JP2006117857A - Luminous light-emitting device and luminous light-emitting optical fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous light-emitting device capable of extending the afterglow time of the luminous material. <P>SOLUTION: This luminous light-emitting device 300 contains a first luminous phosphor 10 excited by a light of a first exciting wavelength zone and emitting a first afterglow in a first light-emitting wavelength zone, and a second luminous phosphor 11 excited by a light of a second exciting wavelength zone and emitting a second afterglow in a second light-emitting wavelength zone in a light-transmitting and light-conducting member 15. By irradiating the luminous phosphor 10, 11 with the first and second exciting lights, and after stopping the irradiation, the first and second afterglows are emitted for a definite time, further, after stopping the exciting lights, the second luminous phosphor 11 is excited by the first afterglow, and it is possible to extend the lasting time of the second afterglow. It is possible to hold the first and second luminous phosphors 10, 11 on the surface or at the inside of the optical fiber or a light-conductive plate to make the luminous light-emitting optical fiber or light-conducting plate, and it is possible to introduce the exciting light from their end surfaces. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a phosphorescent light-emitting device including a phosphorescent material called a phosphorescent phosphor, an afterglow phosphor, or a phosphorescent phosphor.

The present invention relates to a method for extending the afterglow of a phosphorescent light-emitting device that can extend the afterglow time of the phosphorescent light-emitting device including the phosphorescent material.

Conventionally, as a `` light-storing material '', energy is accumulated by irradiation of excitation light in a predetermined wavelength band (spectrum: SPECTRA) such as ultraviolet light and visible light, and fluorescence light is maintained for a predetermined time after irradiation of the excitation light is stopped. There are known phosphors having phosphorescent properties called phosphorescent phosphors (LIGHT STORAGE PHOSPHOR), afterglow phosphors (AFTERGLOW PHOSPHOR), and phosphorescent phosphors (PHOSPHORESCENT PHOSPHOR).

This type of phosphorescent material is, for example, in the form of particulate or powder phosphorescent pigments (LIGHT STORAGE PIGMENT) and afterglow pigments (AFTERGLOW PIGMENT).

This phosphorescent and afterglow pigment is contained in a light-transmitting paint to form a phosphorescent, afterglow paint, and ink, and is widely used for, for example, a luminous sign, a phosphorescent sign, and an ornament.

The phosphorescent and afterglow pigments are contained in light-transmitting inks to form phosphorescent and afterglow paints and inks, and are widely used for, for example, nocturnal signs, phosphorescent signs, and ornaments.

This phosphorescent and afterglow pigment is contained in a synthetic resin, rubber, elastomer resin molded body and the like to form a phosphorescent and afterglow molded body, and is widely used for, for example, a luminous sign, a phosphorescent sign, and a decorative article.

Patent Document 1 (Japanese Patent 2543825) and Patent Document 2 corresponding to Patent Document 1 (US Pat. No. 5,420,006) are compounds represented by MAl ₂ O ₄ , where M is selected from the group consisting of calcium, strontium, and barium. A compound comprising at least one metal element is converted into a mother crystal, europium is added as an activator, and cerium, praseodymium, neodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium are added as coactivators. An aluminate-based phosphorescent phosphor (ALUMINATE PHOSPHORESCENT PHOSPHOR), which is a double oxide of aluminum and metal, to which at least one element of the group consisting of:

Patent Document 2 (US Pat. No. 5,424,006) is a US patent corresponding to Patent Document 1.

Japanese Patent Laid-Open No. 2000-144129 (Patent Document 3) discloses a compound represented by MAl4 O7 (where M is at least one metal element selected from the group consisting of Mg, Ca, Sr, and Ba). As a material, Eu is added as an activator, and Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta, W, Bi, La, Ce, Disclosed is a phosphorescent phosphor excited by visible light, which is constituted by adding at least one element selected from Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. ing.

JP 2000-309775 A publication (Patent Document 4), the chemical composition formula _{MO · aSiO 2 · bR 2 O} · cX · dM '2 O 3: Eu y Ln z ( however, M is Ba, Sr, Ca 1 or 2 or more selected from the group consisting of alkaline earth metals such as Mg, Mg and Zn, R is at least one selected from the group consisting of alkali metal ions of Li, Na and K, and X Is at least one selected from the group consisting of F, Cl, Br, and I, M ′ is B or Al, Eu or Pb is used as the activator, Ln (Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Cr, Mn, Bi, Sn, In, Sb, As, Ti, Zr, Hf, P, At least selected from Nb, Ta, V, Mo, W In addition, the above-mentioned JP-A-2000-309775 discloses a wavelength exceeding 530 nm in the emission spectrum after irradiation with visible light. A phosphorescent phosphor having at least one emission peak in the range of more than 440 nm and less than or equal to 530 nm, and exceeding 400 nm in an excitation spectrum having an emission peak wavelength of more than 530 nm. Visible-light-excited phosphorescent phosphor having a maximum excitation wavelength in the range of 450 nm or less and a maximum excitation wavelength in the range of 300 nm to 400 nm in the excitation spectrum having an emission peak wavelength of more than 440 nm and less than 530 nm. ing.

JP-A-11-236524 (Patent Document 5) discloses a phosphorescent ink composed of a phosphorescent pigment for the purpose of providing a phosphorescent ink composition and phosphorescent material capable of emitting a color different from the color emitted by the phosphor. A phosphorescent ink composition containing a phosphor and a fluorescent pigment that emits light by absorbing light energy in a wavelength region emitted by the phosphor, and a phosphorescent body using the phosphorescent ink composition are disclosed. The 0008th stage of the specification describes that the fluorescent pigment cannot store light energy but emits light using the received light energy.

Japanese Patent Laid-Open No. 9-272867 (Patent Document 6) provides a phosphorescent phosphor having long afterglow characteristics, emitting blue to green light, and being chemically stable and excellent in weather resistance. The objective is that the composition formula is (M ¹ _1-ax , M ² _a ) O · n (Al _1-b , B _b ) ₂ O ₃ : Eu _x , X _y where M ¹ is Sr, Ca , Ba, M ² represents Be, Mg, Zn, Cd, X represents F, Cl, Br, I, and a, b, n, x, y satisfy the following ranges.・ ・ ≦ ・ ・ ≦ ・ ・ ・ ・, 0 <・ ・ ≦ ・ ・ ・ ・, ・ ・ ・ ≦ ・ ・ ≦ ・ ・ ・ ・, ^-5 ≦ x ≦ ・ ・... ⁻¹ ,... ^-5 ≦ y ≦ ・ ・ ・ ・ ・⁻¹ ), Eu-activated aluminate phosphors are disclosed. Further, in the specification of the above-mentioned JP-A-9-272867, the 0029 stage includes an Eu-activated aluminate phosphor having a composition of Sr _0.999 Mg _0.005 Al _1.996 B _0.004 O ₄ : Eu _0.001 F _0.002 at a wavelength of 365 nm. It is disclosed that the emission peak wavelength of the emission spectrum when excited has a green light emission storage property of 520 nm, and that the excitation spectrum extends to the visible range.

In JP-A-9-146484 (Patent Document 7) and a patent publication (2917878) corresponding thereto, a display pattern is formed of an afterglow phosphor on the main surface side of a transparent light guide plate, and At least one place on the end face of the light guide plate is equipped with a light source that emits light that can excite the afterglow phosphor. It is disclosed.

In JP-A-2000-171638 (Patent Document 8), in an optical fiber composed of a core material and a clad material, the light source is turned on when the light source is turned on, for example, by adding a phosphorescent material to all or part of the clad material. An optical fiber is disclosed that emits light by incident light and emits light from the phosphorescent material as a light source for a certain period of time after the light source is extinguished, and does not immediately stop functions such as guide illumination when the light source is extinguished. ing.

Nemoto Special Chemical Co., Ltd. (NEMOTO & CO. LTD, TOKYO, JAPAN) WEB home page (Non-patent Document 1) WEB home page (URL: www.nemoto.co.jp) Superluminous phosphorescent pigments containing an aluminate compound called “Luminova (registered trademark)” and LumiNova (Trade Mark) as main components and a rare earth element activator attached and disclosed are disclosed. According to the WEB home page, Luminova super-afterglow phosphorescent pigment is a substance that has 10 times the brightness of the initial brightness and 10 times the brightness of afterglow compared to the copper-doped zinc sulfide (ZnS: Cu) phosphor. . (Phosphorescent substance mainly composed of aluminate compound described in Patent Documents 1 and 2).

According to the WEB home page, commercially available Luminova (registered trademark) phosphorescent pigments have excitation peak wavelength 365 nanometers (following nm), emission peak wavelength 520 nm, emission color (green), body color (green white), specific gravity 3.6, Chemical composition SrAl ₂ O ₄ : Eu, Dy green luminescent phosphorescent pigment (G-300 series, product names G-300C, G-300M, G-300FF, G-300FFS), excitation peak wavelength 365nm, emission peak wavelength 490nm, luminescence Blue (blue), body color (yellowish white), specific gravity 3.9, chemical composition Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy blue luminous phosphorescent pigment (BG-300 series, product names BG-300M, BG-300F, BG-300FF ), Excitation peak wavelength 325 nm, emission peak wavelength 440 nm, emission color (purple), body color (white), specific gravity 3.0, chemical composition CaAl ₂ O ₄ : Eu, Nd purple emission phosphorescent pigment (V-300 series, product name V -300C, V-300M).

Nemoto Special Chemical Co., Ltd.'s U.S. agency United Mineral and Chemical Corporation (UMC) website (URL: www.umccorp.com) There is disclosed a super afterglow phosphorescent pigment mainly composed of an aluminate compound called “Luminova” (registered trademark) and “LumiNova” (Trade Mark) manufactured by Chemical, and fired with an activator of a rare earth element.

According to Honeywell Specialty Chemicals Shields GMBH, GERMANY website (URL: www.lumiluxpigments.com) (Non-Patent Document 3), "Lumilux (registered trademark)" , ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ "(LONG AFTERGLOW PIGMENTS), which is a long-term phosphorescent pigment that emits ultraviolet light, sunlight, or visible light, is commercially available under the trademark" Trade Mark " .

That is, as a long-time phosphorescent pigment of LUMILUX (registered trademark), a long-time phosphorescent pigment (LONG AFTERGLOW PIGMENTS) that emits ultraviolet light, sunlight, or visible light is used as a long-lasting phosphorescent pigment (LUMILUX (registered trademark) long afterglow pigment). For example, Green SN-F25 (Part No. 50104, excitation light, UV, sunlight, emission color, green, body color, yellowish green), Green SN-F22 (Part No. 50100, LUMILUX TM LONG AFTERGLOW PIGMENTS) Excitation light, UV, sunlight, emission color, green, body color, yellow green), Green SN-F2 (Part No. 50095, excitation light, UV, sunlight, emission color, green, body color, yellow green), Green SN -F3 (Part No. 50097, excitation light, UV, sunlight, luminescent color, green, body color, yellowish green).

Furthermore, as a long-term phosphorescent pigment of LUMILUX (registered trademark), Effect Blue SN (product number 50034, excitation light, UV, solar, commercially available under the name "LUMILUX TM EFFECT PIGMENTS") Light, Emission Color, Blue, Body Color, Yellow), Effect Blue SN-F (Part No. 50036, Excitation Light, UV, Sunlight, Emission Color, Blue, Body Color, Yellow), Effect Green N (Part No. 50000, Excitation Light) , UV, sunlight, luminescent color, green, body color, yellowish green), Effect Green NL (part number 50026, excitation light, UV, sunlight, luminescent color, green, body color, yellowish green), Effect Green NE (part number) 50915, excitation light, UV, sunlight, emission color, green, body color, yellow-green), Effect Green NF (Part No. 50081, excitation light, UV, sunlight, emission color, green, body color, yellow-green), Effect Green N-FG (Part No. 50081, excitation light, UV, sunlight, emission color, green, body color, yellowish green), Effect Green N-FF (Part No. 50018, excitation light, UV, sunlight, emission color, yellow, Body color, yellowish green), Effect Sipi F Yellow SN (Part No. 50080, excitation light, UV, sunlight, emission color, yellow-green, body color, yellow), Effect Sipi Yellow (Part No. 50070, excitation light, UV, sunlight, emission color, yellow-green, body color , Yellow), Effect Sipi Red (Part No. 50071, excitation light, UV, sunlight, emission color, orange, body color, red), Effect Red N100 (Part No. 50031, excitation light, UV, sunlight, emission color, red, Body color, pink).

According to the company's website (URL: www.nichia.co.jp) (Non-Patent Document 4), phosphorescent phosphors commercially available from NICHIA CORPORATION, JAPAN Light-emitting body called “Ultra Glow (trade name)”, ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ”, product number NP-2810: Luminescent color; Blue-violet, Body color; White, Luminescent peak Wavelength; 440 nm, chemical composition; CaAl ₂ O ₄ Eu, Nd, product number NP-2820: Emission color; Blue green, body color; Pale yellow, Emission peak wavelength; 490 nm, Chemical composition; Sr ₄ Al ₁₄ O: Eu, Dy , Part number NP-2830: luminescence color; green, body color; light yellow, luminescence peak wavelength; 520 nm, chemical composition; SrAl ₂ O ₄ : Eu, Dy, NP-2840: luminescence color; orange, body color; light yellow , Emission peak wavelength; 625 nm, chemical composition; Y ₂ O ₂ S: Eu, Mg, Ti, NP-2850: emission color; red, body color; white, emission peak wavelength; 625 nm, chemical composition; Y ₂ O ₂ S : Eu, Mg, Ti etc.

According to the company's website (URL: www.dayglo.com) (Non-Patent Document 5), phosphorescent phosphors commercially available from DAYGLO COLOR CORPORTION, USA (Registered trademark) "," NightGlo "(Trade Mark), an afterglow illuminant, a luminescent pigment (GLOW-IN-THE-DARK PIGMENT), for example, product number NGX-19: emission color; blue, emission peak wavelength; 470nm , Chemical composition; Sr ₂ MgSi ₂ O ₇ : Dy, Eu, product number NGX-6Y or NGX-UF: Emission color; yellowish green, emission peak wavelength; 520 nm, chemical composition; SrAl ₂ O ₄ : Dy, Eu, product number NG25 : Emission color; orange, emission peak wavelength; 620 nm, chemical composition; ZnS: Mn, Cu, etc.

Japanese Patent 2543825 Patent Gazette US Patent 5424006 Patent Gazette JP 2000-144129A Japanese Unexamined Patent Publication No. 2000-309775 Japanese Unexamined Patent Publication No. 11-236524 Japanese Unexamined Patent Publication No. 9-272867 JP 9-146484 A JP 2000-171638 A NEMOTO & CO. LTD, TOKYO, JAPAN website (URL: www.nemoto.co.jp). United homepage of United Mineral & Chemical Corporation (UMC) (URL: www.umccorp.com). Honeywell Specialty Chemicals Shields GmbH, Germany (HONEYWELL SPECIALTY CHEMICALS SEELZE GMBH, GERMANY) WEB home page (URL: www.lumiluxpigments.com). Website on NICHIA CORPORATION, JAPAN (URL: www.nichia.co.jp). USA, Diglo Color Corporation (DAYBLO COLOR CORPORTION, U.S.A.) Website on the web (URL: www.dayglo.com).

