JP6213938B2 - Wavelength control optical member, light emitting device, and lighting fixture - Google Patents

Description

  The present invention relates to a wavelength control optical member, a light emitting device, and a lighting fixture. Specifically, the present invention relates to a wavelength control optical member, a light emitting device, and a lighting fixture that have improved durability of the contained pigment.

  Conventionally, it has been proposed to use a resin composition in which a dye is dissolved in order to increase the brightness and contrast of a color filter used in a liquid crystal display device. However, it is known that a dye has poor light resistance because oxygen is excited by light energy to become singlet oxygen, and the singlet oxygen is oxidized and decomposed to discolor the dye. Therefore, in order to improve the light resistance of the dye, it has been proposed to add a dye to the polymerizable compound and further add both a singlet oxygen quencher and an antioxidant (see, for example, Patent Document 1).

  Moreover, although the infrared absorption filter used for a liquid crystal display device contains a near-infrared absorption pigment | dye, this near-infrared absorption pigment | dye is also low in light resistance. Therefore, in order to improve the light resistance of the near-infrared absorbing dye, a near-infrared absorbing filter in which the near-infrared absorbing dye is contained in fine particles has been proposed (see, for example, Patent Document 2).

JP 2011-141356 A JP 2010-60617 A

  However, in Patent Document 1, since the dye, the singlet oxygen quencher and the antioxidant are uniformly separated in the resin composition, the performance of the singlet oxygen quencher and the antioxidant is in comparison with the dye. It was not fully demonstrated. Moreover, in patent document 2, since the near-infrared absorption pigment | dye is only coat | covered with resin which comprises microparticles | fine-particles, light resistance was inadequate.

  The present invention has been made in view of such problems of the prior art. And the objective of this invention is providing the wavelength control optical member, light-emitting device, and lighting fixture which improved durability, especially light resistance and heat resistance of a pigment | dye.

  The wavelength control optical member according to the first aspect of the present invention includes a matrix resin and pigment-containing fine particles dispersed inside the matrix resin. And the pigment | dye containing microparticles | fine-particles contain the pigment | dye which has the maximum absorption wavelength in the range of 400 nm-650 nm, a singlet oxygen quencher, antioxidant, and an ultraviolet absorber.

  The wavelength control optical member according to the second aspect of the present invention is the optical member according to the first aspect, wherein the matrix resin contains at least one of the following resins. That is, the matrix resin contains at least one selected from the group consisting of acrylic resins, polycarbonate resins, acrylic-styrene copolymers, styrene resins, silicone resins, and cycloolefin resins.

  The wavelength control optical member according to the third aspect of the present invention is the optical member according to the first or second aspect, the dye-containing fine particles, the dye, the singlet oxygen quencher, the antioxidant and the ultraviolet absorber are It is coated with at least one of the following materials. That is, the dye, the singlet oxygen quencher, the antioxidant, and the ultraviolet absorber are coated with at least one of a hydrolysis condensate of alkoxysilane and polysilazane.

  The wavelength control optical member according to a fourth aspect of the present invention is the optical member according to any one of the first to third aspects, wherein the dye is selected from the group consisting of phthalocyanine-based, tetraazaporphyrin-based and porphyrin-based. At least one.

  The wavelength control optical member according to the fifth aspect of the present invention is the optical member according to any one of the first to fourth aspects, wherein the average particle size of the dye-containing fine particles is 100 nm to 30 μm.

  A light emitting device according to a sixth aspect of the present invention includes a light emitting element, a wavelength conversion member that converts the wavelength of light emitted from the light emitting element, and the wavelength control optical member according to any one of the first to fifth aspects. .

  The lighting fixture which concerns on the 7th aspect of this invention is equipped with the light-emitting device which concerns on a 6th aspect.

FIG. 1 is a schematic view showing an example of a wavelength control optical member according to an embodiment of the present invention. (A) is the schematic which shows the pigment | dye containing microparticles | fine-particles disperse | distributed inside a matrix resin, (b) is the schematic which shows an example of pigment | dye containing microparticles | fine-particles. FIG. 2 is a schematic view showing another example of the dye-containing fine particles dispersed in the wavelength control optical member. FIG. 3 is a schematic diagram illustrating an example of a light emitting device according to an embodiment of the present invention. FIG. 4 is a perspective view showing an example of a lighting fixture according to the embodiment of the present invention. FIG. 5 is a schematic diagram illustrating a configuration of a lighting fixture according to the embodiment of the present invention. (A) is a disassembled perspective view of the lamp in a lighting fixture, (b) is a schematic sectional drawing of an LED module, (c) is sectional drawing which shows the filter used for a lamp.

  Hereinafter, the wavelength control optical member, the light emitting device, and the lighting fixture according to the present embodiment will be described in detail with reference to the drawings. In addition, the dimension ratio of drawing quoted by the following embodiment is exaggerated on account of description, and may differ from an actual ratio.

