphors. The present invention relates to various light emitting devices including, for example, a blue light emitting diode (blue LED) or a white light emitting diode (white LED) using an ultraviolet light emitting diode (ultraviolet LED).

  A light emitting device configured using an LED as a light source has a long life, is easily reduced in size compared to a light bulb, and can be driven at a constant voltage, so various lightings such as home lighting and vehicles are possible. Attention is focused on as a next-generation light source such as a lamp for lighting, back light of liquid crystal display element, etc., and research and development are actively promoted in recent years.

  A remote phosphor device (hereinafter, also simply referred to as "remote phosphor") is a device having a configuration in which a wavelength conversion member containing a phosphor is disposed apart from a light source. The remote phosphor is advantageous in that since the wavelength conversion member is separated from the light source, the phosphor is less deteriorated by heat and can be molded by a conventional molding machine.

  For example, by using YAG: Ce phosphor which is a yellow phosphor as in Patent Document 1 and an epoxy casting resin, it is possible to stabilize the color of the light emitted from the light emitting device, and to perform wavelength conversion Mold materials have been proposed. However, yellow phosphors do not provide high color rendering, and epoxy resins have low quality reliability.

  Patent Document 2 proposes a wavelength conversion member capable of suppressing a change in chromaticity and obtaining sufficient color rendering properties by combining a yellow phosphor and a green phosphor or using a green phosphor. However, Patent Document 2 does not describe a combination of a red phosphor and a green phosphor.

  In Patent Document 3, a plurality of phosphor layers are provided, and using a β-SiAlON as a green phosphor, from a phosphor layer containing a phosphor having a long emission wavelength to a phosphor layer containing a phosphor having a short emission wavelength A phosphor-containing multilayer sheet has been proposed in which light is emitted in this order and further fine irregularities are provided on the surface to reduce color unevenness and increase the luminous efficiency. However, Patent Document 3 does not describe the use of the remote phosphor, and also does not show a configuration for obtaining an appropriate chromaticity in the remote phosphor.

  Patent Document 4 discloses a light-emitting element, and a phosphor-containing cover including a first phosphor and a second phosphor of a type different from the first phosphor, covering the light-emitting element apart from the light-emitting element. Wherein the phosphor-containing cover includes the first phosphor and the first region substantially free of the second phosphor, and a front second phosphor. And a second region substantially containing the first phosphor and containing light emitted from the light emitting element and having passed through the first region, and light emitted from the light emitting element and transmitted from the light emitting element to the second region. A light emitting device is described, characterized in that the light passing through the region is mixed outside the phosphor-containing cover. However, in the configuration described in Patent Document 4, although the first region and the second region are alternately arranged, the arrangement direction of the first region and the second region is the irradiation direction of the excitation light. It is parallel to When the arrangement direction is parallel to the irradiation direction of the excitation light, the manufacture of the light emitting device becomes complicated, and there is a problem that the chromaticity is not constant.

Patent No. 3866091 gazette JP, 2014-130998, A JP, 2015-130459, A JP, 2013-223448, A

  The subject of the present invention is a material which emits homogeneous mixed color, which is an applicable technical cost and sufficiently reproducible material, and has high quality reliability and high color rendering, and the total luminous flux of the light emitting device. It is an object of the present invention to provide a wavelength conversion member capable of enhancing the

  The present invention is as follows.

[1] A wavelength conversion member for remote phosphor comprising a phosphor-containing multilayer film sheet satisfying the following conditions (1) to (12).
(1) The phosphor-containing multilayer film sheet is composed of a plurality of layers of a resin composition containing resin A as a main component, and at least two phosphor layers are included in the plurality of layers. The phosphor-containing multilayer film sheet containing at least two phosphor layers includes two or more phosphors including a red phosphor and a green phosphor.
(2) The phosphor-containing multilayer film sheet is provided so as to be laminated in the traveling direction of light passing through the phosphor-containing multilayer film sheet, and is contained in each phosphor layer of the phosphor-containing multilayer film sheets The type of phosphor to be used is one, and a phosphor layer containing a phosphor having a long emission wavelength is sequentially transmitted from the phosphor layer containing a phosphor having a short emission wavelength to the phosphor layer containing a phosphor having a short emission wavelength. Be placed in the direction of travel.
(3) The green phosphor should be one or more selected from the following (3-1) and (3-2).
(3-1) A green phosphor whose base material is a crystal made of alkaline earth silicate, alkaline earth silicate nitride or β-SiAlON, with Eu ²⁺ as an activator.
(3-2) A green phosphor whose base material is a crystal made of garnet-type oxide or alkaline earth metal scandate salt with Ce ³⁺ as an activator.
(4) The red phosphor should be CASN: Eu phosphor.
(5) The green phosphor should have a maximum particle size of ≦ 15.0 μm and an average particle size of 0.5 μm or more and 5.0 μm or less.
(6) The phosphor-containing multilayer film sheet has a micro uneven structure with a height of 0.4 μm or less and a pattern pitch distance of 0.4 μm or less on the surface on which light is incident and the surface on which the incident light is emitted to the outside To do.
(7) The thickness of the phosphor layer should be 0.05 mm or more and 0.20 mm or less.
(8) The volume (volume frequency) of the green phosphor should be 1.0 vol% or more and 20.0 vol% or less.
(9) The volume (volume frequency) of the red phosphor should be 1.0 vol% or more and 20.0 vol% or less.
(10) The resin A is a silicone resin.
(11) The wavelength conversion member is configured to receive light having an emission peak wavelength of 440 to 470 nm.
(12) The wavelength conversion member is configured to receive light having an irradiance of 0.01 mW / mm ² or less.