In a preferred embodiment of the present invention, it is possible to provide a phosphorescent light emitting device capable of extending the afterglow time of prior art phosphorescent materials called phosphorescent phosphors, afterglow phosphors, phosphorescent phosphors and the like. .

Various aspects (1) to (23) of the present invention are listed below.

 (1) a first phosphorescent phosphor that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band, and the first emission wavelength band is partially or A first phosphorescent phosphor comprising a second phosphorescent phosphor that emits a second afterglow beam having a second emission wavelength band that is excited by a light beam of a second excitation wavelength band that is entirely included. And a second phosphorescent phosphor are arranged so that they can be optically coupled to each other.

 (2) a first phosphorescent phosphor that emits a first afterglow light having a first emission wavelength band including a visible light that is excited by a light having a first excitation wavelength band, and a first emission wavelength band A second afterglow ray having a second emission wavelength band including a second emission wavelength band including a visible ray different from the first emission wavelength band, and excited by a light having a second excitation wavelength band partially or entirely including A phosphorescent light emitting device that is arranged so as to be capable of optically coupling the first phosphorescent phosphor and the second phosphorescent phosphor.

 (3) a first phosphorescent phosphor that is excited by light in the first excitation wavelength band and emits first afterglow light having the first emission wavelength band, and the first emission wavelength band is partially or A first phosphorescent phosphor using a second phosphorescent phosphor that emits a second afterglow beam having a second emission wavelength band and is excited by a light beam of a second excitation wavelength band that is entirely included The first and second afterglow rays are generated for a predetermined time after the excitation light is stopped by irradiating the fluorescent material with the excitation light including the first and second excitation wavelength bands, and the first phosphorescence The second afterglow phosphor from the phosphorescent phosphor irradiates and excites the second phosphorescent phosphor, thereby extending the duration of the second afterglow ray from the second phosphorescent phosphor. Method of emitting phosphorescent phosphor.

 (4) the first phosphorescent phosphor that is excited by the light of the first excitation wavelength band and emits the first afterglow light having the first emission wavelength band, and the first emission wavelength band is partially or A first phosphorescent phosphor using a second phosphorescent phosphor that is excited by a light having a second excitation wavelength band including the entire surface and emits a second afterglow light having a second emission wavelength band. Irradiating an excitation light beam including the first excitation wavelength band to generate a first afterglow light beam for a predetermined time after the excitation light beam is stopped, and a first afterglow from the first phosphorescent phosphor A method for emitting a phosphorescent phosphor comprising irradiating and exciting a second phosphorescent phosphor with light.

 (5) The phosphorescent light-emitting device according to (1) or (2), wherein the first phosphorescent phosphor and the second phosphorescent phosphor are phosphorescent fluorescent pigments.

 (6) Phosphorescent fluorescence in which a first phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments and a second phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments are dispersed in a light transmissive binder (binding material). The phosphorescent light-emitting device according to (1) or (2) above, wherein the phosphorescent phosphor layer is partially or entirely formed on the surface of an arbitrary article.

 (7) Place one of the first phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments and the second phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments in the first light transmissive binder (binding material). The first phosphorescent phosphor layer dispersed and the second phosphorescent phosphor layer in which the other one of the first phosphorescent phosphor and the second phosphorescent phosphor is dispersed in the second light-transmitting binder (binding material), The phosphorescent light-emitting device according to (1) or (2), wherein the first and second phosphorescent phosphor layers are formed by being partially or fully laminated on the surface of an arbitrary article.

(8) Place one of the first phosphorescent phosphor made of a plurality of phosphorescent fluorescent pigments and the second phosphorescent phosphor made of a plurality of phosphorescent fluorescent pigments in the first light transmissive binder (binding material). The first phosphorescent phosphor layer dispersed and the second phosphorescent phosphor layer in which the other one of the first phosphorescent phosphor and the second phosphorescent phosphor is dispersed in the second light-transmitting binder (binding material), (1) The first and second phosphorescent phosphor layers are formed on the first and second surfaces, respectively, through any light-transmitting article having the first and second surfaces facing each other. Or the luminous light emitting device according to (2).

 (9) The first phosphorescent phosphor and the second phosphorescent phosphor according to the above (1) or (2) are composed of the first and second phosphorescent fluorescent pigments, respectively. A luminous phosphor in which the phosphorescent fluorescent pigment is dispersed in a paint or ink containing a light-transmitting resin.

 (10) The first phosphorescent phosphor and the second phosphorescent phosphor according to the above (1) or (2) are each composed of a first phosphorescent phosphorescent pigment and a second phosphorescent phosphorescent pigment, respectively. A phosphorescent light-emitting molded article containing the phosphorescent fluorescent pigment dispersed in a light-transmitting resin molding material.

 (11) The first phosphorescent phosphor and the second phosphorescent phosphor described in the above (1) or (2) are each composed of a first phosphorescent phosphorescent pigment and a second phosphorescent phosphorescent pigment, respectively. A phosphorescent light-emitting element containing the phosphorescent fluorescent pigment in a granular or pellet-shaped light-transmitting resin member.

 (12) The first phosphorescent phosphor and the second phosphorescent phosphor according to (1) or (2) are each composed of a first phosphorescent fluorescent pigment and a second phosphorescent fluorescent pigment, Disperse one of the first and second phosphorescent fluorescent pigments in the form of a granular or pellet light transmissive core (core) and the other of the first and second phosphorescent fluorescent pigments And a light-storing light-emitting element comprising a light-transmitting shell member that covers the light-transmitting core member.

 (13) a first phosphorescent phosphor particle that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band; and a first emission wavelength band partially Or the second phosphorescent phosphor particles that are excited by the light of the second excitation wavelength band that is entirely included and emit the second afterglow light having the second emission wavelength band, and the core having the light guiding property The first and second phosphorescent phosphor particles are supported on an optical fiber comprising a core having a light-transmitting clad covering the core and the surface or side surface of the core in whole or in part. Phosphorescent light-emitting optical fiber. (15) A light beam that excites the first and second phosphorescent phosphor particles from the end face of the optical fiber can be introduced into the core. (16) The first and second phosphorescent phosphor particles may be dispersed in the core. (17) Either one of the first and second phosphorescent phosphor particles may be dispersed and contained in the core, and the other may be dispersed and contained in the clad. (d) The first and second phosphorescent phosphor particles may be dispersed and contained in the clad. (18) The clad comprises a first clad and a second clad, and one of the first and second phosphorescent phosphor particles is dispersed in either the first or second clad. May be included.

 (19) a plurality of first phosphorescent phosphor particles that are excited by a light beam in a first excitation wavelength band and emit a first afterglow light beam having a first emission wavelength band; and a first emission wavelength band A plurality of second phosphorescent phosphor particles that emit a second afterglow light beam having a second emission wavelength band that is excited by a light beam of a second excitation wavelength band partially or wholly opposed to each other. The first and second end surfaces are supported on a plate-shaped light-guiding member having a light transmittance composed of a first surface and a second surface, and a first end surface and a second end surface facing each other, from the first end surface and / or the second end surface. A luminous light-emitting device that introduces the light beam into the plate-like light-guiding member. (20) The phosphorescent light emitting layer comprising the first and second phosphorescent phosphor particles dispersed and contained in a light transmissive binder layer, wherein the phosphorescent light emitting layer is the first surface and / or It may be formed partially or entirely on the second surface. (21) Further, at least one light emitting diode for introducing the light beam into the plate light guide member may be provided, and the light emitting diode may be disposed on the first end face and / or the second end face. (22) The first and second phosphorescent phosphor particles may be dispersed and contained in the plate-like light guide member. (23) Either one of the first and second phosphorescent phosphor particles is contained dispersed in the plate-like light guide member, and the other of the first and second phosphorescent phosphor particles is The phosphorescent light emitting layer dispersed and contained in the light transmissive binder layer may be provided, and the phosphorescent light emitting layer may be partially or entirely formed on the first surface and / or the second surface.

The first phosphorescent fluorescence that is preferably used in various forms of the present invention and that emits a first afterglow beam having a first emission wavelength band including a visible light beam that is excited by a light beam having a first excitation wavelength band. As the body, for example, Luminova (registered trademark) phosphorescent pigment manufactured by Nemoto Special Chemical Co., Ltd., excitation peak wavelength 365 nm, emission peak wavelength 490 nm, emission color (blue), body color (yellowish white), specific gravity 3.9 , Chemical composition Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy blue luminous phosphorescent pigment (BG-300 series, product name BG-300M, BG-300F, BG-300FF), excitation peak wavelength 325nm, emission peak wavelength 440nm, emission color (Purple), body color (white), specific gravity 3.0, purple light-emitting phosphorescent pigment (V-300 series, product names V-300C, V-300M) having chemical composition CaAl ₂ O ₄ : Eu, Nd.

Examples of other first phosphorescent phosphors that can be preferably used in various forms of the present invention include, for example, the above-mentioned “LUMILUX (registered trademark) Effect Pigment” manufactured by Honeywell Specialty Chemicals Shield GmbH, Germany. Effect Blue SN (Part No. 50034, excitation light, UV, sunlight, emission color, blue, body color, yellow), Effect Blue SN-F ² (Part No. 50036, excitation light) sold under the name LUMILUX TM EFFECT PIGMENTS) , UV, sunlight, emission color, blue, body color, yellow), Effect Blue-green SN ² (Part No. 50091, excitation light, UV, sunlight, emission color, blue-green, body color, yellow-green), Effect Blue -green SN-F ² (Part No. 50092, excitation light, UV, sunlight, emission color, blue green, body color, yellowish green).

Still other first phosphorescent phosphors that can be preferably used in various forms of the present invention include, for example, phosphorescent phosphors commercially available from the aforementioned NICHIA CORPORATION, JAPAN, long Afterglow illuminator `` Ultra GLOW '', product number NP-2810: Emission color; Blue purple, Body color; White, Emission peak wavelength; 440 nm, Chemical composition; CaAl ₂ O ₄ Eu, Nd NP-2820: luminescent color; blue green, body color; light yellow, luminescence peak wavelength; 490 nm, chemical composition; Sr ₄ Al ₁₄ O: Eu, Dy.

Still another first phosphorescent phosphor that can be preferably used in various forms of the present invention is a phosphorescent phosphor “Nightgro” (registered trademark) commercially available from DAYBLO COLOR CORPORTION, USA. ) "," NightGlo "(Trade Mark), for example product number NGX-19: emission color; blue, emission peak wavelength; 470 nm, chemical composition; Sr ₂ MgSi ₂ O ₇ : Dy, Eu, product number NGX-6Y or NGX-UF : Luminescent color; yellowish green, emission peak wavelength; 520 nm, chemical composition; SrAl ₂ O ₄ : Dy, Eu, etc.

As other first phosphorescent phosphors that can be preferably used in various forms of the present invention, for example, selected from various phosphorescent phosphors described in the specifications of Patent Document 1 to Patent Document 6 are used. Also good.

A second phosphorescent phosphor that emits a second afterglow beam having a second emission wavelength band including a visible light beam that is excited by a light beam having a second excitation wavelength band that can be preferably used in various embodiments of the present invention. For example, a compound represented by MAl4 O7 described in JP-A-2000-144129 (Patent Document 3) mentioned above (where M is at least one selected from the group consisting of Mg, Ca, Sr, Ba) Two or more metal elements) as a base material, Eu is added as an activator, and Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta, Excited by visible light constituted by adding at least one element selected from W, Bi, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Phosphorescent phosphor .

In FIG. 1 and the specification Nos. 0014 and 0015 of the aforementioned Japanese Laid-Open Patent Publication No. 2000-144129, 0.7 mol% of Eu as an activator and 0 as a co-activator are included in SrAl ₄ O ₇ as a base material. The phosphorescent phosphor powder of the chemical formula SrAl ₂ O ₄ : Eu, Dy, which was baked at 1300 ° C. for 4 hours in a reducing atmosphere (Ar + H ₂ , 5%) after adding 3 mol% Dy, Since the peak wavelength of the excitation spectrum is 427 nm, it is also excited by visible light, and the peak wavelength of the emission spectrum is 490 nm, this phosphorescent phosphor is suitable as the second phosphorescent phosphor of the second embodiment of the present invention. Used.

As other visible light excitation phosphorescent phosphors that can be preferably used in the first and second embodiments of the present invention, for example, using the visible light excitation phosphorescent phosphor disclosed in the above-mentioned JP-A-2000-309775 publication Also good.

The visible light excitation phosphorescent phosphors, the chemical composition formula _{MO · aSiO 2 · bR 2 O} · cX · dM '2 O 3: Eu y Ln z ( however, M is Ba, Sr, Ca, alkaline earth such as Mg One or two or more selected from the group consisting of similar metals and Zn, R is at least one selected from the group consisting of alkali metal ions of Li, Na and K, and X is F, Cl, Br And at least one selected from the group consisting of I, M ′ is B or Al, Eu or Pb is used as an activator, and Ln (Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Cr, Mn, Bi, Sn, In, Sb, As, Ti, Zr, Hf, P, Nb, Ta, V, At least one selected from Mo and W For example, it is excited by visible light having a maximum excitation wavelength in the range from 400 nm to 450 nm, emits visible light having an emission peak wavelength exceeding 530 nm, and ranges from 300 nm to 400 nm. It is a visible light-excited and visible-light-emitting phosphor that is excited by visible light having the maximum excitation wavelength and emits visible light having an emission peak wavelength in the range from 440 nm to 530 nm.

Still another second phosphorescent phosphor that can be preferably used in various embodiments of the present invention has an excitation spectrum extending from the ultraviolet to the visible range, for example, Sr _0.999 Mg described in JP-A-9-272867. _Examples include Eu-activated aluminate phosphors having a composition of _0.005 Al _1.996 B _0.004 O ₄ : Eu _0.001 F _0.002 .

With reference to FIG. 1, a phosphorescent light-emitting device and a light-emitting method thereof according to the present invention will be described.

FIG. 1 is a schematic graph showing the relationship between the excitation wavelength and the emission wavelength of the first phosphorescent phosphor and the second phosphorescent phosphor.

In FIG. 1, the vertical axis represents the intensity of the excitation light (arbitrary unit) and the luminance of the emitted light (arbitrary unit), and the horizontal axis represents the emission wavelength.

In FIG. 1, the first phosphorescent phosphor is excited by the light beam EX-1 in the first excitation wavelength band and emits the first afterglow light beam AG-1 having the first emission wavelength band including visible light. The second phosphorescent phosphor is excited by the light beam EX-2 in the second excitation wavelength band, and emits the second afterglow light beam AG-2 having the second emission wavelength band including visible light. Both the first phosphorescent phosphor 10 and the second phosphorescent phosphor 12 have an excitation light wavelength band (spectrum: SPECTRUM) and a maximum wavelength (peak spectrum: PEAK SPECTRUM). An afterglow or phosphorescent phosphor that emits afterglow for a relatively long time.