[Wavelength control optical member]
As shown in FIG. 1, the wavelength control optical member 10 according to the present embodiment includes a matrix resin 1 and pigment-containing fine particles 2 dispersed in the matrix resin 1. Further, the dye-containing fine particles 2 contain a dye 3 having a maximum absorption wavelength in a range of 400 nm to 650 nm, a singlet oxygen quencher 4, an antioxidant 5, and an ultraviolet absorber 6.

  As shown in FIG. 1, the wavelength control optical member 10 of the present embodiment includes a dye 3 having a maximum absorption wavelength within a range of 400 nm to 650 nm, a singlet oxygen quencher 4, an oxidation inside the matrix resin 1. The inhibitor 5 is dispersed. Here, if these are simply dispersed in the matrix resin 1 as in Patent Document 1, the distances between the singlet oxygen quencher 4 and the antioxidant 5 and the dye 3 are too far apart. As a result, the effects of the singlet oxygen quencher 4 and the antioxidant 5 do not sufficiently reach the dye 3, and the deterioration of the dye 3 cannot be suppressed.

  However, in the wavelength control optical member 10 of the present embodiment, the dye 3, the singlet oxygen quencher 4, and the antioxidant 5 are contained inside the dye-containing fine particles 2. That is, the dye 3, the singlet oxygen quencher 4 and the antioxidant 5 as the deterioration suppressing additive are enclosed in the dye-containing fine particles 2. The dye-containing fine particles 2 are dispersed in the matrix resin 1. As a result, since the singlet oxygen quencher 4 and the antioxidant 5 are always arranged in the vicinity of the dye 3, the effects of the singlet oxygen quencher 4 and the antioxidant 5 can be effectively exerted on the dye 3. It becomes possible.

  Further, in the present embodiment, the dye-containing fine particles 2 contain, in addition to the dye 3, the singlet oxygen quencher 4 and the antioxidant 5, an ultraviolet absorber 6 as a deterioration suppressing additive. Therefore, the ultraviolet absorber 6 is disposed in the vicinity of the dye 3 and the ultraviolet light hardly reaches the dye 3, so that it is possible to suppress deterioration of the dye 3 due to absorption of the ultraviolet light.

  The dye 3 according to this embodiment is not particularly limited as long as it has a maximum absorption wavelength in the range of 400 nm to 650 nm. As the dye 3, for example, at least one selected from the group consisting of phthalocyanine, tetraazaporphyrin, and porphyrin can be used. Examples of the phthalocyanine dye include CI Direct Blue 86, 87, 189, and 199. Examples of the phthalocyanine dye include CI Acid Blue 249. Examples of tetraazaporphyrin-based dyes include TAP-2, TAP-18, and TAP-45 (manufactured by Yamada Chemical Co., Ltd.). Examples of porphyrin pigments include 5,10,15,20-tetraphenyl-21H, 23H-porphyrin (manufactured by Wako Chemical Co., Ltd.). These pigment | dyes may be used individually by 1 type, and may be used in combination of 2 or more type.

  The singlet oxygen quencher 4 according to the present embodiment is not particularly limited as long as oxygen in the air is activated by light energy to trap singlet oxygen and inactivate singlet oxygen. . Examples of singlet oxygen quenchers include transition metal complexes, dyes (infrared absorbing dyes), amines, phenols, sulfides, and the like. In the transition metal complex, a dialkyl phosphate, a dialkyl dithiocarbanate, benzene dithiol, or a similar dithiol is exemplified as a ligand, and nickel, copper, or cobalt is exemplified as a central metal. Examples of the dyes include polymethine dyes, cyanine dyes, azurenium dyes, pyrylium dyes, squarylium dyes, croconium dyes, aminium dyes, imonium dyes, and diimonium dyes. In addition, these singlet oxygen quenchers may be used individually by 1 type, and may be used in combination of 2 or more types.

  The antioxidant 5 according to the present embodiment is not particularly limited as long as it can suppress the auto-oxidation of the dye 3. Examples of the antioxidant include phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. In particular, phenol-based antioxidants and amine-based antioxidants are preferable, and hindered amines are particularly preferable among the amine-based antioxidants.

  Examples of the phenolic antioxidant include 2,6-t-butyl-4-methylphenol and n-octadecyl-3- (3'5'-di-t-butyl4'-hydroxyphenyl) propionate. Examples of the phenolic antioxidant include tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl)] methane. Examples of amine-based antioxidants include ADK STAB (registered trademark) LA-77, LA-57, LA-52, LA-62, LA-63, LA-67, and LA-68 (manufactured by ADEKA Corporation). . Examples of the amine antioxidant include TINUVIN (registered trademark) 123, TINUVIN 144, TINUVIN 622, TINUVIN 765, and TINUVIN 944 (manufactured by BASF Japan Ltd.). In addition, these antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ultraviolet absorber 6 according to the present embodiment is not particularly limited as long as it has a characteristic of low transmittance in the wavelength range of 280 nm to 360 nm. Examples of the UV absorber include triazine UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers, hydroxybenzoate UV absorbers, and the like.

