WO2018181328A1 - レーザー光検知具 - Google Patents
レーザー光検知具 Download PDFInfo
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- WO2018181328A1 WO2018181328A1 PCT/JP2018/012456 JP2018012456W WO2018181328A1 WO 2018181328 A1 WO2018181328 A1 WO 2018181328A1 JP 2018012456 W JP2018012456 W JP 2018012456W WO 2018181328 A1 WO2018181328 A1 WO 2018181328A1
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- WIPO (PCT)
- Prior art keywords
- laser light
- light
- laser
- light emitting
- laser beam
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KMKCBOQRRWZRII-UHFFFAOYSA-N diethyl 2,5-diaminobenzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC(N)=C(C(=O)OCC)C=C1N KMKCBOQRRWZRII-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WABMHCVYKWKAAH-UHFFFAOYSA-N dimethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(O)=C(C(=O)OC)C=C1O WABMHCVYKWKAAH-UHFFFAOYSA-N 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- OOJBEQBXIJTMIN-UHFFFAOYSA-N europium 1,1,1-trifluoropentane-2,4-dione Chemical compound FC(C(=O)CC(C)=O)(F)F.[Eu] OOJBEQBXIJTMIN-UHFFFAOYSA-N 0.000 description 1
- VYOQNCIOWJDZTL-UHFFFAOYSA-N europium 1,10-phenanthroline 1,1,1-trifluoropentane-2,4-dione Chemical compound [Eu].N1=CC=CC2=CC=C3C=CC=NC3=C12.FC(C(=O)CC(C)=O)(F)F.FC(C(=O)CC(C)=O)(F)F.FC(C(=O)CC(C)=O)(F)F VYOQNCIOWJDZTL-UHFFFAOYSA-N 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- FJPULUGNRYRRDX-UHFFFAOYSA-N europium;2-pyridin-2-ylpyridine Chemical compound [Eu].N1=CC=CC=C1C1=CC=CC=N1 FJPULUGNRYRRDX-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000001061 forehead Anatomy 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- QIJRBQDGQLSRLG-UHFFFAOYSA-N magnesium;pentane-2,4-dione Chemical compound [Mg].CC(=O)CC(C)=O QIJRBQDGQLSRLG-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003329 sebacic acid derivatives Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
- G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/58—Photometry, e.g. photographic exposure meter using luminescence generated by light
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N5/00—Details of television systems
- H04N5/30—Transforming light or analogous information into electric information
- H04N5/33—Transforming infrared radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
- H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/30—Devices controlled by radiation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a laser beam detector that can easily detect irradiation when irradiated with laser beam.
- a laser pointer is used as an instrument for pointing to a point such as a printed or written chart or an image displayed on a projector in a presentation or education.
- a point such as a printed or written chart or an image displayed on a projector in a presentation or education.
- semiconductor lasers extremely high-power laser pointers have come to be supplied at low cost and have been used in a wide range of fields (for example, Patent Document 1).
- Laser pointers are mainly visible light such as red and green, but ultraviolet or infrared laser pointers that are invisible to human eyes are also commercially available. When such an invisible laser beam is irradiated, it may lead to an accident or blindness without being aware of the irradiation. Moreover, even if it is a visible laser beam, it is hard to notice that it is irradiated as long as the light does not enter the eye directly.
- Patent Document 2 discloses a laser irradiation detection device capable of effective defense against laser-guided bullets, but is an extremely expensive and large-scale device for military purposes and can be applied to general purposes. It wasn't.
- An object of this invention is to provide the laser beam detection tool which can detect irradiation simply, when a laser beam is irradiated in view of the said present condition.
- the present invention relates to a laser beam detector capable of detecting irradiation when irradiated with a laser beam, and comprising a thermoplastic resin and a luminescent material that emits visible light when excited by the laser beam. It is a laser beam detection tool containing.
- the present invention is described in detail below.
- the present inventors radiated laser light onto a light emitting sheet containing a thermoplastic resin and a light emitting material that is excited by laser light and emits visible light.
- the inventors have found that laser light can be easily detected even when the laser light is ultraviolet or infrared invisible light, and the present invention has been completed.
- the laser beam detector of the present invention includes a light emitting sheet containing a thermoplastic resin and a light emitting material.
- the thermoplastic resin is not particularly limited.
- examples thereof include resins and polyethylene terephthalate resins.