As shown in FIG. 1, the first phosphorescent phosphor 10 absorbs and accumulates the energy of the light beam EX-1 by the excitation irradiation of the light beam EX-1 in the first wavelength band, and the wavelength after that even after the irradiation is stopped. This is a Stokes type and down conversion type phosphorescent phosphor that emits a first afterglow beam AG-1 having a long first emission wavelength band for a predetermined time. The second phosphorescent phosphor 12 absorbs and accumulates the energy of the light beam EX-2 by irradiation with the excitation light beam EX-2 in the second wavelength band (spectrum), and has a wavelength longer than that after the irradiation is stopped. A second afterglow ray AG-2 having two emission wavelength bands is emitted for a predetermined time.

The first phosphorescent phosphor and the second phosphorescent phosphor can excite both phosphorescent phosphors, including ultraviolet rays, including visible light, for example, ultraviolet rays, visible rays, solar rays including all infrared rays, or fluorescence. Light, black light, germicidal lamp, xenon lamp, halogen lamp, incandescent bulb, light-emitting diode, semiconductor laser, etc. The first afterglow ray AG-1 and the second afterglow ray AG-2 are emitted for a predetermined time after the stop.

The first phosphorescent phosphor and the second phosphorescent phosphor are arranged so that they can be optically coupled, and the first afterglow beam AG-1 from the first phosphorescent phosphor has the first Since the emission wavelength band partially or completely includes the second excitation wavelength band of the second phosphorescent phosphor, the second phosphorescent phosphor remains the first afterglow even after the irradiation is stopped. The second phosphorescent phosphor keeps emitting the second afterglow ray AG-2 for a longer time than its own afterglow time, and continues to be excited by the light ray AG-1.

Various embodiments of the invention will now be described with reference to the accompanying drawings. In all the drawings, the same or similar components, parts and members are denoted by the same reference numerals.

(First embodiment of the present invention)

The first embodiment of the present invention will be described in detail with reference to FIGS. 1, 2, and 3 again.

FIG. 1 is a conceptual graph showing the relationship between the excitation wavelength and emission wavelength of the first phosphorescent phosphor and the second phosphorescent phosphor as described above.

2 and 3 show the phosphorescent light emitting device 100 of the first embodiment, FIG. 2 is a partially conceptual perspective view partially cut away and FIG. 3 is (3) of FIG. -(3) It is a conceptual expanded sectional view cut | disconnected along the line.

2 and 3, the first phosphorescent phosphor particle 10 is schematically represented by an ellipse, and the second phosphorescent phosphor 11 is schematically represented by a circle. 2 and 3, the phosphorescent light emitting device 100 is a transparent, translucent light transmissive or opaque (non-light transmissive) sheet-like, plate-like support 30 and one surface (or both surfaces) of the support. The phosphorescent light emitting layer 20 is formed on the substrate. In order to distinguish between the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11, the first phosphorescent phosphor particles 10 are schematically represented by an ellipse, and the second phosphorescent phosphor particles 10 The body 11 is schematically represented by a circle.

In FIG. 1, FIG. 2 and FIG. 3, the phosphorescent light emitting layer 20 is excited by the light beam EX-1 in the first excitation wavelength band, and the first afterglow light beam having the first light emission wavelength band including visible light. A plurality of first phosphorescent particles 10 in the form of particles and powder that emit AG-1 and a second emission wavelength band including visible light that is excited by the light EX-2 in the second excitation wavelength band A plurality of particulate and powdery second phosphorescent phosphors 11 emitting a second afterglow ray AG--2 having a light-transmitting binder (binder) The phosphorescent light emitting layer 20 is a mixture of two phosphorescent phosphor particles 10 and 11 which are dispersed, coated, dried, cured, and solidified in 13. At this time, in order to optically couple the first and second phosphorescent phosphors 10 and 11 in the phosphorescent light emitting layer 20, the two phosphorescent phosphors 10 and 11 are adjacent to each other as much as possible. It is desirable that the light-transmitting binder layer 20 be contained so as to be disposed.

For example, two types of phosphorescent phosphor particles (phosphorescent pigments) 10 and 11 are mixed in clear paints such as acrylic resin, acrylic urethane resin, and melamine resin that are transparent to their excitation light and afterglow emission light, Disperse into a phosphorescent paint or phosphorescent ink containing two types of phosphorescent phosphor particles 10 and 11, and apply brush partially or entirely on one or both surfaces of a support 30 such as a sheet or plate. The phosphorescent light emitting layer 20 may be formed by applying and printing by a normal application method or printing method such as spray coating, dip coating, roller coating, or screen printing, and then drying or curing.

In the phosphorescent paint and phosphorescent ink in which two phosphorescent phosphor particles 10 and 11 are mixed and dispersed, the total content of the phosphorescent phosphor particles 10 and 11 varies depending on the application, etc. It may be in the range of about 0.1 to 90 wt% of the light emitting layer 20, usually about 10 to 60 wt%. The actual shapes and dimensions of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11 can be arbitrarily selected depending on the application.For example, the average particle size of the phosphorescent phosphor particles 10, 11 is about 0.1 micrometer. The commercially available phosphorescent pigment having an average particle size of usually about 10 to 50 micrometer may be used. The mixing ratio of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11 can be arbitrarily selected depending on the application, and may be, for example, in the range of 0.1: 1 to 1: 0.1, or may be 1: 1.

For example, sunlight or white fluorescent lamps, black light and white fluorescent lamps, xenon lamps, halogen lamps, UV light-emitting diodes and white light-emitting diodes, etc. The luminescent layer 20 is irradiated for a predetermined time to excite the two types of phosphorescent phosphor particles 10 and 11. This irradiation time varies depending on the type of light source, irradiation intensity, and distance from the light source, but is, for example, about 10 minutes to 1 hour.

This irradiation is via the light transmissive support 30 when using a light transmissive support 30 such as an acrylic resin, polycarbonate resin, polyethylene terephthalate resin or the like, or a transparent polymer or transparent glass. When using any opaque organic or inorganic light shielding support 30 such as resin, metal, colored glass, ceramic, etc. from the luminous phosphor layer 20 side, the exposure is performed from the exposed surface side of the luminous phosphor layer 20.

The first phosphorescent phosphor 10 is mainly excited by the light EX-1 in the first excitation wavelength band rich in ultraviolet rays having a wavelength of 380 nm or less, absorbs and accumulates its light energy, and is purple and blue after excitation for a predetermined time. The afterglow ray AG-1 by the first visible light having a relatively short wavelength such as the afterglow is emitted continuously for a predetermined time.

The second phosphorescent phosphor 20 is excited and absorbed by the light beam EX-2 in the second excitation wavelength band, which is rich in relatively short-wavelength visible light such as purple and blue, and stores the light energy. After the time excitation, the second visible light AG-2 in the second emission wavelength band such as green, yellow, red, etc. having a longer wavelength than the light beam EX-2 in the second excitation wavelength band continuously emits afterglow for a predetermined time. .

The first emission wavelength band of the first afterglow ray AG-1 composed of a relatively short wavelength visible ray from the first phosphorescent phosphor 10 can excite the second phosphorescent phosphor 11. The second excitation wavelength band that is the light beam EX-2 is included partially or entirely. Therefore, the second phosphorescent phosphor 11 is excited by the first afterglow ray AG-1 from the first phosphorescent phosphor 10, absorbs and accumulates its light energy, and after the excitation for a predetermined time, Compared with the afterglow beam AG-1, the second afterglow beam AG-2 by the visible light having a relatively long wavelength such as yellow or red is continuously emitted for a predetermined time.

Thereby the first afterglow light AG-1 for a predetermined time t ₁ lasts from the first phosphorescent phosphor 10, adjacent the second phosphorescent phosphor 10 for a predetermined time t ₁ irradiation, so continues to excite The substantial afterglow time t ₃ of the second phosphorescent phosphor 11 is (t ₃ −t ₂ ) than the afterglow time t ₂ (t ₂ <t ₃ ) of the second phosphorescent phosphor 10 itself. Note that the time can be extended. The first and second afterglow times t1 of the _first afterglow ray AG-1 from the first phosphorescent phosphor 10 are sufficiently longer than the afterglow time t2 of the _second phosphorescent phosphor 10 itself. when using a combination of 2 of the phosphorescent phosphor 10, 11, more substantial decay time t ₃ the second phosphorescent phosphor 10 decay time itself t ₂ of the second phosphorescent phosphor 11 Even can be extended very much.

In the luminous method of the phosphorescent phosphor described above, the first phosphorescence that is excited by the light beam EX-1 in the first excitation wavelength band and emits the first afterglow beam AG-1 having the first emission wavelength band. Phosphor 10 and a second afterglow ray AG- having a second emission wavelength band excited by a light beam in the second excitation wavelength band EX-2 partially or wholly including the first emission wavelength band A plurality of types of phosphorescent phosphors 10 and 11 comprising a second phosphorescent phosphor 11 that emits 2 and the first and second excitation wavelength bands EX-1 Irradiating excitation light containing EX-2 to generate first and second afterglow rays AG-1 and AG-2 for a predetermined time after the excitation light is stopped, and first phosphorescent fluorescence The first afterglow ray AG-1 from the body 10 irradiates and excites the second phosphorescent phosphor 11, and the second afterglow ray AG- from the second phosphorescent phosphor 11 2 duration And it is extended. The light emission color of the phosphorescent light emitting layer 20 is, for example, initially the afterglow ray (for example, purple, blue) AG-1 from the first phosphorescent phosphor 10 and the second phosphorescent phosphor 11 from the second phosphorescent phosphor 11. Afterglow light (e.g., yellow, red) is a mixed color (e.g., green) with AG-2, but the emission color (e.g., purple, blue) of the first phosphorescent phosphor 10 becomes weaker as time elapses. The luminous color (for example, yellow and red) of the phosphorescent phosphor 11 becomes stronger, and finally the luminous color (for example, yellow and red) of only the second phosphorescent phosphor 11 is obtained.

In the above-mentioned JP-A-11-236524 (Patent Document 10), a phosphorescent ink composition capable of emitting a color different from the color emitted by a phosphorescent pigment ((phosphor, phosphorescent phosphor) and phosphorescent substance are described. A phosphorescent ink composition containing a phosphorescent pigment and a fluorescent pigment that emits light by absorbing light energy in a wavelength region emitted by the phosphor, and a phosphorescent body using the phosphorescent ink composition In the technology of Patent Document 10, phosphorescent pigments and fluorescent pigments have completely different chemical compositions, and fluorescent pigments that cannot store light energy due to afterglow rays from phosphorescent pigments and have no phosphorescent action. the excites because merely emit light a different color and luminous pigment, the light emission time t ₃ of the fluorescent pigment is afterglow time of the phosphorescent pigment itself Cannot extend beyond (t ₂ = t ₃ ).

The phosphorescent phosphor preferably used as the first phosphorescent phosphor 10 is, for example, the above-mentioned Luminova (registered trademark) phosphorescent pigment manufactured by Nemoto Special Chemical Co., Ltd., excitation wavelength band of about 200 nm-450 nm, excitation peak wavelength 365 nm, emission peak wavelength 490 nm, emission color (blue), chemical composition Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy blue emission phosphorescent pigment (BG-300 series, product names BG-300M, BG-300F, BG-300FF), Excitation peak wavelength: 325 nm, emission peak wavelength: 440 nm, emission color (purple), purple emission phosphorescent pigment with chemical composition CaAl ₂ O ₄ : Eu, Nd (V-300 series, product names V-300C, V-300M) .

Other first phosphorescent phosphors 10 preferably used include, for example, the above-mentioned “LUMILUX (Effect Pigment)” (LUMILUX TM EFFECT PIGMENTS) by Honeywell Specialty Chemicals Shields GmbH, Germany. Commercially available Effect Blue SN (part number 50034, excitation light: UV, sunlight, emission color: blue), Effect Blue SN-F ² (part number 50036, excitation light: UV, sunlight, emission color: blue) It is done.

Other first phosphorescent phosphors 10 preferably used include, for example, phosphorescent phosphors and long afterglow phosphors “Ultra Glow” commercially available from the aforementioned NICHIA CORPORATION, JAPAN. (Product Name) '' (ULTRA GLOW), product number NP-2810: luminescent color; blue violet, emission peak wavelength; 440 nm, chemical composition; CaAl ₂ O ₄ Eu, Nd, product number NP-2820: luminescent color; blue green, luminescent Peak wavelength; 490 nm, chemical composition; Sr ₄ Al ₁₄ O: Eu, Dy and the like.

As other first phosphorescent phosphors 10 preferably used, for example, as the first phosphorescent phosphor, a phosphorescent phosphor “Night Glo” commercially available from DAYBLO COLOR CORPORTION, USA. “(R)”, “NightGlo” (Trade Mark), for example, product number NGX-19: emission color; blue, emission peak wavelength; 470 nm, chemical composition; Sr ₂ MgSi ₂ O ₇ : Dy, Eu, and the like.

The second phosphorescent phosphor 11 that can be preferably used and emits a second afterglow ray AG-2 having a second emission wavelength band including a visible light ray that is excited by the light ray EX-2 in the second excitation wavelength band. "Is, for example, a compound represented by MAl4 O7 described in JP-A-2000-144129 (Patent Document 3) (wherein M is at least selected from the group consisting of Mg, Ca, Sr, Ba) One or more metal elements) as a base material, Eu is added as an activator, and Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta are added as coactivators. Excitation with visible light composed by adding at least one element selected from W, Bi, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu A phosphorescent phosphor.

In FIG. 1 and the specification Nos. 0014 and 0015 of the aforementioned Japanese Laid-Open Patent Publication No. 2000-144129, 0.7 mol% of Eu as an activator and 0 as a co-activator are included in SrAl ₄ O ₇ as a base material. The phosphorescent phosphor powder of the chemical formula SrAl ₂ O ₄ : Eu, Dy, which was baked at 1300 ° C. for 4 hours in a reducing atmosphere (Ar + H ₂ , 5%) after adding 3 mol% Dy, Since the peak wavelength of the excitation spectrum is 427 nm and it is also excited by visible light and the peak wavelength of the emission spectrum is 490 nm, this phosphorescent phosphor is the second phosphorescent phosphor of the first and second embodiments of the present invention. 11 is preferably used.

The visible light excitation phosphorescent phosphor that can be preferably used is not limited to the visible light excitation phosphorescent phosphor disclosed in the above-mentioned JP-A-2000-144129 publication. For example, the above-mentioned JP-A-2000-309775 publication (Patent Document 4) The visible-light-excited phosphorescent phosphor disclosed in (1) may be used. Visible light excitation phosphorescent phosphor disclosed in Patent Document 4, the chemical composition formula _{MO · aSiO 2 · bR 2 O} · cX · dM '2 O 3: Eu y Ln z ( however, M is Ba, Sr, Ca 1 or 2 or more selected from the group consisting of alkaline earth metals such as Mg, Mg and Zn, R is at least one selected from the group consisting of alkali metal ions of Li, Na and K, and X Is at least one selected from the group consisting of F, Cl, Br, and I, M ′ is B or Al, Eu or Pb is used as the activator, Ln (Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Cr, Mn, Bi, Sn, In, Sb, As, Ti, Zr, Hf, P, Selected from Nb, Ta, V, Mo, W And at least one kind of visible-light-excited phosphorescent phosphor.