  Examples of triazine ultraviolet absorbers include 2,4-bis [hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine. In addition, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine and the like can also be mentioned. Examples of the benzophenone ultraviolet absorber include 2,2′-dihydroxy-4,4′-di (hydroxymethyl) benzophenone, 2,2′-dihydroxy-4,4′-di (2-hydroxyethyl) benzophenone, and the like. It is done. Examples of benzotriazole ultraviolet absorbers include 2- [2′-hydroxy-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole and 2- [2′-hydroxy-5 ′-(2-hydroxyethyl) phenyl. ] -2H-benzotriazole and the like. Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like. Examples of hydroxybenzoate ultraviolet absorbers include phenyl salicylate, 4-t-butylphenyl salicylate, 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, and the like. In addition, these ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more type.

  As described above, the pigment 3, the singlet oxygen quencher 4, the antioxidant 5, and the ultraviolet absorber 6 are covered with the particulate material 7 inside the pigment-containing fine particles 2. Such a particulate material 7 is preferably a resin composed of at least one of a hydrolysis-condensation product of alkoxysilane and polysilazane. These resins have high transmittance in the visible light region of 380 nm to 780 nm and can be further granulated more easily.

  An alkoxysilane hydrolysis condensate is a condensate obtained by hydrolyzing an alkoxysilane and then dehydrating and condensing it. Specific examples of the alkoxysilane include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, and ethyldimethylmethoxysilane. Mention may also be made of methyldiethylmethoxysilane, ethyldimethylethoxysilane, methyldiethylethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane. Examples also include methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane, tert-butoxytrimethylsilane, and butoxytrimethylsilane. Examples also include vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane. Examples also include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Examples also include methyltriacetoxysilane, ethyltriacetoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Examples also include triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetraisopropoxysilane. In addition, the hydrolysis-condensation product of alkoxysilane may be used individually by 1 type, and may be used in combination of 2 or more type.

Polysilazane is a polymer having “— (SiH ₂ —NH) —” as a repeating unit, and examples thereof include chain polysilazane and cyclic polysilazane. At this time, all or part of H may be substituted with a substituent. Examples of the chain polysilazane include perhydropolysilazane, polymethylhydrosilazane, polyN-methylsilazane, polyN- (triethylsilyl) allylsilazane, polyN- (dimethylamino) cyclohexylsilazane, and phenylpolysilazane. In addition, polysilazane may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the matrix resin 1 in which the dye-containing fine particles 2 are dispersed, a resin that stably disperses the dye-containing fine particles 2 and has a high transmittance in the visible light region of 380 nm to 780 nm can be used. The matrix resin 1 may contain at least one selected from the group consisting of acrylic resins, polycarbonate resins, acrylic-styrene copolymers, styrene resins, silicone resins, and cycloolefin resins. preferable.

  The acrylic resin is obtained by polymerizing a (meth) acrylic monomer as a main component, and may contain another monomer copolymerizable with the (meth) acrylic monomer. As the acrylic resin, a resin obtained by polymerizing an acrylic monomer can be used. Examples of such acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and cyclohexyl (meth) acrylate. Also included are β-carboxyethyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. Further, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and 1,6-hexanediol diglycidyl ether di (meth) acrylate are also included. Bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tricyclodecanyl (meth) acrylate are also included. In addition, an acrylic monomer may be used individually by 1 type, and may be used in combination of 2 or more type. In the present specification, “(meth) acrylic” includes acrylic and methacrylic, and “(meth) acrylate” includes acrylate and methacrylate.

  Examples of the polycarbonate-based resin include aromatic polycarbonate polymers obtained by reacting dihydric phenol with phosgene or a carbonic acid diester compound, and aromatic polycarbonate resins that are copolymers thereof. Examples of the polycarbonate-based resin also include an aliphatic polycarbonate resin obtained by a copolymer of carbon dioxide and epoxide. Furthermore, examples of the polycarbonate-based resin include aromatic-aliphatic polycarbonates obtained by copolymerizing them. Further, linear aliphatic divalent carboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like can also be mentioned as copolymer monomers for polycarbonate resins. In addition, a polycarbonate-type resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The acrylic-styrene copolymer is obtained by polymerizing a (meth) acrylic monomer and a styrene monomer as main components. Moreover, the acryl-styrene copolymer may contain the other monomer copolymerizable with a (meth) acrylic-type monomer and a styrene-type monomer. Examples of acrylic-styrene copolymers include styrene- (meth) acrylic acid ester copolymers, styrene-diethylaminoethyl methacrylate copolymers, and styrene-butadiene-acrylic acid ester copolymers. A styrene-butadiene copolymer, a styrene-butadiene-chlorinated paraffin copolymer, and a styrene-methyl methacrylate copolymer can also be used.

  The styrene resin is obtained by polymerizing a styrene monomer as a main component. Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, and p-methoxystyrene. Moreover, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene are also included. These styrenic monomers may be used alone or in combination of two or more.