[2] The wavelength conversion member for remote phosphors according to [1], wherein the green phosphor is LuAG: Ce particles.

[3] Green phosphor has the general formula _{(Lu 1-x Ce x)} 3 Al y Ga z O 12 (0 <x <0.5,0 ≦ z ≦ 0.5,5 ≦ y + z ≦ 5.5) The wavelength conversion member for remote phosphors as described in [1] or [2] which is a green fluorescent substance shown by these.

[4] The wavelength conversion member for remote phosphors according to any one of [1] to [3], wherein the absorption coefficient of the green phosphor is 80.0 / mm or more.

[5] The wavelength conversion member for remote phosphors according to any one of [1] to [4], wherein the pattern pitch distance of the fine concavo-convex structure is 0.05 μm to 0.40 μm.

[6] The wavelength conversion member for remote phosphors according to [1] to [5], wherein the height of the convex portion of the fine concavo-convex structure is 0.05 μm to 0.40 μm.

[7] The wavelength conversion member for remote phosphors according to any one of [1] to [6], wherein a fine concavo-convex structure is formed at the interface of each layer.

[8] A light emitting device comprising: a light source emitting excitation light; and the wavelength conversion member for remote phosphor according to any one of [1] to [7], which converts the wavelength of the excitation light and emits light. .

[9] The light emitting device according to [8], wherein the color temperature of light emitted from the light emitting device is 2700 K to 6500 K according to ANSI C 78. 377-2008.

[10] The light emitting device according to [8] or [9], wherein an emission peak wavelength of the excitation light emitted from the light source is 440 to 470 nm.

[11] The irradiance of the excitation light emitted from the light source to the wavelength conversion member for remote phosphors is 0.01 mW / mm ² or less according to any one of [8] to [10]. Light emitting device.

[12] A remote phosphor provided with the light emitting device according to any one of [8] to [11].

  According to the present invention, for example, the following effects are obtained. It can emit homogeneous mixed colors. Low cost and high quality reliability. High color rendering (color reproduction) can be obtained. The total luminous flux of the light emitting device can be increased and it can be suitably used as a remote phosphor device.

It is a block diagram of the remote phosphor apparatus containing the wavelength conversion member which concerns on this embodiment, and an excitation light source. It is an expanded sectional view of the fine concavo-convex structure provided in the surface of the wavelength conversion member concerning this embodiment. It is explanatory drawing which shows the evaluation method of the permeation | transmission energy efficiency using an integrating sphere.

  Hereinafter, embodiments of a wavelength conversion member according to the present invention and a light emitting device using the same will be described with reference to FIGS. 1 and 2. In addition, in this specification, "-" (tilde symbol) which shows a numerical range is used as a meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

  First, the remote phosphor device (hereinafter also referred to as “light emitting device”) 11 according to the present embodiment emits the wavelength conversion member 12 according to the present embodiment and the excitation light 14 irradiated to the wavelength conversion member 12 And an excitation light source (hereinafter, also simply referred to as “light source”) 13. The light source 13 is configured of a light emitting diode (LED), a laser diode (LD), or the like.

The intensity of the light emitted from the light source 13 emitting the excitation light 14 and irradiated to the wavelength conversion member 12 (that is, the irradiance of the light received by the wavelength conversion member 12) is 0.01 mW / mm ² or less. The irradiance (the intensity of light incident on the wavelength conversion member 12) is an index indicating the intensity of the energy of the incident light normalized by the area of the light receiving surface of the wavelength conversion member 12. The emission peak wavelength of the excitation light 14 is 440 nm to 470 nm. Furthermore, the emission peak wavelength of the excitation light 14 is more preferably 440 nm to 460 nm. When the emission peak wavelength of the excitation light 14 is shorter than 440 nm or longer than 470 nm, the chromaticity of the light 15 emitted from the wavelength conversion member 12 is daylight color or neutral white (neutral) as described later. There is a disadvantage that it is not in the range of white) and not suitable for practical use.