- a polyvinyl acetal resin is preferable because when it is laminated with a transparent plate such as glass, it can be used in combination with a plasticizer to exhibit excellent adhesion to the transparent plate.
- the polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal resin as needed.
- the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 40 mol%, the preferable upper limit is 85 mol%, the more preferable lower limit is 60 mol%, and the more preferable upper limit is 75 mol%.
- the said polyvinyl acetal resin has a preferable minimum of the amount of hydroxyl groups of 15 mol%, and a preferable upper limit of 35 mol%.
- the hydroxyl group amount is 15 mol% or more, the light emitting sheet can be easily molded.
- the hydroxyl group amount is 35 mol% or less, the resulting light-emitting sheet can be easily handled.
- the degree of acetalization and the amount of hydroxyl groups can be measured in accordance with, for example, JIS K6728 “Testing method for polyvinyl butyral”.
- the polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used.
- the preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000.
- the polymerization degree of the polyvinyl alcohol is 500 or more, the penetration resistance is enhanced when the resulting light emitting sheet is laminated with a transparent plate.
- the polymerization degree of the polyvinyl alcohol is 4000 or less, the light emitting sheet can be easily molded.
- the minimum with a more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.
- the aldehyde is not particularly limited, but generally an aldehyde having 1 to 10 carbon atoms is preferably used.
- the aldehyde having 1 to 10 carbon atoms is not particularly limited.
- n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable.
- These aldehydes may be used alone or in combination of two or more.
- the light-emitting material is a light-emitting material that emits visible light when excited by laser light.
- a light emitting sheet containing such a light emitting material when the laser light is irradiated, the light emitting material emits visible light, for example, the laser light is ultraviolet or infrared invisible laser light. However, it can be easily detected. Furthermore, since a part of the energy of the laser light is consumed for light emission of the light emitting material, it is expected that the energy of the laser light is attenuated and damage to the eyes can be reduced.
- the light emitting material examples include a light emitting material that emits light by visible laser light having a wavelength of 380 to 750 nm, a light emitting material that emits light by ultraviolet laser light having a wavelength of 380 nm or less, and an infrared laser light having a wavelength of 750 nm or more.
- the light emitting material to be used can be used. These luminescent materials may be used independently and may use 2 or more types together. By using two or more kinds of light emitting materials in combination, it is possible to detect laser light in a wide wavelength range.
- Examples of the light emitting material include lanthanoid complexes having a multidentate ligand containing a halogen atom.
- a lanthanoid complex having a polydentate ligand containing a halogen atom emits light with high emission intensity when irradiated with laser light.
- Examples of the lanthanoid complex having a polydentate ligand containing a halogen atom include a lanthanoid complex having a bidentate ligand containing a halogen atom, a lanthanoid complex having a tridentate ligand containing a halogen atom, and a tetradentate containing a halogen atom.
- Examples include lanthanoid complexes having a ligand, lanthanoid complexes having a pentadentate ligand containing a halogen atom, and lanthanoid complexes having a hexadentate ligand containing a halogen atom.
- a lanthanoid complex having a bidentate ligand containing a halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom has a wavelength of 580 to 780 nm when irradiated with light having a wavelength of 300 to 410 nm.
- Light with extremely high emission intensity Since this luminescence is extremely high in intensity, the luminescent sheet containing the luminescence can detect the irradiation of laser light with extremely high sensitivity.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is also excellent in heat resistance.
- the luminescent material may be deteriorated due to heat generation at a high temperature.
- a lanthanoid complex having a bidentate ligand containing a halogen atom or a halogen atom By using a lanthanoid complex having a tridentate ligand containing, laser light can be reliably detected without deterioration.
- the lanthanoid includes lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. Since higher emission intensity can be obtained, the lanthanoid is preferably neodymium, europium or terbium, more preferably europium or terbium, and still more preferably europium.
- Examples of the lanthanoid complex having a bidentate ligand containing a halogen atom include tris (trifluoroacetylacetone) phenanthroline europium, tris (trifluoroacetylacetone) diphenylphenanthroline europium, tris (hexafluoroacetylacetone) diphenylphenanthroline europium, and tris (hexa). Fluoroacetylacetone) bis (triphenylphosphine) europium, tris (trifluoroacetylacetone) 2,2′-bipyridine europium, tris (hexafluoroacetylacetone) 2,2′-bipyridine europium, and the like.