  A silicone resin is a resin having a three-dimensional network structure by crosslinking a linear polymer composed of siloxane bonds. Examples of silicone resins include dimethyl silicones whose side chains are composed of, for example, methyl groups, and aromatic silicones that are partially substituted with aromatic molecules. In the present embodiment, aromatic silicone is particularly preferable as the silicone resin.

  The cycloolefin-based resin is a resin having a main chain composed of carbon-carbon bonds and having a cyclic hydrocarbon structure in at least a part of the main chain. Examples of the cycloolefin resin include an addition copolymer of ethylene and norbornene, an addition copolymer of ethylene and tetracyclododecene, and the like.

  In the wavelength control optical member 10 of the present embodiment, the average particle diameter of the dye-containing fine particles 2 is preferably 50 nm to 30 μm, and more preferably 100 nm to 30 μm. When the average particle diameter of the dye-containing fine particles 2 is within this range, the singlet oxygen quencher 4, the antioxidant 5 and the ultraviolet absorber 6 can always be arranged in the vicinity of the dye 3. Therefore, it is possible to efficiently suppress the deterioration of the dye 3. The average particle diameter of the dye-containing fine particles 2 can be measured by observing the cross section of the wavelength control optical member 10 using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like.

  As described above, the wavelength control optical member 10 according to this embodiment includes the matrix resin 1 and the dye-containing fine particles 2 dispersed inside the matrix resin 1. And the pigment | dye containing fine particle 2 contains the pigment | dye 3 which has the maximum absorption wavelength in the range of 400 nm-650 nm, the singlet oxygen quencher 4, the antioxidant 5, and the ultraviolet absorber 6. FIG. Therefore, in the vicinity of the dye 3, the singlet oxygen quencher 4 inactivates the singlet oxygen, the antioxidant 5 suppresses the auto-oxidation of the dye, and the ultraviolet absorber 6 prevents the ultraviolet light 6 from reaching the dye 3. Suppress. As a result, it is possible to improve the durability of the dye 3, particularly the light resistance and heat resistance, and to improve the stability of the dye.

  In addition, since the pigment 3 is covered with the particulate material 7, and the pigment-containing fine particles 2 are dispersed inside the matrix resin 1, the pigment 3 is difficult to come into contact with oxygen in the atmosphere. As a result, it is possible to further suppress oxidation of the dye 3 due to contact with oxygen.

  Furthermore, the singlet oxygen quencher 4, the antioxidant 5, the ultraviolet absorber 6, and the particulate material 7 are unlikely to inhibit light absorption in the visible light region by the dye 3. Therefore, even when these are arranged in the vicinity of the dye 3, the spectral characteristics of the dye 3 can be maintained.

  In the wavelength control optical member of the present embodiment, the dye-containing fine particles 2 may contain the dye 3, the singlet oxygen quencher 4, the antioxidant 5 and the ultraviolet absorber 6 inside, and the structure of the particles. Is not particularly limited. However, from the viewpoint of further suppressing the arrival of ultraviolet rays with respect to the dye 3, it is preferable that the dye 3 is arranged at the center of the dye-containing fine particles 2 and the ultraviolet absorber 6 is arranged at the outer periphery of the dye-containing fine particles 2.

  Specifically, as shown in FIG. 2, the dye-containing fine particles 2 </ b> A may have a core-shell structure having a core portion 8 and a shell portion 9 that covers the periphery of the core portion 8. The core portion 8 preferably contains the dye 3, the singlet oxygen quencher 4 and the antioxidant 5, and the shell portion 9 preferably contains the ultraviolet absorber 6. As described above, the singlet oxygen quencher 4 and the antioxidant 5 are disposed together with the dye 3 in the core portion 8, whereby the oxidation of the dye 3 can be suppressed. Furthermore, since the ultraviolet absorber 6 is disposed on the outer periphery of the dye 3, the short wavelength light is absorbed by the shell portion 9 and the short wavelength light is difficult to reach the dye 3, thereby further suppressing deterioration of the dye 3. It becomes possible to do.

  The core portion 8 may contain an ultraviolet absorber 6 in addition to the dye 3, the singlet oxygen quencher 4 and the antioxidant 5. However, from the viewpoint of promoting the absorption of short-wavelength light and suppressing the deterioration of the pigment, the content of the ultraviolet absorber 6 is preferably higher in the shell portion 9 than in the core portion 8.

  In the core portion 8, the same material as that of the particulate material 7 can be used as the resin covering the dye 3, the singlet oxygen quencher 4, and the antioxidant 5. In the shell portion 9, the same material as that of the particleizing material 7 can be used for the resin covering the ultraviolet absorbent 6. However, it is preferable that the shell portion 9 is made of a material having a high gas barrier property and further suppresses contact between the dye 3 and oxygen. As a material having such a gas barrier property, for example, a high gas barrier resin such as polyvinylidene chloride (PVDC) or polyvinyl alcohol (PVA) can be used. In addition, as a material having gas barrier properties, metal oxides such as silica and derivatives thereof can also be used.