  On the other hand, as shown in FIG. 1, the wavelength conversion member 12 according to the present embodiment receives the excitation light 14 from the light source 13, converts the wavelength, and emits light of a wavelength different from that of the excitation light 14 (emission light) Emit 15 In this embodiment, it is preferable to wavelength convert the excitation light 14 from the light source 13 to emit light 15 of color temperatures 2700 K to 6500 K according to ANSI C 78. 377-2008. More preferably, the emitted light 15 is daylight or daylight white light. Here, the daylight color and the daylight white are terms defined in JIS Z9112: 2012. That is, daylight color is a color temperature 6500 K on ANSI C 78. 377-2008, and color temperature 6500 K is 0.306 色度 x CIE 0.320, 0.320 on the chromaticity coordinate (CIE 1931) of the light. It means that it is the range of <= y <= 0.340 and y <= x + 0.028. In addition, the daytime white color is 5700 K on ANSI C 78. 377-2008, and the color temperature 5700 K is 0.323 x x 、 0.336, 0 on the chromaticity coordinate of light (CIE 1931). It means that it is in the range of .25 ≦ y ≦ 0.355, y ≦ 0.911x + 0.054.

  The wavelength conversion member 12 includes at least layers 101a and 101b of a resin composition containing resin A as a main component, and the phosphors 103 and 104 are contained in the layers 101a and 101b of the respective resin compositions. . For this reason, this resin composition is also referred to as phosphor layer 101a and phosphor layer 101b. Each layer of the wavelength conversion member 12 including the phosphor layer 101 a and the phosphor layer 101 b is configured to be stacked along the traveling direction of the excitation light 14. By the wavelength conversion member 12 having such a laminated structure, the chromaticity can be stabilized, and the manufacture of the remote phosphor device 11 can be simplified.

  In FIG. 1, the dimensions of the surface of the phosphor layers 101 a and 101 b facing the incident direction of the excitation light 14 and the surface on the opposite side are arbitrary, and may be larger or smaller than the size of the excitation light source 13. . This is also the case in FIG.

  As the resin A, it is preferable to use a silicone resin (that is, a resin containing a silicone component). The silicone resin is excellent in the reliability as a light emitting device part such as weather resistance and moisture resistance, and exhibits an effect of improving the dispersibility of the fluorescent substance.

  The refractive index of the resin A is preferably 1.3 to 1.8 from the viewpoint of light extraction efficiency. Further, those of 1.4 to 1.5 are more preferable.

  On the other hand, with respect to the phosphors 103 and 104 to be contained in the resin composition, the phosphor 103 is preferably a red phosphor. The phosphor 104 is preferably a green phosphor. That is, for the phosphor layer laminated along the traveling direction of the excitation light 14, the phosphor layer 101a closer to the light source 13 includes the phosphor 103 which is a red phosphor, and the fluorescence far from the light source 13 An embodiment in which the body layer 101b includes the phosphor 104 which is a green phosphor is preferable. By adopting such a configuration, the emission intensity from the wavelength conversion member 12 can be increased.

A phosphor that emits light (emission wavelength) in a red-orange region (600 nm to 630 nm) or a red region (630 nm to 800 nm) is defined as a red phosphor. A CASN: Eu phosphor is used as the red phosphor in the present embodiment. The CASN: Eu phosphor refers to, for example, a CaAlSiN ₃ : Eu ²⁺ phosphor, and a red phosphor having Eu ²⁺ as an activator and a crystal made of an alkaline earth silicon nitride as a base. It should be noted that the definition of CASN: Eu phosphor in the present specification excludes SCASN: Eu phosphor.

A phosphor that emits light in the green region (500 nm to 555 nm) is defined as a green phosphor. The green phosphor in the present embodiment is one or more selected from the following (3-1) and (3-2).
(3-1) A green phosphor whose base material is a crystal made of alkaline earth silicate, alkaline earth silicate nitride or β-SiAlON, with Eu ²⁺ as an activator.
(3-2) A green phosphor whose base material is a crystal made of garnet-type oxide or alkaline earth metal scandate salt with Ce ³⁺ as an activator. For example, a green phosphor or the like represented by the general formula _{(Lu 1-x Ce x)} 3Al y Ga z O 12 and the like.

  In the wavelength conversion member 12 according to the present embodiment, the red phosphor 103 uses CASN: Eu phosphor. The average particle size of the red phosphor 103 is preferably in the range of 10.0 μm to 20.0 μm, and the maximum particle size is preferably 100.0 μm or less. If the average particle size of the red phosphor 103 is more than 20.0 μm or less than 10.0 μm, a problem may occur that the luminous efficiency of the red phosphor is reduced. Although hypothesized, such a problem is considered to be caused by the poor crystal quality of the red phosphor.

The green phosphor 104 according to the present embodiment, the general formula _{(Lu 1-x Ce x)} 3 Al y Ga z O 12 (0 <x <0.5,0 ≦ z ≦ 0.5,5 ≦ y + z ≦ The phosphor (LuAG: Ce phosphor) which has LuAG as a main component shown by 5.5) is preferable. The average particle size of the green phosphor 104 is preferably in the range of 0.5 to 5.0 μm, and the maximum particle size is preferably 15.0 μm or less. When the average particle diameter of the green phosphor 104 is more than 5.0 μm or less than 0.5 μm, problems may occur that the color unevenness and light distribution color unevenness of light emitted from the wavelength conversion member 12 become large. . Although hypothesized, it is believed that such problems occur because light dispersion in the phosphor layer is adversely affected if the average particle size is too large or too small.