- Examples of the lanthanoid complex having a tridentate ligand containing a halogen atom include terpyridine trifluoroacetylacetone europium, terpyridine hexafluoroacetylacetone europium, and the like.
- a halogen atom of the lanthanoid complex having a bidentate ligand containing a halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be used. .
- a fluorine atom is preferable because the structure of the ligand is stabilized.
- the lanthanoid complex having a halogen atom and an acetylacetone skeleton containing a halogen atom is particularly excellent.
- Lanthanoid complexes having a bidentate ligand are preferred.
- Examples of the lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing a halogen atom include Eu (TFA) 3 phen, Eu (TFA) 3 dpphen, Eu (HFA) 3 phen, and [Eu (FOD) 3 ].
- the structure of a lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing these halogen atoms is shown.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is preferably particulate. By being particulate, it becomes easier to finely disperse the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom in a light emitting sheet.
- the preferred lower limit of the average particle size of the lanthanoid complex is 0.01 ⁇ m, preferably The upper limit is 10 ⁇ m, the more preferable lower limit is 0.03 ⁇ m, and the more preferable upper limit is 1 ⁇ m.
- a light emitting material having a terephthalic acid ester structure can also be used.
- the light emitting material having the terephthalic acid ester structure emits light when irradiated with light.
- Examples of the light emitting material having the terephthalic acid ester structure include a compound having a structure represented by the following general formula (1) and a compound having a structure represented by the following general formula (2). These may be used alone or in combination of two or more.
- R 1 represents an organic group, and x is 1, 2, 3 or 4. Since the transparency of the light emitting sheet is further increased, x is preferably 1 or 2, more preferably a hydroxyl group at the 2-position or 5-position of the benzene ring, and the 2-position and 5-position of the benzene ring. More preferably, it has a hydroxyl group.
- the organic group for R 1 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms. When the hydrocarbon group has 10 or less carbon atoms, the light emitting material having the terephthalic acid ester structure can be easily dispersed in the light emitting sheet.
- the hydrocarbon group is preferably an alkyl group.
- Examples of the compound having the structure represented by the general formula (1) include diethyl-2,5-dihydroxyterephthalate, dimethyl-2,5-dihydroxyterephthalate and the like. Among them, since a higher contrast image can be displayed, the compound having the structure represented by the general formula (1) is diethyl-2,5-dihydroxyterephthalate (“2,5-dihydroxyterephthalic acid manufactured by Aldrich). Diethyl ”) is preferred.
- R 2 represents an organic group
- R 3 and R 4 represent a hydrogen atom or an organic group
- y is 1, 2, 3, or 4.
- the organic group for R 2 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms.
- the hydrocarbon group is preferably an alkyl group.
- NR 3 R 4 is an amino group.
- R 3 and R 4 are preferably hydrogen atoms.
- one hydrogen atom may be the amino group, and two hydrogen atoms may be the amino group.
- the three hydrogen atoms may be the amino group, and the four hydrogen atoms may be the amino group.
- diethyl-2,5-diaminoterephthalate (manufactured by Aldrich) is preferable because an image with higher contrast can be displayed.
- the content of the light emitting material in the light emitting sheet may be appropriately adjusted according to the type of the light emitting material, but the preferable lower limit with respect to 100 parts by weight of the thermoplastic resin is 0.001 part by weight, and the preferable upper limit is 10 parts by weight. is there.
- the content of the light emitting material is 0.001 part by weight or more, irradiation with laser light can be reliably detected while reducing the irradiation intensity.
- the content of the luminescent material is 10 parts by weight or less, the transparency of the luminescent sheet is further increased.
- the more preferable lower limit of the content of the light emitting material is 0.01 parts by weight, the more preferable upper limit is 8 parts by weight, the still more preferable lower limit is 0.1 parts by weight, and the still more preferable upper limit is 5 parts by weight.
- the light emitting sheet may further contain a plasticizer.
- the plasticizer is not particularly limited, and examples thereof include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers, and the like. Is mentioned.
- the plasticizer is preferably a liquid plasticizer.
- the said monobasic organic acid ester is not specifically limited,
- the glycol ester obtained by reaction of glycol and a monobasic organic acid etc. are mentioned.
- the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
- the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and the like.
- triethylene glycol dicaproate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-octylate, triethylene glycol di-2-ethylhexylate and the like are preferable.