[Method for Manufacturing Wavelength Control Optical Member]
Next, the manufacturing method of a wavelength control optical member is demonstrated. The manufacturing method of the wavelength control optical member according to the present embodiment is not particularly limited as long as the dye-containing fine particles 2 can be dispersed in the matrix resin 1.

  Specifically, first, the above-mentioned pigment-containing fine particles are dispersed in a solvent, and then the matrix resin is dissolved in the dispersion. Then, the wavelength control optical member can be obtained by applying the dispersion liquid on the substrate and removing the solvent. The method for applying the dispersion liquid to the substrate is not particularly limited, and for example, a spray coating method, a spin coating method, a slit coating method, a roll coating method, or the like can be used. Moreover, when removing a solvent, you may use a vacuum dryer, a convection oven, IR oven, a hotplate, etc.

  A transparent substrate can be used as the substrate to which the dispersion is applied, and for example, a glass plate such as soda lime glass, low alkali borosilicate glass, or non-alkali aluminoborosilicate glass can be used. In addition, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can also be used.

  The wavelength control optical member can also be manufactured by the following method. First, after the above-mentioned pigment-containing fine particles are dispersed in a solvent, a matrix resin precursor is dissolved in the dispersion. In that case, a polymerization initiator is added as needed. Then, the wavelength control optical member can be obtained by applying the dispersion to a substrate and polymerizing and curing the precursor of the matrix resin. When the matrix resin is a thermosetting resin, it is cured by heating, and when it is an active energy ray curable resin, it is cured by an active energy ray (electromagnetic wave, ultraviolet ray, visible ray, infrared ray, electron beam, γ ray, etc.). It can be carried out.

  In addition to the matrix resin and the pigment-containing fine particles, other additives may be added to the above dispersion. Examples of the additive include a plasticizer, a polymerization stabilizer, an optical brightener, a magnetic powder, an ultraviolet absorber, an antistatic agent, and a flame retardant.

  The manufacturing method of the pigment | dye containing fine particle 2 will not be specifically limited if it can be set as the particle | grains which contain the above-mentioned pigment | dye 3, the singlet oxygen quencher 4, the antioxidant 5, and the ultraviolet absorber 6 in the particle-ized material 7. FIG. The pigment-containing fine particles 2 can be produced by, for example, an interfacial polymerization method, a W / O-based in-liquid drying method, a stover method, and a spray drying method. The dye-containing fine particles 2 can also be produced, for example, by an in situ polymerization method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melt dispersion cooling method, or an air suspension coating method.

  The interfacial polymerization method is a method in which a hydrophobic monomer and a hydrophilic monomer are combined to form particles using a chemical reaction at the interface of emulsion droplets. Specifically, first, an oil phase premix in which oil-soluble monomers (precursor of particulate material) and active ingredients (pigment, singlet oxygen quencher, antioxidant and ultraviolet absorber) are uniformly mixed is prepared. Make it. Furthermore, an aqueous phase containing a water-soluble monomer and an emulsifying dispersant for reacting with an oil-soluble monomer to form a film is prepared. Next, the oil phase premix is dispersed in the prepared aqueous phase. The obtained emulsified dispersion (O / W emulsion or W / O emulsion) is heated and polymerized by heating at the interface between the oil phase and the water phase, whereby the dye-containing fine particles 2 can be obtained. .

  In the W / O-in-liquid drying method, first, a solution of a wall film material (precursor of particulate material) in which a core material (pigment, singlet oxygen quencher, antioxidant and ultraviolet absorber) is emulsified or dispersed. Is made. Next, the solution in which the wall membrane material is dissolved is removed by dispersing the wall membrane material solution in a water medium and heating or reducing the pressure while stirring. Thereby, the pigment | dye containing microparticles | fine-particles 2 can be produced in an aqueous medium.

  When the particulate material is made of a silica-based material, the dye-containing fine particles 2 can be produced by a Stover method. In other words, the above-described alkoxysilane and catalyst are added to an alcohol solution in which a dye, a singlet oxygen quencher, an antioxidant and an ultraviolet absorber are mixed, and the mixture is stirred, heated and dried to produce the dye-containing fine particles 2. be able to.

  Thus, the wavelength control optical member of this embodiment can be produced by a known film forming method. Furthermore, the pigment-containing fine particles 2 in the wavelength control optical member can also be produced by a known granulation method. Therefore, the wavelength control optical member of this embodiment can be manufactured at low cost.

[Light emitting device]
Next, the light emitting device according to this embodiment will be described. The light emitting device of this embodiment includes a light emitting element, a wavelength conversion member that converts the wavelength of light emitted from the light emitting element, and the above-described wavelength control optical member.