  Here, the average particle diameter of the phosphor means the passage from the small particle diameter side in the volume-based particle size distribution obtained by measurement using a laser diffraction / scattering particle size distribution measurement method (manufactured by Beckman Coulter, LS13-320). It refers to the particle diameter of 50% of cumulative minutes (accumulated passage fraction).

The extinction coefficient of the green phosphor that can be used in the present embodiment is preferably 80.0 / mm or more (80.0 mm ⁻¹ or more). If the light absorption coefficient of the green phosphor is less than 80.0 / mm, a problem may occur in that the thickness unevenness of the wavelength conversion member becomes large. Although this is a hypothesis, such a problem arises because when the absorption coefficient is small, the concentration of the phosphor contained in the resin A increases, the viscosity of the resin A increases, and the production of the wavelength conversion member is adversely affected. it is conceivable that. Although not limited to a particular theory, it is considered that in the present embodiment, the larger the extinction coefficient of the green phosphor, the better the wavelength conversion member for remote phosphors.

  There are solid phase method, liquid phase method, sol-gel method and so on for synthesis method of red phosphor and green phosphor, and there is no particular limitation. For example, precursor compounds of elements constituting phosphor are mixed and fired Methods are included. As needed, it can synthesize | combine, applying the process of a baking, a grinding | pulverization, washing | cleaning, classification etc. suitably, etc. suitably.

  The thickness of each of the phosphor layers 101a and 101b is preferably in the range of 0.05 mm to 0.20 mm. If the thickness of the phosphor layer is more than 0.20 mm, there is a disadvantage that an appropriate chromaticity can not be obtained when used in a remote phosphor device. When the thickness of the phosphor layer is less than 0.05 mm, it becomes difficult to form a multilayer film sheet.

  Further, the composition of each phosphor in the volume ratio of the phosphor and the resin A contained in each of the phosphor layers 101a and 101b (the volume of each component is the mass of each component divided by the specific gravity of each component) The (volume frequency) is preferably 1.0 vol% or more and 20.0 vol% or less. If the volume frequency deviates from this range, there is a disadvantage that the chromaticity of the light emitted from the wavelength conversion member 12 does not fall within the daylight color or the daylight white range, and is not suitable for practical use.

The composition of the phosphor is indicated by the volume frequency of the phosphor. The volume frequency (%) of the phosphor is replaced by the following equation (Equation 1).
Volume frequency of fluorescent substance {%} = (m _phos / ρ _phos ) / (m _phos / ρ _phos + m _matrix / ρ _matrix ) × 100 (Equation 1)
m _phos : mass of phosphor in the phosphor layer [g]
ρ _phos : density of phosphor [g / cm ³ ]
m _matrix : mass of resin A in the phosphor layer [g]
ρ _matrix : Density of resin A [g / cm ³ ]

  In the wavelength conversion member 12 according to the present embodiment, the wavelength of visible light (400 to 800 nm) on the surface of the wavelength conversion member 12 (that is, the surface on which the light from the light source 13 enters and the surface on which light is emitted to the outside) It is preferable to provide a fine asperity mechanism 16 having a concavo-convex pattern structure in which the size of the pattern is small. More preferably, the fine asperity mechanism 16 can be formed at the interface of each layer of the wavelength conversion member 12. The fine structure of the fine asperity mechanism 16 is shown enlarged in FIG.

  The pattern pitch distance D and the height (height of the convex portion) H of the fine asperity mechanism 16 shown in FIG. 2 are each preferably 0.40 μm or less, and are in the range of 0.05 μm to 0.40 μm. Is more preferred.

  It is preferable that the light emission peak wavelength of the light which the excitation light source 13 which concerns on this Embodiment emits is 440-470 nm. More preferably, it is 440-460 nm.

  As described above, the total luminous flux (brightness) of the light emitting device 11 using the wavelength conversion member 12 according to the present embodiment can be improved. Here, it is possible to obtain a light emitting device 11 that emits homogeneous mixed color, is a material that is sufficiently reproducible with applicable technical cost, has high reliability of quality, and has high color rendering. it can.

  A method of producing the phosphor-containing multilayer film sheet of the present invention will be described. The slurry obtained by kneading and vacuum defoaming the sealing resin and the phosphor at the above ratio is laminated using a known sheet forming method such as vacuum forming, pressure forming, press forming, etc., cutting method, nano imprint method, A fluorescent substance containing multilayer film sheet can be obtained by providing a fine concavo-convex structure on the surface using laser micro processing, an etching method or the like. The phosphor-containing multilayer film sheet of the present invention is composed of a plurality of layers of a resin composition containing resin A as a main component. And, at least two phosphor layers are included in the plurality of layers, and the at least two phosphor layers contain two or more phosphors including a red phosphor and a green phosphor. It is a body containing multilayer film sheet.