Further, as the second phosphorescent phosphor 11, the visible light excitation and visible light emitting phosphorescent material disclosed in the above-mentioned JP 2000-309775 A (Patent Document 4) may be used.

That is, the visible light excitation and visible light emission phosphorescent phosphor disclosed in JP-A-2000-309775 (Patent Document 4) has an emission peak with a wavelength exceeding 530 nm in the emission spectrum after irradiation with visible light. In addition, a phosphorescent phosphor having at least one emission peak in the range of more than 440 nm and not more than 530 nm, and in the excitation spectrum of the emission peak wavelength exceeding 530 nm, the range of more than 400 nm and not more than 450 nm And a phosphorescent phosphor having a maximum excitation wavelength in a range of 300 nm to 400 nm in an excitation spectrum having an emission peak wavelength of more than 440 nm and not more than 530 nm. That is, this phosphorescent phosphor is excited by visible light having a maximum excitation wavelength in the range from 400 nm to 450 nm, emits visible light having an emission peak wavelength exceeding 530 nm, and has a maximum excitation wavelength in the range from 300 nm to 400 nm. It is excited by visible light and emits visible light having an emission peak wavelength in the range from 440 nm to 530 nm.

(Second embodiment of the present invention)

A second embodiment of the present invention will be described in detail with reference to FIG. 1, FIG. 4, and FIG.

In the description of the second embodiment, descriptions that are the same as or overlapped with those of the first embodiment will be omitted as much as possible.

4 and 5 show the phosphorescent light emitting device 200 of the second embodiment, FIG. 4 is a partially conceptual perspective view in which a section is partially cut away, and FIG. 5 is (4) of FIG. -(4) It is the partial conceptual expanded sectional view cut | disconnected along the line.

4 and 5, in order to distinguish the first phosphorescent phosphor particle 10 and the second phosphorescent phosphor 11, the first phosphorescent phosphor particle 10 is schematically represented by an ellipse. The second phosphorescent phosphor 11 is schematically represented by a circle. The actual shapes and dimensions of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11 are arbitrary.

In FIG. 1, FIG. 4, and FIG. 5, the phosphorescent light-emitting device 200 of the second embodiment is excited by the light beam EX-1 in the first excitation wavelength band and has a first light emission wavelength band that includes visible light. Excited by a plurality of particulate and powdery first phosphorescent phosphors 10 emitting a first afterglow ray AG-1 and a light beam EX-2 in the second excitation wavelength band, A plurality of particulate and powdery second phosphorescent phosphors 11 emitting a second afterglow beam AG--2 having a second emission wavelength band including a light-transmitting organic polymer, inorganic glass The two types of phosphorescent phosphors 10 and 11 dispersed directly in the film-like, sheet-like, or plate-like light-transmissive member 17 are mixed and contained. At this time, in order to optically couple the first and second phosphorescent phosphors 10 and 11 in the phosphorescent light emitting layer 20, the two phosphorescent phosphors 10 and 11 are adjacent to each other as much as possible. It is desirable that the light transmissive member 17 is contained so as to be disposed.

As the light transmissive member 17, any film-like, sheet-like, or plate-like light transmissive member such as a transparent polymer having transparency, such as acrylic resin, polycarbonate resin, polyethylene terephthalate resin, transparent silicone rubber, or transparent glass Is used.

When two types of phosphorescent phosphor particles 10 and 11 are mixed and dispersed in the molding material of the light transmissive member 17 to form a phosphorescent molded article such as a sheet or plate, depending on the application, etc. The total content of the phosphorescent phosphor particles 10, 11 may be, for example, in the range of about 0.1 to 90 wt% of the phosphorescent molded article 200, and usually about 5 to 60 wt%.

(Third embodiment of the present invention)

A third embodiment will be described in detail with reference to FIGS.

In the description of the third embodiment, the description common to the first embodiment will be omitted as much as possible.

FIG. 6 shows a phosphorescent light emitting device 300 according to a third embodiment, and FIG. 5 is a conceptual perspective view with a part cut away.

1 and 6, the phosphorescent light emitting device 300 according to the third embodiment is excited by a light beam EX-1 having a first excitation wavelength band, and has a first light emission wavelength band including visible light. A plurality of particulate and powdery first phosphorescent phosphors 10 that emit afterglow rays AG-1 and a second light that is excited by the light beam EX-2 in the second excitation wavelength band and includes visible light. A plurality of particulate and powdery second phosphorescent phosphors 11 emitting a second afterglow beam AG--2 having a light emission wavelength band of light such as an organic polymer or an inorganic glass having light transmittance It is a phosphorescent molded product that is mixed and contained in the transparent molding material 17 and molded into a three-dimensional arbitrary shape (a substantially star-shaped solid is illustrated in FIG. 6).

As the light transmissive molding material 17, any thermoplastic resin having a known light permeability or any heat or light curable resin is used.

Examples of the thermoplastic resin molding material 17 include acrylic resin, polycarbonate resin, polyethylene terephthalate resin, vinyl chloride resin, ethylene vinyl alcohol copolymer, polyethylene, polypropylene, polystyrene, ABS resin, polyacetal resin, polybutylene terephthalate resin, polyamide. And their copolymers, such as polyurethane, and thermoplastic elastomers such as polyurethane and polyethylene. Examples of the thermosetting or photocurable resin molding material 17 include silicone resin, silicone rubber, epoxy resin, unsaturated polyester resin, phenol resin, and melamine resin.

When the two types of phosphorescent phosphor particles 10 and 11 are mixed and dispersed in the molding material of the light transmissive member 17 and molded into a phosphorescent molded article 300 having an arbitrary three-dimensional shape, depending on the application, The total content of the phosphorescent phosphor particles 10 and 11 may be, for example, in the range of about 0.1 to 90 wt%, usually about 5 to 60 wt% of the phosphorescent molded article.

(Fourth embodiment of the present invention)

A fourth embodiment of the present invention will be described in detail with reference to FIGS. 1, 7, 8A, 8B, and 8C.

In the description of the fourth embodiment, descriptions that are the same as or overlapped with the first to third embodiments are omitted as much as possible.

FIG. 7 shows a phosphorescent light emitting device 400 according to a fourth embodiment, and FIG. 7 is a conceptual perspective view partially cut away and taken as a cross section.

8A, 8B, and 8C are conceptual enlarged cross-sectional views showing various phosphorescent members 40, 50, and 60. FIG.

In FIG. 7 (FIGS. 8A, 8B, and 8C), the phosphorescent light-emitting device 400 of the fourth embodiment is excited by the light beam EX-1 in the first excitation wavelength band, and includes the first light beam that includes visible light. Excited by a plurality of particulate and powdery first luminous phosphors 10 emitting a first afterglow ray AG-1 having an emission wavelength band, and a light beam EX-2 in a second excitation wavelength band And a plurality of particulate and powdery second luminous phosphors 11 that emit a second afterglow ray AG--2 having a second emission wavelength band including visible light An organic polymer having a light-transmitting phosphor (granular) -like, granular, pellet-like, or bead-like phosphor-containing member (element containing phosphorescent phosphor) 40, 50, 60, such as inorganic glass. , Any three-dimensional shape mixed in light-transmitting molding material 17 such as inorganic glass (Fig. 7 shows a nearly star-shaped solid), etc. Molded was a luminous molded product.

FIG. 8A shows a granule-like, pellet-like, or bead-like phosphorescent phosphor-containing member (phosphorescent phosphor-containing element) 40. The plurality of first phosphorescent particles are in the form of particles or powders. Body 10 and a plurality of second luminous phosphors 11 in the form of particles and powder, light-transmitting organic polymer, granule such as inorganic glass, pellets, and beads It is dispersed and contained in the permeable material 17. Examples of the light transmissive material 17 include thermosetting resins such as the above-described thermosetting epoxy resins, unsaturated polyester resins, phenol resins, and melamine resins, and thermoplastics such as the above-described acrylic resins, polycarbonate resins, and polyethylene terephthalate resins. A relatively high melting point that does not melt at the molding temperature of the resin is used.

The granule (granule) -like, pellet-like, and bead-like phosphorescent member 50 shown in FIG. 8B is composed of a plurality of particulate, powdery plurality of first phosphorescent phosphors 10, and an organic polymer having optical transparency. A light-transmitting core (core) 17 such as inorganic glass dispersed in a first phosphorescent phosphor-containing core, and a plurality of second phosphorescent phosphors 11 on the surface of the core, a light-transmitting binder (binder) A phosphor-containing phosphor-containing member (phosphorescent phosphor-containing element) having a core-shell structure composed of a shell dispersed and contained in 17 (shell).

The granule (granule) shape, pellet shape, and bead-shaped phosphorescent member 60 shown in FIG. 8C includes a plurality of particulate and powdery second phosphorescent phosphors 11 and a light-transmitting organic polymer. A light-transmitting core (core) 17 such as inorganic glass dispersed in a second phosphorescent phosphor-containing core, and a plurality of first phosphorescent phosphors 10 on the surface of the core, a light-transmitting binder (binder) A phosphor-containing phosphor-containing member (phosphorescent phosphor-containing element) having a core-shell structure composed of a shell dispersed and contained in 17 (shell).

(Fifth embodiment of the present invention)

The fifth embodiment of the present invention will be described in detail with reference to FIGS. 1, 9, and 10 again. In order to distinguish between the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11, the first phosphorescent phosphor particles 10 are schematically represented by an ellipse, and the second phosphorescent phosphor particles 10 The body 11 is schematically represented by a circle. The actual shapes and dimensions of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor 11 are arbitrary.

9 and 10 show a phosphorescent light emitting device 500 of the fifth embodiment, FIG. 9 is a partially conceptual perspective view in which a section is partially cut away, and FIG. 10 is (10) in FIG.・ (10) It is a conceptual enlarged sectional view cut along the line.

In the fifth embodiment, points different from the above-described various embodiments will be described, and description of points similar to or overlapping with those of the above-described embodiments will be omitted.

9 and 10, the luminous light-emitting device 500 is a transparent, translucent light-transmitting or opaque non-light-transmitting sheet-like, plate-like support 30 and one surface (or both surfaces) of the support. A first phosphorescent light emitting layer 80 containing a plurality of first phosphorescent phosphors 10 and a second phosphorescent phosphor 11 formed on the first phosphorescent light emitting layer 80. And a second phosphorescent light emitting layer 70.

The first phosphorescent light emitting layer 80 is excited by the light beam EX-1 in the first excitation wavelength band, and emits a plurality of first afterglow light beams AG-1 having the first light emission wavelength band including visible light. A plurality of first phosphorescent phosphor pigments (afterglow pigments) 10 in the form of particles or powder are dispersed in a light-transmitting binder (binder) 14 such as a light-transmitting organic polymer, and the support 30 A kind of first phosphorescent phosphor (phosphorescent pigment, afterglow pigment) 10 that is applied to one surface (or both surfaces), dried, cured, and solidified.

The second phosphorescent light-emitting layer 70 is excited by the light beam EX-2 in the second excitation wavelength band, and emits a second afterglow light beam AG--2 having a second light emission wavelength band including visible light. A plurality of second phosphorescent phosphor pigments (afterglow pigments) 11 in the form of particles and powder are dispersed in a light transmissive binder (binder) 19 such as a light transmissive organic polymer, It is applied on the first phosphorescent light emitting layer 80, dried, cured and solidified.

(Sixth embodiment of the present invention)

A sixth embodiment of the present invention will be described in detail with reference to FIG. 1, FIG. 11, and FIG. In order to distinguish between the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11, the first phosphorescent phosphor particles 10 are schematically represented by an ellipse, and the second phosphorescent phosphor particles 10 The body 11 is schematically represented by a circle. The actual shapes and dimensions of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor 11 are arbitrary.

11 and 12 show a phosphorescent light emitting device 600 according to the sixth embodiment. FIG. 11 is a partially conceptual perspective view in which a section is partially cut away and FIG. 12 is (12) in FIG. (12) It is a conceptual enlarged cross-sectional view cut along the line.

In the sixth embodiment, points different from the above-described various embodiments will be described, and description of points that are the same as or overlapped with the above-described embodiments will be omitted.

In FIG. 11 and FIG. 12, the phosphorescent light emitting device 600 is a transparent sheet, a translucent light-transmitting or opaque non-light-transmitting sheet-like or plate-like support 30 and one surface of the support (or A second phosphorescent light emitting layer 70 containing a second phosphorescent phosphor formed on both sides) and a first phosphor containing a first phosphorescent phosphor formed on the second phosphorescent light emitting layer 70 And a phosphorescent light emitting layer 80.

The second phosphorescent light-emitting layer 70 is excited by the light beam EX-2 in the second excitation wavelength band, and emits a second afterglow light beam AG--2 having a second light emission wavelength band including visible light. A plurality of second phosphorescent phosphor pigments (afterglow pigments) 11 in the form of particles and powder are dispersed in a light transmissive binder (binder) 19 such as a light transmissive organic polymer, It is applied to one surface (or both surfaces) of the support 30 and dried, cured, and solidified.

The first phosphorescent light emitting layer 80 is excited by the light beam EX-1 in the first excitation wavelength band, and emits a plurality of first afterglow light beams AG-1 having the first light emission wavelength band including visible light. A plurality of first phosphorescent particles (phosphorescent pigment, afterglow pigment) 10 in the form of particles and powder are dispersed in a light-transmitting binder (binder) 14 such as a light-transmitting organic polymer. It is applied on the second phosphorescent light emitting layer 70, dried, cured and solidified.

(Seventh embodiment of the present invention)

The seventh embodiment of the present invention will be described in detail with reference to FIGS. 1, 13, and 14 again. In order to distinguish between the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor particles 11, the first phosphorescent phosphor particles 10 are schematically represented by an ellipse, and the second phosphorescent phosphor particles 10 The body 11 is schematically represented by a circle. The actual shapes and dimensions of the first phosphorescent phosphor particles 10 and the second phosphorescent phosphor 11 are arbitrary.

FIGS. 13 and 14 show a phosphorescent light emitting device 700 according to the seventh embodiment, FIG. 13 is a partially conceptual perspective view partially cut away and FIG. 14 is (14) of FIG. -(14) It is a conceptual expanded sectional view cut | disconnected along the line. In FIGS. 13 and 14, the first phosphorescent phosphor particle 10 is schematically represented by an ellipse, and the second phosphorescent phosphor 11 is schematically represented by a circle.

In the seventh embodiment, points different from the above-described embodiment will be described, and description of points that are the same as or overlapped with the above-described embodiment will be omitted.

In FIG. 13 and FIG. 14, the phosphorescent light emitting device 700 is a transparent, semi-transparent sheet-like, plate-like support 30 and the first phosphorescent formed on one surface of the support 30. It consists of a first phosphorescent light emitting layer 80 containing a phosphor and a second phosphorescent light emitting layer 70 containing a second phosphorescent phosphor formed on the other surface of the support 30.

The first phosphorescent light emitting layer 80 is excited by the light beam EX-1 in the first excitation wavelength band, and emits a plurality of first afterglow light beams AG-1 having the first light emission wavelength band including visible light. A plurality of first phosphorescent particles (phosphorescent pigment, afterglow pigment) 10 in the form of particles and powder are dispersed in a light-transmitting binder (binder) 14 such as a light-transmitting organic polymer. It is coated on one surface of the support 30, dried, cured and solidified.