  In FIG. 3, the LED module 11 which is an example of a light-emitting device is shown. In the LED module 11, an LED element 13 as a light emitting element is mounted on a circuit board 12. The LED element 13 is covered with a wavelength conversion member 14.

  The LED element 13 is a blue LED element that has a main light emission peak in a range of, for example, 380 to 500 nm and emits blue light. Examples of such LED elements 13 include gallium nitride-based LED elements.

  The wavelength conversion member 14 contains, for example, at least one phosphor 15 of a blue phosphor, a green phosphor, a yellow phosphor, and a red phosphor in a translucent material such as a silicone resin. The blue phosphor is excited by the light emitted from the LED element 13 and emits blue light. The green phosphor and the yellow phosphor are also excited by the light emitted from the LED element 13, and emit green light and yellow light, respectively.

The blue phosphor has an emission peak in the wavelength range of 470 nm to 500 nm, the green phosphor has an emission peak in the wavelength range of 500 nm to 540 nm, and the yellow phosphor has an emission peak in the wavelength range of 545 nm to 595 nm. . Examples of the blue phosphor include BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Ba ₃ MgSi ₂ O ₈ : Eu ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ^{2+, and the} like. Examples of the green phosphor include (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ , Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Mn ^2+. Can be mentioned. Examples of the yellow phosphor include (Sr, Ba) ₂ SiO ₄ : Eu ²⁺ , (Y, Gd) ₃ Al ₅ O ₁₂ : Ce ³⁺ , and α-Ca-SiAlON: Eu ²⁺ .

The red phosphor is excited by the LED element 13 and / or the emitted light of at least one of the green phosphor and the yellow phosphor, and emits red light. The red phosphor has an emission peak in the wavelength region of 600 nm to 650 nm. Examples of the red phosphor include Sr ₂ Si ₅ N ₈ : Eu ²⁺ , CaAlSiN ₃ : Eu ²⁺ , SrAlSi ₄ N ₇ : Eu ²⁺ , CaS: Eu ²⁺ , La ₂ O ₂ S: Eu ³⁺ , Y ₃ Mg ₂ ( AlO ₄ ) (SiO ₄ ) ₂ : Ce ³⁺ .

  A wavelength control optical member 10 that reduces the radiation intensity of at least a part of the light emitted from the LED element 13 or the phosphor 15 is disposed on the emission surface side of the LED module 11. By reducing the intensity of part of the emitted light using such a wavelength control optical member 10, for example, the whiteness of the paper surface irradiated with the emitted light can be increased and the visibility can be improved.

  The light emitting device of the present embodiment uses a wavelength control optical member that has high durability, particularly light resistance and heat resistance. Therefore, desired spectral characteristics can be obtained over a long period of time. Further, when the wavelength control optical member is used as a color filter of, for example, a liquid crystal display device or an organic EL display device, it becomes possible to contribute to high brightness and optical contrast over a long period of time.

[lighting equipment]
Next, the lighting fixture which concerns on this embodiment is demonstrated. The lighting fixture of this embodiment is provided with the above-mentioned light-emitting device.

  In FIG. 4, the desk stand 20 provided with the LED module 11 is shown as an example of a lighting fixture. As shown in FIG. 4, the desk stand 20 has a lighting main body 22 mounted on a substantially disc-shaped base 21. The illumination body 22 has an arm 23, and the lamp module 30 on the distal end side of the arm 23 includes the LED module 11. The illumination main body 22 is provided with a switch 22a, and the lighting state of the LED module 11 is changed by turning on / off the switch 22a.

  As shown in FIG. 5A, the lamp 30 includes a substantially cylindrical base portion 31, a light source unit 32, an orientation control portion 33, a filter 34 made of the above-described wavelength control optical member, and a cover 35. Prepare. The light source unit 32 includes the LED module 11 as shown in FIG. The orientation controller 33 is used to control the light from the light source unit 32 to a desired light distribution, and includes a lens in this embodiment. However, the orientation control unit 33 may have a reflection plate or a light guide plate in addition to the lens depending on the configuration of the illumination device.

  The filter 34 and the orientation control unit 33 may be integrated. As an example, for example, as shown in FIG. 5C, a coating portion 34 b that acts as a filter 34 may be formed by coating the surface of the transparent resin portion 34 a constituting the orientation control portion 33.

  The lighting fixture of the present embodiment uses a wavelength control optical member that has high durability, particularly light resistance and heat resistance of the pigment. Therefore, desired spectral characteristics can be obtained over a long period of time. That is, the lighting fixture of this embodiment can improve the visibility by increasing the whiteness of the paper surface irradiated with radiated light, for example.

  Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to these examples.