  The remote phosphor of the present invention is manufactured such that the wavelength conversion member is less susceptible to the heat from the light source by arranging the wavelength conversion member containing the phosphor away from the light source. In the remote phosphor of the present invention, it is preferable to arrange the wavelength conversion member at a distance of, for example, 1 mm to 10 cm, more preferably, 1 mm to 5 cm from the light source.

  The present invention will be more specifically illustrated using examples, but the present invention is not limited by the contents described in the examples.

  The chromaticity, the optical characteristics (total luminous flux, color rendering index, color unevenness, light distribution color unevenness), and reliability of the light emitting devices according to Examples 1 to 6 and Comparative Examples 1 to 10 were evaluated. Each of the light emitting device and the wavelength conversion member according to the first to sixth embodiments has the same configuration as the light emitting device 11 and the wavelength conversion member 12 shown in FIG.

Example 1
A phosphor was melt-kneaded as a resin A into a two-component silicone resin (KER-2500, manufactured by Shin-Etsu Chemical Co., Ltd.) using a vacuum degassing apparatus (ARV-310, manufactured by THINKY) to prepare a phosphor paste. . The red phosphor used is RE-650W (CASN: Eu) having an average particle diameter of 16 μm among Aron Bright (registered trademark) manufactured by Denka Co., Ltd. The green phosphor is a red phosphor manufactured by Sakai Chemical Industry Co., Ltd. LuAG: Ce phosphor (green phosphor 1) was used. The green phosphor had an average particle size of 5.0 μm and an extinction coefficient of 89.2 / mm. Next, the phosphor paste was poured into the openings using a spacer frame having an opening of 50 mm × 50 mm and an adjusted depth. Thereafter, it was cured by heating at 150 ° C. for 1 hour. By performing the said operation twice, the fluorescent substance containing sheet | seat of size 50 mm x 50 mm was produced.

  It is mixed with the silicone resin so that the concentration (volume frequency) of the red phosphor RE-650W becomes 3.7 vol% so that the color temperature of the light emitting device becomes 5700 K (chromaticity: 0.329, 0.342) The phosphor layer 101a was manufactured such that the thickness of the layer was 0.10 mm. Similarly, the green phosphor 1 is mixed with the silicone resin so that the concentration (volume frequency) of the green phosphor 1 is 8.6 vol%, and the phosphor layer 101 b is manufactured by the manufacturing method so that the thickness of the layer is 0.10 mm. did. Furthermore, the red phosphor-containing layer 101a of the phosphor-containing sheet is disposed at a position close to the excitation light source, and the green phosphor-containing layer is disposed at a position far from the excitation light source. Finally, a fine asperity mechanism was formed on the surface on which the light of the excitation light is incident and on the surface on which the incident light is emitted to the outside, and the wavelength conversion member 12 was produced.

(light source)
The excitation light 14 emitted from the light source 13 of Example 1 had an emission peak wavelength of 450 nm. Moreover, the irradiance with which the wavelength conversion member 12 is irradiated was 0.01 mW / mm ² . The distance 20 from the light source 13 to the fine asperity mechanism 16 of the resin composition 101a of the wavelength conversion member 12 was 1 cm.

Example 2
The wavelength conversion member 12 according to the second embodiment is a green phosphor (3.1 vol% of red phosphor) so that the color temperature of the light emitting device is 5700 K (chromaticity: 0.329, 0.342). The same as Example 1, except that the average particle diameter of the green phosphor 2 (manufactured by Sakai Chemical Industry Co., Ltd.) is 2.6 μm, the absorption coefficient is 136.4 / mm, and the concentration of the green phosphor is 5.4 vol%. did. Concentrations are given by volume frequency.

Example 3
In the wavelength conversion member 12 according to the third embodiment, the concentration of the red phosphor is 2.8 vol%, so that the color temperature of the light emitting device is 5700 K (chromaticity: 0.329, 0.342); The green phosphor 3 manufactured by Sakai Chemical Industry Co., Ltd. was the same as Example 1 except that the average particle diameter was 4.6 μm, the absorptivity was 105.9 / mm, and the concentration was 7.3 vol%.

Comparative Example 1
In the wavelength conversion member 12 according to Comparative Example 1, the concentration of the red phosphor is 3.4 vol%, so that the color temperature of the light emitting device is 5700 K (chromaticity: 0.329, 0.342); It is the same as Example 1 except that the average particle diameter of Denka Co., Ltd.) is 0.3 μm, the light absorption coefficient is 60.0 / mm, and the concentration is 12.0 vol%.

Comparative Example 2
In the wavelength conversion member 12 according to Comparative Example 2, the concentration of the red phosphor is 3.4 vol%, so that the color temperature of the light emitting device is 5700 K (chromaticity: 0.329, 0.342); The green phosphor 4 manufactured by Sakai Chemical Industry Co., Ltd. was the same as Example 1 except that the average particle diameter was 8.0 μm, the light absorption coefficient was 62.4 / mm, and the concentration was 12.9 vol%.