The second phosphorescent light-emitting layer 70 is excited by the light beam EX-2 in the second excitation wavelength band, and emits a second afterglow light beam AG--2 having a second light emission wavelength band including visible light. A plurality of second phosphorescent phosphors (phosphorescent pigments and afterglow pigments) 11 in the form of particles and powder are dispersed in a light-transmitting binder (binder) 19 such as a light-transmitting organic polymer. Then, it is applied onto the other surface of the support 30 and dried, cured, and solidified.

The first phosphorescent light emitting layer 80 and the second phosphorescent light emitting layer 70 are optically coupled to each other via a sheet-like, plate-like support 30 having light transmissivity interposed therebetween. Yes.

For example, when irradiating light for exciting the first phosphorescent light emitting layer 80 and the second phosphorescent light emitting layer 70 from the first phosphorescent light emitting layer 80 and / or the second phosphorescent light emitting layer 70 side for a predetermined time. The first afterglow ray AG-1 and the second afterglow ray AG-2 are emitted from the first phosphorescent fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11, respectively, after the irradiation stop, and the first The afterglow ray AG-1 excites the second phosphorescent fluorescent pigment 11 via the support 30. As a result, the second afterglow ray AG-2 from the second phosphorescent fluorescent pigment 11 is extended for a predetermined time.

(Eighth embodiment of the present invention)

In an eighth embodiment of the present invention, a first phosphorescent phosphor that emits a first afterglow beam having a first emission wavelength band and excited by a light beam in a first excitation wavelength band, And a second phosphorescent phosphor that emits a second afterglow beam having a second emission wavelength band that is excited by a light beam in a second excitation wavelength band partially or entirely including the emission wavelength band of By using a plurality of types of phosphorescent phosphors and irradiating the first phosphorescent phosphor with an excitation beam including the first excitation wavelength band, the first afterglow beam is generated for a predetermined time after the excitation beam is stopped. And a method for emitting a phosphorescent phosphor comprising irradiating and exciting the second phosphorescent phosphor with a first afterglow beam from the first phosphorescent phosphor.

In the eighth embodiment, in the various embodiments described above, the second phosphorescent phosphor 10 is hardly excited, and a light beam that excites only the first phosphorescent phosphor 10 is irradiated. In this case, the afterglow time of the second phosphorescent phosphor 11 cannot be substantially extended.For example, the emission color of the phosphorescent light emitting layer 20 is initially the afterglow ray AG from the first phosphorescent phosphor 10. -1 emission color (e.g., purple, blue, green), but the second phosphorescent phosphor 11 is excited by the afterglow ray AG-1 over time, and the first phosphorescent phosphor 10 , The emission color of the second phosphorescent phosphor 11 (for example, yellow, orange, pink, red) becomes strong, and finally the emission color of only the second phosphorescent phosphor 11 is obtained.

In the phosphorescent light emitting device according to another aspect of the present invention, the particulate first luminous phosphor 10 and the particulate second phosphorescent light are formed on the light guiding member composed of a light guiding member (light guide, light pipe). Fluorescent phosphor 11 is supported.

In the ninth to eighteenth embodiments of the present invention described below, the light guide member is used as a support member for supporting the first phosphorescent phosphor 10 and the particulate second phosphorescent phosphor 11. An optical fiber is used as (light guide, light pipe).

(Ninth embodiment of the present invention)

With reference to FIG. 15, an optical fiber luminous storage device 800 according to a ninth embodiment of the present invention will be described.

FIG. 15 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 800 according to the ninth embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 800 is arranged in an optical fiber core (core) 71 and a core (core) 71 made of a light guide material having a long and flexible length of arbitrary length. It consists of a particulate first phosphorescent phosphor 10 (a plurality of first phosphorescent fluorescent pigments) and a particulate second phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments).

The plurality of first phosphorescent fluorescent pigments 10 and the plurality of second phosphorescent fluorescent pigments 11 are mixed as uniformly as possible so that they are long and flexible made of an organic polymer such as acrylic resin, polycarbonate resin, or silicone resin. The light guide core (core) 71 having light transmittance and high refractive index is dispersed and contained from one end face (end face) EF1 to the other end face EF1.

The first phosphorescent fluorescent pigment 10 and a plurality of second phosphorescent fluorescent materials in the light guiding core (core) 71 from one end surface EF-1 and / or the other end surface EF-2 of the optical fiber type phosphorescent light emitting device 800 When a light beam that can excite the pigment 11 is incident, a part of the light beam is formed between the surface (side surface) of the light guide core (core) 71 having a high refractive index and air having a lower refractive index than the light guide core (core) 71. The total internal reflection is repeated at the interface and transmitted over its length.

The content of the first and second phosphorescent fluorescent pigments 10 and 11 in the light-guiding core 71 is about 0.1 wt% to 50 wt%, preferably about 1 wt% to 20 wt%.

When the content in the light-guiding core (core) 71 of the first and second phosphorescent fluorescent pigments 10 and 11 exceeds 50 wt%, incident light from one end face EF-1 and / or the other end face EF-1 It becomes difficult to transmit far, and if the content is less than 0.1 wt%, the probability of being absorbed by the first and second phosphorescent fluorescent pigments 10 and 11 that can transmit incident light far is reduced. The amount of afterglow rays (first afterglow ray AG-1 and second afterglow ray AG-2 shown in FIG. 1) from the second phosphorescent fluorescent pigments 10 and 11 decreases.

A part of the light beam is absorbed by the first and second phosphorescent fluorescent pigments 10 and 11 in the light guide core 71, and the first and second phosphorescent fluorescent pigments after the irradiation of the light beam is stopped. Afterglow rays 10 and 11 (first afterglow ray AG-1, second afterglow ray AG-2) are emitted and last for a predetermined time.

Part of the first and second afterglow rays AG-1 and AG-2 are emitted from the surface (side surface) of the light guide core 71 to the outside and observed.

The other part from the first phosphorescent fluorescent pigment 10 is absorbed by the adjacent second phosphorescent fluorescent pigment 11, or is transmitted through the light-guiding core 71 by total internal reflection, and the second phosphorescent property. It is absorbed by the fluorescent pigment 11 and continues to excite the second phosphorescent fluorescent pigment 11 during the duration of the first afterglow ray AG-1. As a result, the second phosphorescent fluorescent pigment 11 extends the duration of the second afterglow beam AG-2.

(Tenth embodiment of the present invention)

With reference to FIG. 16, an optical fiber type phosphorescent light emitting device 810 according to a tenth embodiment of the present invention will be described.
FIG. 16 is a conceptual perspective view showing an optical fiber type luminous light emitting device 810 according to a tenth embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 810 is long and flexible with an arbitrary length in which particulate first phosphorescent phosphors 10 (a plurality of first phosphorescent fluorescent pigments) are dispersed and arranged. And an optical fiber core (core) 71 made of a light-transmissive member having optical transparency and a high refractive index, and the surface (side surface) of the core (core) 71 is coated, and the second luminous property in the form of particles It comprises a clad (covering layer, sheath: sheath) made of phosphor 11 (a plurality of second phosphorescent fluorescent pigments) and a light-transmitting binder (binding material) 72.

The plurality of first phosphorescent fluorescent pigments 10 are contained in the optical fiber core 71 in a dispersed manner from one end surface EF-1 to the other end surface EF-1. The clad containing the plurality of second phosphorescent fluorescent pigments 11 is entirely covered on the surface (side surface) of the core 71 as shown in FIG.

An optical fiber core (core) 71 having a refractive index n ₁ and a light-transmitting binder (binding material) 72 having a refractive index n ₂ have a refractive index relationship of n ₁ = n ₂ , n ₁ > In order to satisfy n ₂ or n ₁ <n ₂ , for example, an organic polymer having a light transmitting property and a light guiding property such as an acrylic resin, a polycarbonate resin, a silicone resin, a silicone rubber, and a fluorine resin can be used.

The content of the first luminous fluorescent pigment 10 in the light-guiding core 71 is about 0.1 wt% to 50 wt%, preferably about 1 wt% to 20 wt%. The content of the second luminous phosphor pigment 11 in the light transmissive binder and clad 72 is about 0.1 wt% to 50 wt%, preferably about 1 wt% to 20 wt%.

When the refractive index relationship is set as n ₁ = n ₂ , the light transmissive binder, the clad 72 is the same as the light guide core (core) 71 in terms of optical fiber, one end surface EF-1 and, Alternatively, the light beam incident on the light guide core (core) 71, the light transmissive binder, and the clad 72 from the other end face EF-1 is totally reflected at the interface between the surface (side face) of the clad 72 and air having a lower refractive index than the clad 72. The light guide core (core) 71, the light transmissive binder, and the clad 72 are transmitted in the length direction of the optical fiber 810 by repeating the above.

When the refractive index relationship is set as n ₁ > n ₂ , the light incident on the light guide core (core) 71 from the one end face EF-1 or the other end face EF-1 ) Repeated total reflection at the interface between the surface of 71 and the light guide core (core) 71 and the inner surface of the cladding 72 having a lower refractive index than that of the light guide core (core) 71 in the length direction of the optical fiber 810. introduce. In addition, when the refractive index relationship is set as n ₁ <n ₂ , the light beam incident on the light guide core (core) 71 from the one end face EF-1 or the other end face EF-1 of the optical fiber 810 is guided. Since the optical core (core) 71 leaks into the cladding 72 having a higher refractive index than that of the light guide core (core) 71, the optical fiber 810 functions as a light leakage type (LEAKY) optical fiber.

Since the first phosphorescent fluorescent pigment 10 exists in the light guide core (core) 71, a part of the light beam transmitted in the length direction of the optical fiber 810 in the light guide core (core) 71 is the first. The phosphorescent fluorescent pigment 10 absorbs the afterglow ray (first afterglow ray AG-1 shown in FIG. 1) from the first phosphorescent fluorescent pigment 10 and lasts for a predetermined time.

The light beam that enters the clad 72 from the light guiding core (core) 71 excites the second phosphorescent fluorescent pigment 11 existing in the clad 72, and the afterglow beam from the second phosphorescent fluorescent pigment 11 (FIG. 1). A second afterglow ray AG-2) shown in FIG. Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

In the tenth embodiment described above, the clad 72 containing a plurality of second phosphorescent fluorescent pigments 11 may be partially coated on the surface (side surface) of the core 71, the clad An example of partially covering 72 will be described in the following eleventh and twelfth embodiments of the present invention.

(Eleventh embodiment of the present invention)

The eleventh embodiment of the present invention is a modification of the above-described tenth embodiment, and portions that are the same as or overlapped with the description of the tenth embodiment are omitted as much as possible.

With reference to FIG. 17, an optical fiber luminous storage device 820 according to an eleventh embodiment of the present invention will be described.

FIG. 17 is a conceptual perspective view showing an optical fiber type luminous light emitting device 820 according to an eleventh embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 820 has a long and flexible length of arbitrary length containing a dispersion of the particulate first phosphorescent phosphor 10 (a plurality of first phosphorescent fluorescent pigments). And an optical fiber core (core) 71 made of a light-guiding member having optical transparency and a high refractive index, and partially coated on the surface (side surface) of the core (core) 71 to form a particulate second Phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) and a light-transmitting fluorescent pigment-containing clad (covering layer, sheath: sheath) comprising a light-transmitting binder (binding material) 72 .

In the eleventh embodiment, as shown in FIG. 17, the second phosphorescent fluorescent pigment-containing clad 72 is continuous along the length direction on the surface (side surface) of the core 71 of the phosphorescent optical fiber 820. Thus, the surface (side surface) is partially covered so as to be almost spirally wound.

A light beam incident on the light guide core (core) 71 from the one end face EF-1 and / or the other end face EF-1 of the phosphorescent optical fiber 820 is transmitted through the light guide core (core) 71 to guide the light. Exciting the first phosphorescent fluorescent pigment 10 in the core 71, and entering the spiral second phosphorescent fluorescent pigment-containing cladding 72 to excite the second phosphorescent fluorescent pigment 11, A first afterglow beam AG-1 is emitted from the phosphorescent fluorescent pigment 10 for a predetermined time, and a second afterglow beam AG-2 is emitted from the second phosphorescent fluorescent pigment 11 for a predetermined time.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the light guide core (core) 71 or the surface (side surface) of the clad 72 to the outside and observed.

(Twelfth embodiment of the present invention)

The twelfth embodiment of the present invention is a modification of the above-described tenth embodiment, and portions that are the same as those in the description of the tenth embodiment and that overlap are omitted as much as possible.

With reference to FIG. 18, an optical fiber type phosphorescent light emitting device 830 according to a twelfth embodiment of the present invention is described.

FIG. 18 is a conceptual perspective view showing an optical fiber-type phosphorescent light-emitting device 830 according to a twelfth embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 830 has a long and flexible length of any length containing a dispersed particulate first phosphorescent phosphor 10 (a plurality of first phosphorescent fluorescent pigments). And an optical fiber core (core) 71 made of a light-guiding member having optical transparency and a high refractive index, and partially coated on the surface (side surface) of the core (core) 71 to form a particulate second Phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) and a light-transmitting fluorescent pigment-containing clad (covering layer, sheath: sheath) comprising a light-transmitting binder (binding material) 72 .

In the twelfth embodiment, as shown in FIG. 18, the second phosphorescent fluorescent pigment-containing clad 72 is formed along the length direction of the surface (side surface) of the core 71 of the phosphorescent optical fiber 820. One or a plurality of strips or stripes of the clad 72 are partially covered on the surface (side surfaces). The light beam incident on the light guide core (core) 71 from the one end face EF-1 and / or the other end face EF-1 of the phosphorescent optical fiber 830 is transmitted through the light guide core (core) 71 to guide the light. Exciting the first phosphorescent fluorescent pigment 10 in the core (core) 71, and exciting the second phosphorescent fluorescent pigment 11 entering the band-like, striped second phosphorescent fluorescent pigment-containing clad 72, A first afterglow beam AG-1 is emitted from the first phosphorescent fluorescent pigment 10 for a predetermined time, and a second afterglow beam AG-2 is emitted from the second phosphorescent fluorescent pigment 11 for a predetermined time.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the light guide core (core) 71 or the surface (side surface) of the clad 72 to the outside and observed.

(Thirteenth embodiment of the present invention)

With reference to FIG. 19, an optical fiber type luminous storage device 840 according to a thirteenth embodiment of the present invention will be described.

FIG. 19 is a conceptual perspective view showing an optical fiber type luminous light emitting device 840 according to a thirteenth embodiment of the present invention.

In the description of the thirteenth embodiment of the present invention, portions that are the same as or overlapped with the descriptions of the various embodiments described above are omitted as much as possible.

As shown in FIG. 19, an optical fiber type luminous light emitting device 840 includes an optical fiber core (core) 71 made of a long and flexible light guide member having an arbitrary length, and one end face (end).・ Face) Clad (coating layer, sheath :) consisting of a light-transmitting binder (binding material) coated on the surface (side surface) of the core (core) 71 almost entirely from EF-1 to the other end surface EF-1. (Sheath) 72, and in the clad 72, the particulate first phosphorescent phosphor 10 (plurality of first phosphorescent fluorescent pigments) and the particulate second phosphorescent phosphor 11 (plurality of second phosphorescent phosphors 11). Phosphorescent fluorescent pigments).