[Example 1]
(Preparation of pigment-containing fine particles)
First, a mixed solution is prepared by dissolving a tetraazaporphyrin dye (TAP dye), a singlet oxygen quencher, an antioxidant, and an ultraviolet absorber in a mixed solvent of isopropyl alcohol: ethanol = 1: 4 and stirring. Produced. Next, tetraethoxysilane was added to the mixed solution and stirred, and then a mixed solution of ethanol, ion-exchanged water and ammonia water was added and stirred for 5 hours. Thereafter, the precipitate was filtered and dried to prepare the dye-containing fine particles of this example. The average particle size of the obtained dye-containing fine particles was 1.2 μm. The product name and addition amount of each raw material are as follows.
TAP dye: TAP18 manufactured by Yamada Chemical Co., Ltd .; 1 part by mass Singlet oxygen quencher: CIR-965i manufactured by Nippon Carlit Co., Ltd .; 2 parts by mass UV absorber: IRGANOX (registered trademark) -1010 manufactured by BASF Japan Ltd .; 2.4 parts by mass Antioxidant: TINUVIN (registered trademark) PA144 manufactured by BASF Japan Ltd .; 2 parts by mass Metal alkoxide: Tetraethoxysilane manufactured by Wako Pure Chemical Industries, Ltd .; 5 parts by mass Ion exchange water: 1 mass by mass of tetraethoxysilane 1.8 parts by mass with respect to parts Ammonia water (1N): 0.1 parts by mass with respect to 1 part by mass of tetraethoxysilane

(Production of wavelength control optical member)
The dye-containing fine particles prepared as described above were dispersed in toluene, and then an acrylic resin was added and stirred to prepare a dye-dispersed coating solution. And the test sample of this example was produced by apply | coating the produced pigment dispersion coating liquid on a slide glass plate with a bar coater, and drying and forming a coating film. As the acrylic resin, Acrypet (registered trademark) VH manufactured by Mitsubishi Rayon Co., Ltd. was used.

[Example 2]
A test sample of this example was produced in the same manner as in Example 1 except that the amount of tetraethoxysilane added was 10 parts by mass. The average particle size of the dye-containing fine particles obtained in this example was 1.2 μm.

[Example 3]
(Preparation of pigment-containing fine particles)
First, a mixed solution was prepared by dissolving a tetraazaporphyrin dye (TAP dye), a singlet oxygen quencher, an antioxidant, and an ultraviolet absorber in anhydrous dibutyl ether and stirring. Next, polysilazane was added to the mixed solution and stirred for 12 hours. Thereafter, the precipitate was filtered and dried to prepare the dye-containing fine particles of this example. The average particle size of the obtained pigment-containing fine particles was 1.1 μm. The product name and addition amount of each raw material are as follows.
TAP dye: TAP18 manufactured by Yamada Chemical Co., Ltd .; 1 part by mass Singlet oxygen quencher: CIR-965i manufactured by Nippon Carlit Co., Ltd .; 2 parts by mass UV absorber: IRGANOX-1010 manufactured by BASF Japan Ltd .; 2.4 mass Part Antioxidant: TINUVIN PA144 manufactured by BASF Japan Ltd .; 2 parts by mass Polysilazane: AQUAMICA (registered trademark) NAX120 manufactured by AZ Electronic Materials; 5 parts by mass

(Production of wavelength control optical member)
The dye-containing fine particles prepared as described above were dispersed in toluene, and then an acrylic resin was added and stirred to prepare a dye-dispersed coating solution. The mixing amount of the pigment-containing fine particles and the acrylic resin was the same as that in Example 1. And the test sample of this example was produced by apply | coating the produced pigment dispersion coating liquid on a slide glass plate with a bar coater, and drying and forming a coating film. The acrylic resin used was Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.

[Example 4]
A test sample of this example was produced in the same manner as in Example 3 except that the amount of polysilazane added was 10 parts by mass. The average particle size of the dye-containing fine particles obtained in this example was 0.8 μm.

[Example 5]
(Preparation of pigment-containing fine particles)
First, a mixed solution is prepared by dissolving a tetraazaporphyrin dye (TAP dye), a singlet oxygen quencher, an antioxidant, and an ultraviolet absorber in a toluene: butanol = 1: 4 mixed solvent and stirring. did. Next, an acrylic resin was added to the mixed solution and sufficiently stirred. And ion-exchange water was thrown into this mixed solution, and also after adding a nonionic surfactant, it stirred at 1500 rpm for 2 hours. Thereafter, the precipitate was filtered and dried to prepare the dye-containing fine particles of this example. The average particle size of the obtained pigment-containing fine particles was 0.8 μm. The product name and addition amount of each raw material are as follows. Moreover, the stirrer used at the time of agitation is a lab solution (registered trademark) manufactured by PRIMIX Corporation.
TAP dye: TAP18 manufactured by Yamada Chemical Co., Ltd .; 1 part by mass Singlet oxygen quencher: CIR-965i manufactured by Nippon Carlit Co., Ltd .; 2 parts by mass UV absorber: IRGANOX-1010 manufactured by BASF Japan Ltd .; 2.4 mass Part Antioxidant: TINUVIN PA144 manufactured by BASF Japan Ltd .; 2 parts by mass Acrylic resin: A-165 manufactured by DIC Corporation; 5 parts by mass Ion exchange water: 200 parts by mass with respect to 1 part by mass of acrylic resin Surfactant: Kishida 0.005 parts by mass per 1 part by mass of Bridge 35 manufactured by Chemical Co., Ltd.