Example 4
In the wavelength conversion member 12 according to Example 4, the thickness of each phosphor-containing layer (101a, 101b) is 0 so that the color temperature of the light emitting device is 6500 K (chromaticity: 0.313, 0.329). .20 mm, concentration of red phosphor is 1.2 vol%, average particle diameter of green phosphor (green phosphor 2, manufactured by Sakai Chemical Industry Co., Ltd.) is 2.6 μm, extinction coefficient is 136.4 / mm, concentration is 2 Example 6 was the same as Example 1 except that the content was 6 vol%.

Example 5
In the wavelength conversion member 12 according to Example 5, the thickness of each phosphor-containing layer (101a, 101b) is 0.10 mm, the concentration of the red phosphor is 2.4 vol%, and the green phosphor (green phosphor 2; Example 4 was the same as Example 4 except that the concentration of Chemical Industry Co., Ltd. was 5.1 vol%.

Example 6
In the wavelength conversion member 12 according to Example 6, the thickness of each phosphor-containing layer (101a, 101b) is 0.05 mm, the concentration of the red phosphor is 4.9 vol%, and the green phosphor (green phosphor 2; Example 4 was the same as Example 4 except that the concentration of Chemical Industries, Ltd. was 10.2 vol%.

Comparative Example 3
In the wavelength conversion member 12 according to Comparative Example 3, the thickness of each phosphor-containing layer (101a, 101b) is 0.10 mm, the concentration of the red phosphor is 0.47 vol%, and the green phosphor (green phosphor 2; Example 5 was the same as Example 5 except that the concentration of chemical industry Co., Ltd. was 0.99 vol%.

Comparative Example 4
In the wavelength conversion member 12 according to Comparative Example 4, the thickness of each phosphor-containing layer (101a, 101b) is 0.10 mm, the concentration of the red phosphor is 9.9 vol%, and the green phosphor (green phosphor 2; Example 5 was the same as Example 5 except that the concentration of Chemical Industries, Ltd. was 21.0 vol%.

Comparative Example 5
The wavelength conversion member 12 according to Comparative Example 5 was the same as Example 5 except that the thickness of each of the phosphor-containing layers (101a and 101b) was 0.04 mm.

Comparative Example 6
The wavelength conversion member 12 according to Comparative Example 6 was the same as Example 5 except that the thickness of each of the phosphor-containing layers (101a, 101b) was 0.21 mm.

Comparative Example 7
The wavelength conversion member 12 according to Comparative Example 7 was the same as Example 5 except that the resin A was changed to a bisphenol A epoxy resin (trade name Epicoat 806, manufactured by Japan Epoxy Resins Co., Ltd.).

Comparative Example 8
Comparative Example 8 is the same as Example 5 except that the emission peak wavelength of the excitation light 14 emitted from the light source 13 is 420 nm.

Comparative Example 9
The comparative example 9 was the same as the example 5 except that the irradiance irradiated to the wavelength conversion member 12 was 0.02 mW / mm ² .

Comparative Example 10
In the wavelength conversion member 12 according to Comparative Example 10, the red phosphor is RE-622C (SCASN: Eu phosphor, manufactured by Denka Co., Ltd.), the concentration of the red phosphor is 1.4 vol%, and the concentration of the green phosphor is Example 5 was the same as Example 5 except that it was 5.1 vol%.

<Evaluation method>
(Maximum particle size)
In the volume-based particle size distribution obtained by measurement using a laser diffraction / scattering particle size distribution measurement method (manufactured by Beckman Coulter, LS 13-320), the largest observed particle diameter is taken as the maximum value of the particle diameter.

(Average particle size)
In a volume-based particle size distribution obtained by measurement using a laser diffraction / scattering particle size distribution measurement method (manufactured by Beckman Coulter, LS 13-320), particles of 50% of passing integration (integral passing fraction) from the small particle diameter side The diameter was taken as the average particle diameter.

(Absorptivity)
A sheet formed of one type of phosphor and resin A was prepared for measuring the light absorption coefficient. The effective thickness of the produced sheet was calculated. The effective thickness is obtained by multiplying the volume frequency of the phosphor in the sheet by the thickness of the phosphor layer and dividing by 100. The effective thickness (% × mm) is replaced by the following equation (Equation 2).
Effective thickness (% × mm) = volume frequency of phosphor (%) × thickness of phosphor layer (mm) / 100 (% × mm) (Equation 2)

  Next, as shown in FIG. 3, the sheet was measured for transmitted energy using a spectrophotometer (U-4100 manufactured by Hitachi High-Tech Co., Ltd.) having an integrating sphere having an entrance and a detector. Excitation light with a wavelength of 450 nm is incident from the light source on the surface of the measurement sample fixed to the entrance of the integrating sphere, and the detector detects the emitted light that passes through the measurement sample and is emitted from the back side into the integrating sphere. did.

The transmitted energy efficiency is obtained by determining the transmitted light intensity I ₁ (wavelength 450 ± 20 nm) from the excitation light spectrum when the measurement sample is not set, and transmitted light intensity I ₂ (wavelength 450 ± 20 nm) not transmitted from the fluorescence spectrum of the sample Was calculated according to the following equation 3.
Transmission energy efficiency = −log ₁₀ (I ₁ / I ₂ ) (Equation 3)
Next, the measurement result is plotted as the effective thickness on the horizontal axis and the transmission energy efficiency on the vertical axis, and the value of the slope of the straight line connecting the plotted point and the origin is taken as the extinction coefficient.