An optical fiber core (core) 71 having a refractive index n ₁ and a light-transmitting binder (binding material) 72 having a refractive index n ₂ have a refractive index relationship of n ₁ = n ₂ , n ₁ > In order to satisfy n ₂ or n ₁ <n ₂ , for example, an organic polymer having a light transmitting property and a light guiding property such as an acrylic resin, a polycarbonate resin, a silicone resin, a silicone rubber, and a fluorine resin can be used.

The content of the first phosphorescent fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11 in the cladding 72 is about 0.1 wt% to 90 wt%, preferably about 10 wt% to 70 wt%.

When the refractive index relationship is set as n ₁ = n ₂ , the light transmissive binder, the clad 72 is the same as the light guide core (core) 71 in terms of optical fiber, one end surface EF-1 and, Alternatively, the light guide core (core) 71, the light transmissive binder, and a part of the light beam incident on the clad 72 from the other end face EF-1 are part of the surface of the clad 72 (side face) and the air having a lower refractive index than the clad 72. Then, total reflection is repeated, and the light guide core (core) 71, the light transmissive binder, and the clad 72 are transmitted in the length direction of the optical fiber 840.

The other part of the incident light beam is the first luminous property that is dispersed in the light-transmitting binder and clad 72 in the middle of transmitting the light-guiding core 71 and the light-transmitting binder and clad 72. The fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11 are absorbed to excite the first and second phosphorescent fluorescent pigments 10 and 11, and afterglow rays (the first afterglow ray and the second afterglow shown in FIG. 1). Light) for a certain period of time.

Further, the second afterglow fluorescent pigment 11 is irradiated and excited by the first afterglow beam from the first phosphorescent fluorescent pigment 10, and the second afterglow beam from the second phosphorescent fluorescent pigment 11 is left behind. Light time is extended.

When the refractive index relationship is set as n ₁ > n ₂ , part of the light beam incident on the light guide core (core) 71 from the one end face EF-1 or the other end face EF-1 is light guide The total length of the optical fiber 810 in the light guiding core (core) 71 is repeated by repeating total reflection at the interface between the surface of the core (core) 71 and the inner surface of the cladding 72 having a lower refractive index than that of the light guiding core (core) 71. Transmit in the right direction.

A light beam incident on the light guide core (core) 71 at an angle not satisfying the condition of total reflection enters the inside of the cladding 72 from the surface of the light guide core (core) 71 and is dispersed in the cladding 72. The phosphorescent fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11 are absorbed into the first and second phosphorescent fluorescent pigments 10 and 11 to excite the afterglow rays (first afterglow rays shown in FIG. Afterglow).

A light beam incident on the light guide core (core) 71 at an angle that does not satisfy the condition of total reflection enters the inside of the cladding 72 from the surface of the light guide core (core) 71 and is dispersed in the cladding 72. The phosphorescent fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11 are absorbed into the first and second phosphorescent fluorescent pigments 10 and 11 to excite the afterglow rays (first afterglow rays shown in FIG. Afterglow).

In addition, in order to generate a light leakage part in the optical fiber type phosphorescent light emitting device 840 in advance, for example, it is partially bent or arranged on the surface of the light guide core 71 to provide a light leakage type. (Leaky: LEAKY) When using an optical fiber, light transmitted through the light guide core (core) 71 by total internal reflection enters the inside of the cladding 72 from the light guide core (core) 71 at the light leakage part, Absorbed by the first phosphorescent fluorescent pigment 10 and the second phosphorescent fluorescent pigment 11 dispersed in the cladding 72 to excite the first and second phosphorescent fluorescent pigments 10 and 11, and the afterglow rays (in FIG. The first afterglow ray AG-1 and the second afterglow ray AG-2) are emitted for a predetermined time.

When the refractive index relationship is set as n ₁ <n ₂ , a light beam incident on the light guide core (core) 71 from one end surface EF-1 and / or the other end surface EF-1 of the optical fiber 810 is guided. The optical fiber 810 functions as a light leakage type (LEAKY) optical fiber because the light leaks from the conductive core (core) 71 into the clad 72 having a higher refractive index than the light guiding core (core) 71.

Since the first phosphorescent fluorescent pigment 10 exists in the light guide core (core) 71, a part of the light beam transmitted in the length direction of the optical fiber 810 in the light guide core (core) 71 is the first. The phosphorescent fluorescent pigment 10 absorbs the afterglow ray (first afterglow ray AG-1 shown in FIG. 1) from the first phosphorescent fluorescent pigment 10 and lasts for a predetermined time.

The light beam that enters the clad 72 from the light guiding core (core) 71 excites the second phosphorescent fluorescent pigment 11 existing in the clad 72, and the afterglow beam from the second phosphorescent fluorescent pigment 11 (FIG. 1). A second afterglow ray AG-2) shown in FIG.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

In the thirteenth embodiment described above, the clad 72 containing a plurality of first and second phosphorescent fluorescent pigments 10 and 11 is partially coated on the surface (side surface) of the core 71. An example in which the cladding 72 is partially covered will be described in the following fourteenth and fifteenth embodiments of the present invention.

(Fourteenth embodiment of the present invention)

The fourteenth embodiment of the present invention is a modification of the thirteenth embodiment described above, and portions that are the same as those in the description of the thirteenth embodiment and that overlap are omitted as much as possible.

An optical fiber type luminous light emitting device 850 according to a fourteenth embodiment of the present invention will be described with reference to FIG.

FIG. 20 is a conceptual perspective view showing an optical fiber type luminous light emitting device 850 according to a fourteenth embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 850 includes an optical fiber core (core) 71 made of a light-guiding member having an arbitrary length and flexibility and having light transmission properties, and a core (core) 71 Partly coated on the surface (side surface) of the first particulate phosphorescent particulate 10 (a plurality of first phosphorescent phosphors) and a second phosphorescent particulate 11 (a plurality of phosphors). A second phosphorescent fluorescent pigment-containing clad (coating layer, sheath: sheath) 72 comprising a light-transmitting binder (binding material) in which a second phosphorescent fluorescent pigment) is dispersed.

In the fourteenth embodiment, as shown in FIG. 20, the first and second phosphorescent fluorescent pigment-containing clads 72 are arranged on the surface (side surface) of the core (core) 71 of the phosphorescent optical fiber 850 in the length direction. It is partially covered so as to be continuously spiraled along the spiral.

The light beam incident on the light guide core (core) 71 from the one end surface EF-1 and / or the other end surface EF-1 of the phosphorescent optical fiber 850 is transmitted through the light guide core (core) 71, and the light beam Are incident on the first and second light-storing fluorescent pigment-containing clads 72 spirally from the light-guiding core 71, and the first and second phosphorescent fluorescent pigments 10 dispersed in the clad 72 , 11 and emits a first afterglow ray AG-1 for a predetermined time from the first phosphorescent fluorescent pigment 10 and a second afterglow ray AG-2 for a predetermined time from the second phosphorescent fluorescent pigment 11. To emit.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the surface (side surface) of the cladding 72 and observed.

(Fifteenth embodiment of the present invention)

The fifteenth embodiment of the present invention is a modification of the above-described thirteenth embodiment, and portions that are the same as or overlapped with the description of the thirteenth embodiment are omitted as much as possible.

With reference to FIG. 21, an optical fiber type luminous light emitting device 860 according to a fifteenth embodiment of the present invention will be described.

FIG. 21 is a conceptual perspective view showing an optical fiber type luminous light emitting device 860 according to a fifteenth embodiment of the present invention.

The optical fiber type phosphorescent light emitting device 860 has an optical fiber core (core) 71 made of a light-guiding member having an arbitrary length and flexibility and having light transmission properties, and a core (core) 71 Particulate first phosphorescent phosphor 10 (a plurality of first phosphorescent phosphors 10) partially coated on the surface (side surface) of the material and dispersed and contained in a light-transmitting binder (binding material) Pigment) and particulate second phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) 72, first and second phosphorescent fluorescent pigment-containing clads (covering layer, sheath: sheath) 72 and Consists of.

In the fifteenth embodiment, as shown in FIG. 21, the first and second phosphorescent fluorescent pigment-containing clads 72 have a length on the surface (side surface) of the core 71 of the phosphorescent optical fiber 820. The surface (side surface) is partially covered as one or a plurality of strips or stripes of clad 72 along the direction.

The light beam incident on the light guide core (core) 71 from the one end face EF-1 and / or the other end face EF-1 of the phosphorescent optical fiber 860 is transmitted through the light guide core (core) 71 and guided. The first and second phosphorescent fluorescent pigments 10 and 11 are excited by entering the first and second phosphorescent fluorescent pigment-containing clads 72 in the form of strips and stripes from within the core 71. The first afterglow beam AG-1 is emitted from the fluorescent fluorescent pigment 10 for a predetermined time, and the second afterglow beam AG-2 is emitted from the second phosphorescent fluorescent pigment 11 for a predetermined time.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the light guide core (core) 71 or the surface (side surface) of the clad 72 to the outside and observed.

(Sixteenth embodiment of the present invention)

The sixteenth embodiment of the present invention is a modification of the optical fiber type phosphorescent light emitting device 840 of the thirteenth embodiment of the present invention described with reference to FIG. 19, and the thirteenth embodiment. Parts that are the same as those described above and overlapping points are omitted as much as possible.

With reference to FIG. 22, an optical fiber type luminous light emitting device 870 according to a sixteenth embodiment of the present invention will be described.

FIG. 22 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 870 according to a sixteenth embodiment of the present invention.

As shown in FIG. 22, the optical fiber type luminous light emitting device 870 includes an optical fiber core (core) 71 made of a long and flexible light guide member having an arbitrary length, and one end surface (end).・ Face) The first clad made of a light-transmitting binder (binding material) coated on the entire surface (side surface) of the core (core) 71 almost entirely from EF-1 to the other end surface EF-1. (Coating layer, sheath: sheath) 72 and a second cladding comprising a first clad (coating layer, sheath: sheath) 72 and a light-transmitting binder (binding material) entirely covered on the surface (side surface) of 72 (Coating layer, sheath: sheath) 72, and further dispersed in the first clad 72, the particulate first phosphorescent phosphor 10 (a plurality of first phosphorescent fluorescent pigments), The second clad (covering layer, sheath: sheath) in which the particle-like second phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) is dispersed and contained in 72 It is.

Optical fiber core (core) 71 having refractive index n ₁ and light transmissive binder (binding material) of first cladding 72 having refractive index n ₂ , light transmission of first cladding 72 having refractive index n ₃ For example, n ₁ = n ₂ = n ₃ , n ₁ > n ₂ = n ₃ , n ₁ <n ₂ = n ₃ , n ₁ = n ₂ > Light transmission of acrylic resin, polycarbonate resin, silicone resin, silicone rubber, fluororesin, etc., so that any combination such as> n ₃ , n ₁ <n ₂ <n ₃ , n ₁ > n ₂ > n ₃ etc. It can be used by selecting from organic polymers having light and light guiding properties.

The content of the first phosphorescent fluorescent pigment 10 in the first clad 72 is about 0.1 wt% to 90 wt%, preferably about 10 wt% to 70 wt%.

The content of the second phosphorescent fluorescent pigment 11 in the second cladding 73 is about 0.1 wt% to 90 wt%, preferably about 10 wt% to 70 wt%.

When the refractive index relationship is set as n ₁ = n ₂ = n ₃ , the first light-transmitting binder of the first cladding 72 and the light-transmitting binder of the second cladding 73 are optical fiber optically Same as the light guide core (core) 71, and enters the light guide core (core) 71, the first clad 72, and the second clad 73 from the one end face EF-1 and / or the other end face EF-1. A part of the light beam repeats total reflection at the interface between the surface (side surface) of the second cladding 73 and the air having a lower refractive index than that of the second cladding 73, and the light guiding core (core) 71 and the first cladding 72. Then, the inside of the second cladding 73 is transmitted in the length direction of the optical fiber 870.

The other part of the incident light ray is distributed in the first clad 72 while being transmitted through the light guide core (core) 71, the first clad 72, and the second clad 73. The phosphorescent fluorescent pigment 10 is absorbed by the second phosphorescent fluorescent pigment 11 dispersed in the second cladding 73 to excite the first and second phosphorescent fluorescent pigments 10 and 11, and afterglow from each. Light rays (first afterglow ray AG-1 and second afterglow ray AG-2 shown in FIG. 1) are emitted for a certain period of time.

Further, the second afterglow fluorescent pigment 11 is irradiated and excited by the first afterglow ray AG-1 from the first phosphorescent fluorescent pigment 10, and the second afterglow from the second phosphorescent fluorescent pigment 11 is excited. The afterglow time of the ray AG-2) is extended for a certain time.

When the refractive index relationship is set as n ₁ > n ₂ = n ₃ , one end face EF-1 and or part of the light beam incident on the light guide core (core) 71 from the other end face EF-1, An optical fiber is formed in the light guide core (core) 71 by repeating total reflection at the interface between the surface of the light guide core (core) 71 and the inner surface of the clad 72 having a lower refractive index than the light guide core (core) 71. Transmit in the length direction of 810.

Light incident on the light guide core (core) 71 at an angle that does not satisfy the conditions for total reflection enters the first clad 72 and the second clad 73 from the surface of the light guide core (core) 71. Absorbed by the first phosphorescent fluorescent pigment 10 dispersed in the first cladding 72 and the second phosphorescent fluorescent pigment 11 dispersed in the second cladding 73, the first and second phosphorescent fluorescent pigments 11 are absorbed. The pigments 10 and 11 are excited to emit afterglow rays (first afterglow ray AG-1 and second afterglow ray AG-2 shown in FIG. 1) for a certain period of time.

Light incident on the light guide core (core) 71 at an angle that does not satisfy the conditions for total reflection enters the first clad 72 and the second clad 73 from the surface of the light guide core (core) 71. First and second phosphorescent fluorescent pigments absorbed by the first phosphorescent fluorescent pigment 10 dispersed in the first cladding 72 and the second phosphorescent fluorescent pigment 11 dispersed in the second cladding 73 10 and 11 are excited to emit afterglow rays (first afterglow ray and second afterglow ray shown in FIG. 1) for a certain period of time.

In addition, in order to generate a light leakage part in the optical fiber type phosphorescent light emitting device 870 in advance, for example, it is partially bent or arranged on the surface of the light guide core 71 to provide a light leakage type. (Leaky: LEAKY) When an optical fiber is used, light transmitted through the light guide core (core) 71 by total internal reflection is transmitted from the light guide core (core) 71 to the first clad 72, Is absorbed in the first luminous fluorescent pigment 10 and the second luminous fluorescent pigment 11 respectively dispersed in the first cladding 72 and the second cladding 73. The two phosphorescent fluorescent pigments 10 and 11 are excited to emit afterglow rays (first afterglow ray AG-1 and second afterglow ray AG-2 shown in FIG. 1) for a certain period of time.