(Production of wavelength control optical member)
The dye-containing fine particles prepared as described above were dispersed in toluene, and then an acrylic resin was added and stirred to prepare a dye-dispersed coating solution. The mixing amount of the pigment-containing fine particles and the acrylic resin was the same as that in Example 1. And the test sample of this example was produced by apply | coating the produced pigment dispersion coating liquid on a slide glass plate with a bar coater, and drying and forming a coating film. The acrylic resin used was Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.

[Example 6]
A test sample of this example was produced in the same manner as in Example 3 except that the amount of the acrylic resin used in the dye-containing fine particles was 10 parts by mass. The average particle size of the dye-containing fine particles obtained in this example was 1.0 μm.

[Comparative Example 1]
The TAP pigment | dye of Example 1, a singlet oxygen quencher, antioxidant, and the ultraviolet absorber were thrown into the acrylic resin, and the pigment dispersion coating liquid was produced by stirring. At this time, the concentration of the TAP dye, singlet oxygen quencher, antioxidant and ultraviolet absorber in the acrylic resin was adjusted to be the same as in Example 1.

  And the test sample of this example was produced by apply | coating the produced pigment dispersion coating liquid on a slide glass plate with a bar coater, and drying and forming a coating film. The acrylic resin used was Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.

[Evaluation]
The test samples of Examples and Comparative Examples were deteriorated using a metal weather (registered trademark) tester manufactured by Daipura Wintes Co., Ltd. The total light transmittance of the test sample before and after deterioration was measured with a spectrophotometer (U4100 manufactured by Hitachi High-Technologies Corporation).

From the obtained total light transmittance, the initial transmittance (transmittance before deterioration test, T0) and the transmittance after deterioration test (T1) of the maximum absorption wavelength (595 nm) of the dye are measured. The residual rate was calculated. Table 1 shows the results of the residual ratios of the examples and comparative examples.
[Equation 1]
Residual rate (%) = [transmittance after deterioration test (T1)] / [transmittance before deterioration test (T0)] × 100

  As shown in Table 1, the test samples of Examples 1 to 6 had a residual rate of 60% or more, whereas the test sample of Comparative Example 1 had a residual rate of 55%. From this, it is understood that the durability is improved by making the pigment, the singlet oxygen quencher, the antioxidant and the ultraviolet absorber fine. Further, when Examples 1, 3 and 5 are compared with Examples 2, 4 and 6, respectively, it can be seen that the durability is improved by increasing the amount of the particulate material.

  The entire contents of Japanese Patent Application No. 2014-117245 (filing date: June 6, 2014) are incorporated herein.

  As described above, the contents of the present embodiment have been described according to the examples. However, the present embodiment is not limited to these descriptions, and it is obvious to those skilled in the art that various modifications and improvements are possible. is there.

  In the wavelength control optical member of the present embodiment, a singlet oxygen quencher, an antioxidant, and an ultraviolet absorber as a deterioration inhibiting additive are arranged in the vicinity of the pigment. Therefore, since the effect of the degradation inhibitor is easily exerted on the dye, it is possible to improve the durability of the dye 3, particularly the light resistance and the heat resistance, and to increase the stability of the dye.

DESCRIPTION OF SYMBOLS 1 Matrix resin 2,2A Dye containing fine particle 3 Dye 4 Singlet oxygen quencher 5 Antioxidant 6 Ultraviolet absorber 10 Wavelength control optical member

Claims (7)

A matrix resin, and pigment-containing fine particles dispersed inside the matrix resin,
The wavelength-controlling optical member, wherein the dye-containing fine particles contain a dye having a maximum absorption wavelength in a range of 400 nm to 650 nm, a singlet oxygen quencher, an antioxidant, and an ultraviolet absorber.   2. The matrix resin according to claim 1, wherein the matrix resin contains at least one selected from the group consisting of acrylic resins, polycarbonate resins, acrylic-styrene copolymers, styrene resins, silicone resins, and cycloolefin resins. Wavelength control optical member.   3. The dye according to claim 1, wherein the dye, the singlet oxygen quencher, the antioxidant and the ultraviolet absorber are coated with at least one of an alkoxysilane hydrolysis condensate and polysilazane in the dye-containing fine particles. Wavelength control optical member.   The wavelength control optical member according to any one of claims 1 to 3, wherein the dye is at least one selected from the group consisting of phthalocyanine, tetraazaporphyrin, and porphyrin.   The wavelength control optical member according to any one of claims 1 to 4, wherein an average particle size of the dye-containing fine particles is 100 nm to 30 µm.   A light-emitting device comprising: a light-emitting element; a wavelength conversion member that converts the wavelength of light emitted from the light-emitting element; and the wavelength control optical member according to claim 1.   A lighting fixture comprising the light emitting device according to claim 6.

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