(optical properties)
The excitation light 14 from the light source 13 is irradiated to the wavelength conversion member 12 and the total luminous flux, chromaticity, color temperature and color rendering index of the light emitted from the light emitting device 11 are total luminous flux measuring instruments (total luminous flux measurement system HM Series, Otsuka It measured using the electronic company make).

(Color unevenness evaluation)
For the measurement samples (Examples 1 to 6 and Comparative Examples 1, 2, 7, 9, and 10), the chromaticity of the sheet was measured using a phosphor distribution measuring apparatus (YWafer Mapper G53, manufactured by Y. Systems) . In the color unevenness evaluation, the amounts of change Δx and Δy on the chromaticity coordinates (CIE 1931) in the sheet plane are determined, and are calculated according to the following equation 4.
It was evaluated that the smaller the value of the color unevenness C, the better.

(Light distribution color unevenness evaluation)
For the measurement samples (Examples 1 to 6, Comparative Examples 1, 2, 7, 9, 10), the angular distribution of chromaticity was measured using an LED light distribution measurement system (GP-1000, manufactured by Otsuka Electronics Co., Ltd.).

In the light distribution color unevenness evaluation, the amounts of change Δx and Δy on the chromaticity coordinates (CIE 1931) were determined by the angle of the light emitted from the light emitting device 11, and were calculated according to the following Equation 5.
The smaller the value of the light distribution color unevenness E, the better.

(Measurement of luminescence intensity maintenance rate and reliability evaluation)
A measurement sample (Examples 1 to 6, Comparative Examples 1, 2, 7, 9, 10) is caused to emit light, and a multiphotometer (total luminous flux measurement (φ 1000 mm) system, manufactured by Otsuka Electronics Co., Ltd.) is used to expose 30 milliseconds The luminescence intensity was measured by the above-mentioned method to obtain "emission intensity before test". After leaving a measurement sample (Examples 1 to 6, Comparative Examples 1, 2, 7, 9, and 10) to emit light and standing in an oven at an environmental temperature of 85 ° C. for 500 hours, visual observation was performed. In addition, the measurement samples (Examples 1 to 6, Comparative Examples 1, 2, 7, 9, 10) are caused to emit light, and the exposure time 30 is measured using a multiphotometer (total luminous flux measurement (φ 1000 mm) system, manufactured by Otsuka Electronics Co., Ltd.) The luminescence intensity was measured in milliseconds, and it was referred to as "emission intensity after test". And it calculated | required as [luminescence intensity after a test] / [luminescence intensity before a test] x 100 = [luminescence intensity maintenance rate].

  The reliability evaluation was evaluated as follows. The case where the sheet had a color change by visual observation, the color change between the electrodes was confirmed, or the luminous intensity maintenance ratio was 97% or less was evaluated as a defect. The case where there was no discoloration of the sheet and the luminous intensity maintenance rate was 98% or more was evaluated as good.

  The breakdown and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 10 are shown in Tables 1 to 2. "N / A" in the table means that measurement was not possible or not applicable. Also, "←" in the table means that it is the same left.

  From Table 1 to Table 2, in both Examples 1 to 3 and Comparative Examples 1 to 2, the chromaticity was in the range of 5700 K of ANSI C 78. 377-2008. On the other hand, from the evaluation results of color unevenness and light distribution color unevenness, it can be seen that color unevenness is small in Examples 1 to 3. This is considered to be one of the factors that the green phosphors used in Examples 1 to 3 have an appropriate particle size for uniformly dispersing the light emitted from the light emitting device 11.

  Furthermore, the concentration of the phosphor is smaller in Examples 1 to 3 than in Comparative Examples 1 and 2. That is, the amount of phosphor used is small. This is considered to be one of the factors which reduce the usage-amount of fluorescent substance that the absorption coefficient of the green fluorescent substance of Examples 1-3 is 80 / mm or more.

  Examples 4-6 were in the range of 6500 K for ANSI C 78. 377-2008. On the other hand, Comparative Examples 3 to 6 deviated from the range of ANSI C 78. 377-2008 6500 K.

  In Comparative Example 7 in which an epoxy resin was used as the resin A, the resin turned yellow in the reliability evaluation.

  Comparative Example 8 using a light source with an emission peak wavelength of 420 nm as the light source 13 deviates from the range of 6500 K of ANSI C 78. 377-2008.

Comparative Example 9 in which the irradiance irradiated to the wavelength conversion member 12 was 0.02 mW / mm ² was in the range of 6500 K according to ANSI C 78. 377-2008 immediately after the light source was turned on. It became impossible to measure. This is considered to be because the calorific value generated at the time of wavelength conversion of light in the wavelength conversion member 12 exceeds the allowable calorific value of the resin A due to the increase of the irradiance from the light source.