When the refractive index relationship is set as n ₁ <n ₂ = n ₃ , the light beam incident on the light guide core (core) 71 from the one end face EF-1 and / or the other end face EF-1 of the optical fiber 870 is Since the light guide core (core) 71 leaks into the first clad 72 and the second clad 73 having a higher refractive index than that of the light guide core (core) 71, this optical fiber 870 is a light leak type (leaky type). : LEAKY) Functions as an optical fiber.

Since the first phosphorescent fluorescent pigment 10 is present in the first cladding 72, a part of the light beam transmitted in the length direction of the optical fiber 810 in the light guiding core (core) 71 becomes the light leakage. The first phosphorescent fluorescent pigment 10 absorbs the afterglow ray (first afterglow ray AG-1 shown in FIG. 1) from the first phosphorescent fluorescent pigment 10 and lasts for a predetermined time.

The leakage light beam that has entered the second cladding 73 from the first cladding 72 excites the second phosphorescent fluorescent pigment 11 present in the second cladding 73, and the afterglow from the second phosphorescent fluorescent pigment 11. A light beam (second afterglow beam AG-2 shown in FIG. 1) is emitted and lasts for a predetermined time.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

In the sixteenth embodiment described above, the first clad 72 and the second clad 73 each containing a plurality of first and second phosphorescent fluorescent pigments 10 and 11 are arranged on the surface (side surface) of the core 71. An example in which the first clad 72 and the second clad 73 are partially covered may be partially covered on the following in the seventeenth embodiment and the eighteenth embodiment of the present invention. explain.

(Seventeenth embodiment of the present invention)

The seventeenth embodiment of the present invention is a modification of the optical fiber type phosphorescent light emitting device 870 of the sixteenth embodiment of the present invention described with reference to FIG. 22, and the sixteenth embodiment Parts that are the same as those described above and overlapping points are omitted as much as possible.

With reference to FIG. 23, an optical fiber luminous storage device 880 according to a seventeenth embodiment of the present invention will be described.

FIG. 23 is a conceptual perspective view showing an optical fiber type luminous light emitting device 880 according to a seventeenth embodiment of the present invention.

As shown in FIG. 23, an optical fiber type phosphorescent light emitting device 880 is composed of an optical fiber core (core) 71 made of a long and flexible light guide member having an arbitrary length, and one end face (end).・ Face) The first clad made of a light-transmitting binder (binding material) partially covered on the surface (side surface) of the core 71 from the EF-1 to the other end surface EF-1. (Coating layer, sheath: sheath) 72 and a second cladding (coating layer) comprising a light-transmitting binder (binding material) coated on the surface (side surface) of the first cladding (coating layer, sheath: sheath) 72 , Sheath: sheath) 73 and further containing the first luminous phosphor 10 in the form of particles (a plurality of first luminous fluorescent pigments) dispersed in the first cladding 72, and the second In the clad (covering layer, sheath: sheath) 73, the particulate second phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) is dispersed and contained.

In the seventeenth embodiment, as illustrated in FIG. 23, the first clad 72 containing the first luminous fluorescent pigment in a dispersed manner and the second luminous fluorescent pigment in a dispersed manner are contained. One or a plurality of strip-like or strip-like multi-layer clads 72 and 73 formed of the second clad 73 are formed along the length direction of the surface (side surface) of the core 71 of the optical fiber 880. Covered.

The light beam that has entered the light guide core (core) 71 from the one end surface EF-1 and / or the other end surface EF-1 of the phosphorescent optical fiber 880 is transmitted through the light guide core (core) 71 and also incident light. Leaks into the multilayer clads 72 and 73, excites the first and second phosphorescent fluorescent pigments 10 and 11 in the multilayer clads 72 and 73, and the first and second phosphorescent fluorescence. A first afterglow beam AG-1 and a second afterglow beam AG-2 for a predetermined time are emitted from the pigments 10 and 11, respectively.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the surfaces (side surfaces) of the multilayer clads 72 and 73 to the outside and observed.

(Eighteenth embodiment of the present invention)

The eighteenth embodiment of the present invention is a modification of the optical fiber type phosphorescent light emitting device 870 of the sixteenth embodiment of the present invention described with reference to FIG. 22, and the sixteenth embodiment Parts that are the same as those described above and overlapping points are omitted as much as possible.

With reference to FIG. 24, an optical fiber type luminous light emitting device 890 according to an eighteenth embodiment of the present invention will be described.

FIG. 24 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 890 according to an eighteenth embodiment of the present invention.

As shown in FIG. 24, an optical fiber type phosphorescent light emitting device 890 is composed of an optical fiber core (core) 71 made of a long and flexible light guide member having an arbitrary length, and one end face (end).・ Face) The first clad made of a light-transmitting binder (binding material) partially covered on the surface (side surface) of the core 71 from the EF-1 to the other end surface EF-1. (Coating layer, sheath: sheath) 72 and a second cladding (coating layer) comprising a light-transmitting binder (binding material) coated on the surface (side surface) of the first cladding (coating layer, sheath: sheath) 72 , Sheath: sheath) 73 and further containing the first luminous phosphor 10 in the form of particles (a plurality of first luminous fluorescent pigments) dispersed in the first cladding 72, and the second In the clad (covering layer, sheath: sheath) 73, the particulate second phosphorescent phosphor 11 (a plurality of second phosphorescent fluorescent pigments) is dispersed and contained.

In the eighteenth embodiment, as illustrated in FIG. 24, the first clad 72 containing the first luminous fluorescent pigment in a dispersed manner and the second luminous fluorescent pigment in a dispersed manner are contained. One or a plurality of ring-shaped clads 72 and 73 formed of the second clad 73 are partially formed on the surface (side surface) of the core 71 of the optical fiber 880 along the length direction thereof. Is covered.

The light beam that has entered the light guide core (core) 71 from the one end surface EF-1 and / or the other end surface EF-1 of the phosphorescent optical fiber 890 is transmitted through the light guide core (core) 71 and is also incident. Leaks into the multilayer clads 72 and 73, excites the first and second phosphorescent fluorescent pigments 10 and 11 in the multilayer clads 72 and 73, and the first and second phosphorescent fluorescence. A first afterglow beam AG-1 and a second afterglow beam AG-2 for a predetermined time are emitted from the pigments 10 and 11, respectively.

Further, the first afterglow ray pigment AG-1 from the first phosphorescent fluorescent pigment 10 irradiates the second phosphorescent fluorescent pigment 11, and the second phosphorescent fluorescent pigment 11 becomes the first afterglow ray AG- 1 is absorbed and excited, and the duration of the second afterglow ray AG-2 is extended.

The first and second afterglow rays AG-1 and AG-2 are emitted from the surfaces (side surfaces) of the ring-shaped multilayer clads 72 and 73 to the outside and observed.

As a modification of the eighteenth embodiment, the multi-layer clads 72 and 73 containing the first and second phosphorescent fluorescent pigments 10 and 11 are shown in FIG. 20 instead of the ring-shaped shape illustrated in FIG. It is good also as a spiral shape as shown.

(Nineteenth embodiment of the present invention)

In the nineteenth embodiment of the present invention, a light guide plate is used as the light guide member (light guide, light pipe) for supporting the first phosphorescent phosphor 10 and the second phosphorescent phosphor 11 described above. Used.

FIG. 25 is a conceptual perspective view showing an edge light irradiation / light guide plate type luminous light emitting device 900 of the nineteenth embodiment.

The nineteenth embodiment of the present invention is a modification of the optical fiber type phosphorescent light emitting device of the ninth to eighteenth embodiments, and is common to the description of the ninth to eighteenth embodiments. The overlapping parts are omitted as much as possible.

The edge light irradiation / light guide plate type phosphorescent light emitting device 900 is, for example, a plate-shaped light guide member, a light guide plate 71A, and the first main surface MF1 (and / or the first main surface MS1) of the light guide plate 71A. A plurality of parts formed on the second main surface MS2) partially or entirely, or a single phosphorescent fluorescent layer 90, and a plurality of first end faces EF1 and / or second end faces EF2 arranged opposite to each other. It consists of a light emitting diode LED.

The phosphorescent phosphor layer 90 can contain a plurality of first phosphorescent phosphor pigments 10 and a plurality of second phosphorescent phosphors 11 dispersed in a single or a plurality of light transmissive binder layers.

The plurality of phosphorescent fluorescent layers 90 can be, for example, a plurality of strips or stripes of parallel phosphorescent fluorescent layers spaced apart from each other at a constant interval or a variable interval.

In the example shown in FIG. 25, the plurality of phosphorescent fluorescent layers (luminescent phosphorescent layers) 90 include a substantially rectangular light guide plate 71A, and a plurality of strip-like and striped phosphorescent phosphor layers 90 and the first end face EF1. Between the two end surfaces EF2, the first main surface MS1 of the light guide plate 71A is formed and arranged in parallel with a predetermined distance from each other.

As the luminous phosphor layer (luminous luminous layer) 90, the plurality of first phosphorescent phosphor pigments 10 and the plurality of second phosphorescent properties in the first embodiment described with reference to FIGS. A phosphorescent phosphor layer (a phosphorescent light emitting layer) 20 in which the phosphor 11 is dispersed in a single light transmissive binder layer 12 may be used.

As the phosphorescent phosphor layer (phosphorescent light emitting layer) 90, phosphorescence in the fourth embodiment described with reference to FIG. 9 and FIG. 10 or the fifth embodiment described with reference to FIG. 11 and FIG. Fluorescent layers (light-emitting luminescent layers) 70 and 80 may be used.

Instead of providing the phosphorescent fluorescent layer (luminescent phosphorescent layer) 90, a plate-shaped light guide member like the phosphorescent fluorescent molded member 200 of the second embodiment described with reference to FIGS. 4 and 5, The plurality of first phosphorescent phosphor pigments 10 and the plurality of second phosphorescent phosphors 11 may be dispersed and contained directly in the light guide plate 71A. One of the first and second phosphorescent phosphor pigments 10 and 11 is dispersed and contained in the plate-like light guide member 71A, and the first and second phosphorescent phosphor pigments 10 are included. , 11 is provided with a phosphorescent light emitting layer dispersed and contained in a light transmissive binder layer, and the phosphorescent light emitting layer is partially or entirely formed on the first surface and / or the second surface. You may do it.

A plurality of first phosphorescent phosphor pigments 10 are dispersed and contained directly in a plate-shaped light guide member, light guide plate 71A, and a plurality of second phosphorescent phosphors 11 are dispersed in a light transmissive binder. The second phosphorescent phosphor 11 containing a phosphorescent phosphor layer (a phosphorescent light emitting layer) is partially or entirely formed and disposed on the light guide member, the main surface MS1 and / or the main surface MS2 of the light guide plate 71A. May be.

As a plurality of light emitting diodes LED, at least one of which can excite the first phosphorescent phosphor pigment 10 and the second phosphorescent phosphor pigment 11, for example, short-wavelength visible light such as near ultraviolet, purple, blue, or white Those that emit light can be used.

The light emitted from the light emitting diode LED is introduced into the light guide plate 71A from the first end surface EF1 and / or the second end surface EF2 of the edge light irradiation / light guide plate type phosphorescent light emitting device 900, and the light guide plate 71A Between the first main surface MF1 and the second main surface MF2, the total internal reflection is repeated and transmitted to the first end surface EF1 and / or the central portion away from the second end surface EF2.

Some of the light rays enter the plurality of phosphorescent phosphor layers 90 along the way, and irradiate the first phosphorescent phosphor pigment 10 and the second phosphorescent phosphor pigment 11 dispersed in the phosphorescent phosphor layer 90. And excited.

After the light emission from the light-emitting diode LED is stopped, the first phosphorescent phosphor pigment 10 emits a first afterglow beam composed of short-wavelength visible light such as blue, and the second phosphorescent phosphor pigment 11 emits, for example, green , Yellow, red, etc., which emit a second afterglow beam consisting of a relatively long wavelength visible ray can be used.

When using the first phosphorescent phosphor pigment 10 that can excite the second phosphorescent phosphor pigment 11 by the first afterglow light from the first phosphorescent phosphor pigment 10, The afterglow time of the second afterglow light from the second phosphorescent phosphor pigment 11 can be extended.

(20th embodiment of the present invention)

The twentieth embodiment of the present invention is a modification of the twentieth embodiment of the present invention described above.

The twentieth embodiment of the present invention is a modification of the edge light irradiation / light guide plate type phosphorescent light emitting device 900 of the nineteenth embodiment described above, and is a modification of the nineteenth embodiment. Parts that are the same as in the explanation and overlapping points are omitted as much as possible.

FIG. 26 is a conceptual perspective view showing an edge light irradiation / light guide plate type phosphorescent light emitting device 910 according to a twentieth embodiment of the present invention.

The edge light irradiation / light guide plate type phosphorescent light emitting device 910 is, for example, a plate-shaped light guide member, the light guide plate 71B, and the first main surface MF1 (and / or the first main surface MS1) of the light guide plate 71B. A plurality of parts arranged on the second main surface MS2) partially or entirely, or a single phosphorescent fluorescent layer 92 and a plurality of first end faces EF1 and / or a second end face EF2 arranged opposite to each other. It can consist of a light emitting diode LED.

In the edge light irradiation / light guide plate type luminous light emitting device 910 of the twentieth embodiment of the present invention, a plurality of light emitting diodes LED are arranged on one end face EF1 of the light guide plate 71B.

In the edge light irradiation / light guide plate type phosphorescent light emitting device 910 of the twentieth embodiment of the present invention, the thickness of the light guide plate 71B from one end surface EF1 to the other end surface as the light guide plate 71B (end surfaces EF1 and EF2) As shown in FIG. 26, a substantially tapered light guide member is used so that the distance between them decreases continuously or intermittently (not shown).

As shown in FIG. 26, the plurality of phosphorescent phosphor layers 91 are composed of a light-transmitting binder layer in which the first and second phosphorescent pigments 10 and 11 are dispersed, and the first main surface MF1 and / or the second It may be a phosphorescent fluorescent layer having a plurality of dot-like and island-like patterns arranged uniformly or non-uniformly on the main surface MS2.

The phosphorescent phosphor layer 91 having the dot-like and island-like patterns shown in FIG. 26 may be replaced with a strip-like phosphorescent phosphor layer 90 shown in FIG.

Light rays emitted from the light emitting diode LED are introduced into the light guide plate 71A from the first end face EF1 of the edge light irradiation / light guide plate type luminous light emitting device 910, and the first main surface MF1 and the second main surface MF1 of the light guide plate 71A. Is transmitted in the direction of the second end face EF2 by repeating total internal reflection.

In the twentieth embodiment of the present invention, since the light guide plate 71B uses a substantially tapered light guide member whose thickness decreases from one end face EF1 to the other end face toward EF2, internal total reflection is repeated. The light rays traveling through the light guide plate 71B are introduced into the phosphorescent phosphor layer 91 because the angle at which they strike the first main surface MF1 gradually does not satisfy the conditions for total reflection, and are contained in the phosphorescent phosphor layer 91. Two luminous pigments 10, 11 are excited. The first and second afterglow rays are emitted from the first and second luminous pigments 10 and 11, and the first and second afterglow rays are observed from the outside.