  In Comparative Example 10 using the SCASN: Eu phosphor as the red phosphor, although the total luminous flux is larger than that of the example, the color rendering indexes Ra and R9 are significantly reduced.

  The wavelength conversion member according to the present invention and the light emitting device using the same are not limited to the above embodiment, and it goes without saying that various configurations can be adopted without departing from the scope of the present invention.

  The present invention has the following features.

  In the present invention, since the amount of the phosphor used is small and the thickness of the layer containing the phosphor is small, the cost is reduced.

11 Remote Phosphor Device (Light Emitting Device)
12 wavelength conversion member 13 excitation light source (light source)
14 excitation light 15 emission light 16 fine asperity mechanism 20 distance 101 a between excitation light source and wavelength conversion member phosphor layer (red phosphor-containing resin layer)
101b Phosphor layer (green phosphor-containing resin layer)
103 Phosphor (red phosphor)
104 Phosphor (green phosphor)
D Pattern pitch distance H Height (height of convex part)

Claims (12)

The wavelength conversion member for remote phosphors provided with the fluorescent substance containing multilayer film sheet which satisfy | fills following condition (1)- (10) .
(1) The phosphor-containing multilayer film sheet is composed of a plurality of layers of a resin composition containing resin A as a main component, and at least two phosphor layers are included in the plurality of layers. The phosphor-containing multilayer film sheet containing at least two phosphor layers includes two or more phosphors including a red phosphor and a green phosphor.
(2) The phosphor-containing multilayer film sheet is provided so as to be laminated in the traveling direction of light passing through the phosphor-containing multilayer film sheet, and is contained in each phosphor layer of the phosphor-containing multilayer film sheets The type of phosphor to be used is one, and a phosphor layer containing a phosphor having a long emission wavelength is sequentially transmitted from the phosphor layer containing a phosphor having a short emission wavelength to the phosphor layer containing a phosphor having a short emission wavelength. Be placed in the direction of travel.
(3) The green phosphor should be one or more selected from the following (3-1) and (3-2).
(3-1) A green phosphor whose base material is a crystal made of alkaline earth silicate, alkaline earth silicate nitride or β-SiAlON, with Eu ²⁺ as an activator.
(3-2) A green phosphor whose base material is a crystal made of garnet-type oxide or alkaline earth metal scandate salt with Ce ³⁺ as an activator.
(4) the red phosphor, CASN: Eu phosphor der is, and ≦ 100.0 maximum particle size and 10.0μm or more 20.0μm have an average particle size of less.
(5) The green phosphor should have a maximum particle size of ≦ 15.0 μm and an average particle size of 0.5 μm or more and 5.0 μm or less.
(6) The phosphor-containing multilayer film sheet has a micro uneven structure with a height of 0.4 μm or less and a pattern pitch distance of 0.4 μm or less on the surface on which light is incident and the surface on which the incident light is emitted to the outside To do.
(7) The thickness of the phosphor layer should be 0.05 mm or more and 0.20 mm or less.
(8) The volume (volume frequency) of the green phosphor should be 1.0 vol% or more and 20.0 vol% or less.
(9) The volume (volume frequency) of the red phosphor should be 1.0 vol% or more and 20.0 vol% or less.
(10) The resin A is a silicone resin .   The wavelength conversion member for remote phosphors according to claim 1, wherein the green phosphor is a LuAG: Ce particle. Green phosphor is represented by the general formula _{(Lu 1-x Ce x)} 3 Al y Ga z O 12 (0 <x <0.5,0 ≦ z ≦ 0.5,5 ≦ y + z ≦ 5.5) The wavelength conversion member for remote phosphors according to claim 1 or 2, which is a green phosphor.   The wavelength conversion member for remote phosphors according to any one of claims 1 to 3, wherein the absorption coefficient of the green phosphor is 80.0 / mm or more.   The wavelength conversion member for remote phosphors according to any one of claims 1 to 4, wherein the pattern pitch distance of the fine concavo-convex structure is 0.05 μm to 0.40 μm.   The height of the convex part of a fine concavo-convex structure is 0.05 micrometer-0.40 micrometer, The wavelength conversion member for remote phosphors of any one of Claims 1-5.   The wavelength conversion member for remote phosphors according to any one of claims 1 to 6, wherein a fine uneven structure is formed at the interface of each layer.   A light emitting device comprising: a light source emitting excitation light; and the wavelength conversion member for remote phosphor according to any one of claims 1 to 7, which converts the wavelength of the excitation light to emit light.   9. A light emitting device according to claim 8, wherein the color temperature of the light emitted by the light emitting device is between 2700 K and 6 500 K according to ANSI C 78. 377-2008.   The light emitting device according to claim 8 or 9, wherein an emission peak wavelength of the excitation light emitted by the light source is 440 to 470 nm. The light emitting device according to any one of claims 8 to 10, wherein an irradiance of the excitation light emitted from the light source to the wavelength conversion member for remote phosphor is 0.01 mW / mm ² or less.   The remote phosphor provided with the light-emitting device of any one of Claims 8-11.