Furthermore, various constituent elements in the various embodiments described above can be arbitrarily combined to obtain a phosphorescent fluorescent device and a phosphorescent light emitting device of still another embodiment.

Various embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to these embodiments, and various modifications, based on the spirit of the present invention and the claims, It should be noted that design changes, improvements, and equivalents can be provided.

FIG. 1 is a schematic graph showing the relationship between the excitation wavelength and the emission wavelength of the first phosphorescent phosphor and the second phosphorescent phosphor. The vertical axis represents the intensity of the excitation light (arbitrary unit) and the luminance of the emitted light (arbitrary unit), and the horizontal axis represents the emission wavelength. FIG. 2 is a partial conceptual perspective view showing the phosphorescent light emitting device 100 according to the first embodiment, partially cut away to have a cross section. FIG. 3 is a conceptual partial enlarged sectional view of a partial phosphorescent light emitting device 100 cut along line (3)-(3) in FIG. FIG. 4 is a conceptual perspective view showing a phosphorescent light emitting device 200 according to the second embodiment, partially cut away and taken as a cross section. FIG. 5 is a conceptual partial enlarged cross-sectional view taken along line (5)-(5) in FIG. FIG. 6 is a conceptual perspective view showing a phosphorescent light emitting device 300 according to a third embodiment, partially cut away and taken as a cross section. FIG. 7 is a conceptual perspective view showing a phosphorescent light emitting device 400 according to the fourth embodiment, partially cut away and taken as a cross section. 8A, FIG. 8B, and FIG. 8C are conceptual enlarged sectional views showing various phosphorescent members 40, 50, and 60 contained in the phosphorescent light emitting device 400. FIG. FIG. 9 is a conceptual perspective view showing a phosphorescent light emitting device 500 of the fifth embodiment, partially cut away and taken as a cross section. FIG. 10 is a conceptual partial enlarged cross-sectional view taken along line (10)-(10) in FIG. FIG. 11 is a conceptual perspective view showing a phosphorescent light emitting device 600 according to the sixth embodiment, partially cut away and taken as a cross section. FIG. 12 is a conceptual partial enlarged cross-sectional view of phosphorescent light emitting device 600 cut along line (12)-(12) in FIG. FIG. 13 is a conceptual perspective view showing a phosphorescent light emitting device 700 according to a seventh embodiment, partially cut away and taken in a cross section. FIG. 14 is a conceptual partial enlarged cross-sectional view of phosphorescent light emitting device 700 cut along line (14)-(14) in FIG. FIG. 15 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 800 of the ninth embodiment. FIG. 16 is a conceptual perspective view showing an optical fiber-type phosphorescent light-emitting device 810 of the tenth embodiment. FIG. 17 is a conceptual perspective view showing an optical fiber type luminous light emitting device 820 of the eleventh embodiment. FIG. 18 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 830 of the twelfth embodiment. FIG. 19 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 840 according to a thirteenth embodiment. FIG. 20 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 850 according to the fourteenth embodiment. FIG. 21 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 860 of the fifteenth embodiment. FIG. 22 is a conceptual perspective view showing an optical fiber type luminous light emitting device 870 of the sixteenth embodiment. FIG. 23 is a conceptual perspective view showing an optical fiber type luminous light emitting device 880 of a seventeenth embodiment. FIG. 24 is a conceptual perspective view showing an optical fiber-type luminous light emitting device 890 of the eighteenth embodiment. FIG. 25 is a conceptual perspective view showing an edge light irradiation / light guide plate type luminous light emitting device 900 of the nineteenth embodiment. FIG. 26 is a conceptual perspective view showing an edge light irradiation / light guide plate type phosphorescent light emitting device 910 of the twentieth embodiment.

Explanation of symbols

10: first phosphorescent phosphor (afterglow phosphor), first phosphorescent phosphor particle (afterglow phosphor particle), first phosphorescent fluorescent pigment (afterglow phosphor pigment)
11... Second phosphorescent phosphor (afterglow phosphor), second phosphorescent phosphor particle (afterglow phosphor particle), second phosphorescent phosphor pigment (afterglow phosphor pigment)
12 ... Light transmissive binder (binding material)
DESCRIPTION OF SYMBOLS 13 ... Light transmissive member 14 ... Light transmissive member 15 ... Light transmissive member 16 ... Light transmissive core (core) member 17 ... Light transmissive shell (shell) member 19 ... Light transmissive member 20 ... Luminescent phosphor layer, light emitting layer 30 ... Support, film, sheet, plate support 40 ... Luminescent phosphor-containing member (Luminescent phosphor) Contained element)
50 ... Luminescent phosphor-containing member (Luminescent phosphor-containing element)
60 ... Luminescent phosphor-containing member (Luminescent phosphor-containing element)
70: luminous phosphor layer, light emitting layer
71 ... Optical fiber core (core) (light transmissive member, light guide member)
71A ... Light guide plate (light transmissive member, light guide member)
71B ... Light guide plate (light transmissive member, light guide member)
72: Light transmissive member, optical fiber coating, sheath, (clad, sheath)
73 ... Light transmissive member, optical fiber coating, sheath, (clad, sheath)
80: luminous phosphor layer, light emitting layer
90: luminous phosphor layer, light emitting layer
91 ... luminous phosphor layer, light emitting layer 100 ... support holding type luminous phosphor sheet-like, plate-like or film-like article (luminous luminous device, luminous fluorescent device)
200 ... Self-supporting luminous phosphorescent sheet-like, plate-like or film-like article (luminous luminous light-emitting device, luminous fluorescent device)
300 ... Luminescent luminescent molded article (Luminescent luminescent device, luminescent fluorescent device)
400 ... Luminescent luminescent molded article (Phosphorescent luminescent device, luminescent fluorescent device)
500 ... Support-holding type luminous phosphorescent sheet-like, plate-like or film-like article (luminous luminous light-emitting device, luminous fluorescent device)
600 ... Support-holding phosphorescent light-emitting sheet-like, plate-like or film-like article (luminous phosphorescent device, phosphorescent fluorescent device)
7000 ... Support-holding phosphorescent light-emitting sheet-like, plate-like or film-like article (phosphorescent light-emitting device, phosphorescent fluorescent device)
800 ... Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
810 ・ ・ ・ Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
820 ... Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
830 ... Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
840 ... Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
850 ... Optical fiber type phosphorescent light emitting device (phosphorescent fluorescent optical fiber)
860 ... Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
870 ・ ・ ・ Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
880 ・ ・ ・ Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
890 ・ ・ ・ Optical fiber type phosphorescent light emitting device (Phosphorescent fluorescent optical fiber)
900 ... Edge light irradiation / light guide plate type phosphorescent light emitting device
910 ・ ・ ・ Edge light irradiation / light guide plate type phosphorescent light emitting device (phosphorescent fluorescent light guide plate)
EX-1: First excitation wavelength band (excitation spectrum)
EX-2: Second excitation wavelength band (excitation spectrum)
AG-1: First emission wavelength band (emission spectrum)
AG-2 ... Second emission wavelength band (emission spectrum)
EF1 ... one end face, first end face (one end face of an optical fiber type phosphorescent light emitting device, one end face of an edge light irradiation / light guide plate type phosphorescent light emitting device)
EF2 ... the other end surface, the second end surface (the other end surface of the optical fiber type phosphorescent light emitting device, the other end surface of the edge light irradiation / light guide plate type phosphorescent light emitting device)
MS1 ... first main surface
MS2 ... Second main surface

Claims (23)

A first phosphorescent phosphor that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band;
A second phosphorescent phosphor that emits a second afterglow beam having a second emission wavelength band, which is excited by a light beam in a second excitation wavelength band partially or entirely including the first emission wavelength band; A phosphorescent light emitting device comprising: a first phosphorescent phosphor and a second phosphorescent phosphor arranged so as to be optically coupled.
A first phosphorescent phosphor that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band including visible light;
A second residual wavelength having a second emission wavelength band that is excited by a light beam having a second excitation wavelength band partially or entirely including the first emission wavelength band and includes a visible light beam different from the first emission wavelength band; A phosphorescent light emitting device comprising a second phosphorescent phosphor that emits a light beam and arranged so as to be capable of optically coupling the first phosphorescent phosphor and the second phosphorescent phosphor.
A first phosphorescent phosphor that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band; and the first emission wavelength band partially or entirely Using a second phosphorescent phosphor that is excited by a light beam of a second excitation wavelength band including and emits a second afterglow light beam having a second emission wavelength band,
By irradiating the first and second phosphorescent phosphors with excitation light including the first and second excitation wavelength bands, the first and second afterglow rays are generated for a predetermined time after the excitation light is stopped. And the first afterglow ray from the first phosphorescent phosphor, irradiating and exciting the second phosphorescent phosphor,
A method for emitting a phosphorescent phosphor that extends a duration of a second afterglow ray from the second phosphorescent phosphor.
A first phosphorescent phosphor that is excited by a light beam in a first excitation wavelength band and emits a first afterglow light beam having a first emission wavelength band; and the first emission wavelength band partially or entirely Using a second phosphorescent phosphor that is excited by a light beam of a second excitation wavelength band including and emits a second afterglow light beam having a second emission wavelength band,
By irradiating the first phosphorescent phosphor with an excitation light beam including the first excitation wavelength band, the first afterglow light beam is generated for a predetermined time after the excitation light beam is stopped, and the first phosphorescent fluorescence material A method for emitting a phosphorescent phosphor comprising irradiating and exciting a second phosphorescent phosphor with a first afterglow beam from a body.
3. The phosphorescent light emitting device according to claim 1, wherein the first phosphorescent phosphor and the second phosphorescent phosphor are made of phosphorescent fluorescent pigments.
A first phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments and a phosphorescent phosphor layer in which a second phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments is dispersed in a light-transmitting binder (binding material). Become
3. The phosphorescent light emitting device according to claim 1, wherein the phosphorescent phosphor layer is formed partially or entirely on the surface of an arbitrary article.
A first phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments and a second phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments are dispersed in a first light-transmitting binder (binding material). 1 luminous phosphor layer;
A second phosphorescent phosphor layer in which the other of the first and second phosphorescent phosphors is dispersed in a second light-transmitting binder (binding material),
3. The phosphorescent light-emitting device according to claim 1, wherein the first and second phosphorescent phosphor layers are formed by being partially or fully laminated on the surface of an arbitrary article.
A first phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments and a second phosphorescent phosphor composed of a plurality of phosphorescent fluorescent pigments are dispersed in a first light-transmitting binder (binding material). 1 luminous phosphor layer;
A second phosphorescent phosphor layer in which the other of the first and second phosphorescent phosphors is dispersed in a second light-transmitting binder (binding material),
The first and second phosphorescent phosphor layers are formed on the first and second surfaces, respectively, through any article having light transmission properties having the first and second surfaces facing each other. The luminous light-emitting device according to claim 2.
The first phosphorescent phosphor and the first phosphorescent phosphor according to claim 1 or 2, respectively, comprising the first and second phosphorescent fluorescent pigments, respectively. A luminous phosphor in which is dispersed in a paint or ink containing a light-transmitting resin.
The first phosphorescent phosphor and the first phosphorescent phosphor according to claim 1 or 2, respectively, comprising the first and second phosphorescent fluorescent pigments, respectively. Luminescent light-emitting molded article that contains a dispersed in a light-transmitting resin molding material.
The first phosphorescent phosphor and the first phosphorescent phosphor according to claim 1 or 2, respectively, comprising the first and second phosphorescent fluorescent pigments, respectively. Luminescent light-emitting element containing a light-transmitting resin member in the form of granules or pellets.
The first phosphorescent phosphor and the second phosphorescent phosphor according to claim 1 or claim 2 are composed of a first phosphorescent fluorescent pigment and a second phosphorescent fluorescent pigment, respectively. A granular or pellet-shaped light-transmitting core (core) member containing dispersed one of the phosphorescent fluorescent pigments of
A phosphorescent light emitting device comprising a light transmissive shell (shell) member that disperses the other of the first and second phosphorescent fluorescent pigments and covers the light transmissive core (core) member.
A plurality of first phosphorescent phosphor particles that are excited by a light beam having a first excitation wavelength band and emit a first afterglow light beam having a first emission wavelength band;
A plurality of second phosphorescent fluorescence that is excited by a light beam in a second excitation wavelength band partially or entirely including the first light emission wavelength band and emits a second afterglow light having a second light emission wavelength band Body particles,
Luminescent light-emitting optical fiber comprising a core having a light guide property or carried on an optical fiber comprising the core and a light-transmitting clad that covers the entire surface or side surface of the core. .
14. The phosphorescent light-emitting optical fiber according to claim 13, wherein a light beam that excites the first and second phosphorescent phosphor particles from the end face of the optical fiber is introduced into the core.
14. The phosphorescent light emitting optical fiber according to claim 13, wherein the first and second phosphorescent phosphor particles are dispersed and contained in the core.
14. The phosphorescent light-emitting optical fiber according to claim 13, wherein either one of the first and second phosphorescent phosphor particles is dispersed and contained in the core, and the other is dispersed and contained in the cladding. .
14. The phosphorescent light-emitting optical fiber according to claim 13, wherein the first and second phosphorescent phosphor particles are dispersed in the clad.
The clad is composed of a first clad and a second clad, and either one of the first and second phosphorescent phosphor particles is dispersed and contained in either the first or second clad. 14. The phosphorescent light-emitting optical fiber according to claim 13, wherein the other of the first and second phosphorescent phosphor particles is dispersed and contained in the other of the first and second claddings.
A plurality of first phosphorescent phosphor particles that are excited by a light beam having a first excitation wavelength band and emit a first afterglow light beam having a first emission wavelength band;
A plurality of second phosphorescent fluorescence that is excited by a light beam in a second excitation wavelength band partially or entirely including the first light emission wavelength band and emits a second afterglow light having a second light emission wavelength band Body particles,
The first and second surfaces facing each other, and the plate-like light-guiding member having light transmittance composed of the first end surface and the second end surface facing each other are carried,
A luminous light-emitting device that introduces the light beam from the first end surface and / or the second end surface into the plate-shaped light guide member.
The first and second phosphorescent phosphor particles are provided with a phosphorescent light emitting layer that is dispersed and contained in a light transmissive binder layer, and the phosphorescent light emitting layer is the first surface and / or the second surface. 20. The phosphorescent light-emitting device according to claim 19, wherein the phosphorescent light-emitting device is partially or entirely formed.
20. The light emitting diode according to claim 19, further comprising at least one light emitting diode for introducing the light beam into the plate-shaped light guide member, wherein the light emitting diode is disposed on the first end face and / or the second end face. Luminescent light emitting device.
20. The phosphorescent light emitting device according to claim 19, wherein the first and second phosphorescent phosphor particles are dispersed and contained in the plate-like light guide member.
Either one of the first and second phosphorescent phosphor particles is dispersed and contained in the plate-shaped light guide member, and the other of the first and second phosphorescent phosphor particles is light transmissive. 20.A phosphorescent light emitting layer dispersed and contained in a binder layer, wherein the phosphorescent light emitting layer is partially or entirely formed on the first surface and / or the second surface. Luminescent light emitting device.

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