- the polybasic organic acid ester is not particularly limited.
- an ester compound of a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferable.
- the organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl Butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di- -Ethylhexanoate, dipropylene glycol di-2-ethylbutyrate,
- the organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- dihexyl adipate DHA
- triethylene glycol di-2-ethylhexanoate 3GO
- tetraethylene glycol di-2-ethylhexanoate 4GO
- the preferable minimum with respect to 100 weight part of the said thermoplastic resins is 30 weight part, and a preferable upper limit is 100 weight part.
- the content of the plasticizer is 30 parts by weight or more, the melt viscosity becomes low, so that the light emitting sheet can be easily molded.
- the content of the plasticizer is 100 parts by weight or less, the light emitting sheet has high transparency.
- a more preferred lower limit of the plasticizer content is 35 parts by weight, a more preferred upper limit is 80 parts by weight, a still more preferred lower limit is 45 parts by weight, a still more preferred upper limit is 70 parts by weight, a particularly preferred lower limit is 50 parts by weight, and a particularly preferred upper limit. Is 63 parts by weight.
- the light emitting sheet preferably contains an adhesive force adjusting agent.
- an alkali metal salt or alkaline-earth metal salt is used suitably, for example.
- salts, such as potassium, sodium, magnesium, are mentioned, for example.
- the acid constituting the salt include organic acids of carboxylic acids such as octylic acid, hexyl acid, 2-ethylbutyric acid, butyric acid, acetic acid and formic acid, or inorganic acids such as hydrochloric acid and nitric acid.
- the light emitting sheet may contain potassium, sodium, and magnesium derived from raw materials such as a neutralizing agent used at the time of manufacturing the thermoplastic resin, in addition to the adhesive strength adjusting agent.
- the light emitting property of the light emitting material may be lowered.
- the light-emitting material is a lanthanoid complex having a bidentate ligand containing a halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom. Therefore, the total content of potassium, sodium and magnesium contained in the light emitting sheet is preferably 50 ppm or less. By setting the total content of potassium, sodium and magnesium to 50 ppm or less, it is possible to prevent the light emitting property of the light emitting material from being lowered.
- the light emitting sheet preferably further contains a dispersant.
- a dispersant is, for example, a compound having a sulfonic acid structure such as a linear alkylbenzene sulfonate, or an ester structure such as a diester compound, a ricinoleic acid alkyl ester, a phthalic acid ester, an adipic acid ester, a sebacic acid ester, or a phosphoric acid ester.
- Compounds having an ether structure such as polyoxyethylene glycol, polyoxypropylene glycol and alkylphenyl-polyoxyethylene-ether, compounds having a carboxylic acid structure such as polycarboxylic acid, laurylamine, dimethyllauryl
- Compounds having an amine structure such as amines, oleylpropylenediamine, secondary amines of polyoxyethylene, tertiary amines of polyoxyethylene, and diamines of polyoxyethylene
- polyalkylenepolyaminealkyleneoxy Dispersants such as compounds having a polyamine structure such as amides, compounds having an amide structure such as oleic acid diethanolamide and alkanol fatty acid amide, and compounds having a high molecular weight amide structure such as polyvinylpyrrolidone and polyester acid amide amine salts Can be used.
- high molecular weight dispersing agents such as polyoxyethylene alkyl ether phosphoric acid (salt), high molecular polycarboxylic acid, and condensed ricinoleic acid ester.
- the high molecular weight dispersant is defined as a dispersant having a molecular weight of 10,000 or more.
- the dispersant for 100 parts by weight of the luminescent material in the luminescent sheet
- the preferable lower limit of the content of is 1 part by weight, and the preferable upper limit is 50 parts by weight.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is uniformly dispersed in a light emitting sheet.
- the more preferable lower limit of the content of the dispersant is 3 parts by weight, the more preferable upper limit is 30 parts by weight, the still more preferable lower limit is 5 parts by weight, and the still more preferable upper limit is 25 parts by weight.
- the light emitting sheet may contain additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye as necessary.
- additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye as necessary.
- the light emitting sheet preferably has a visible light transmittance of 70% or more.
- the visible light transmittance is 70% or more, it can be used for various applications such as vehicle window glass.
- the visible light transmittance is more preferably 80% or more, and still more preferably 90% or more.
- the light emitting sheet may preferable lower limit is 1 cd / m 2 in luminance when irradiated with a laser beam, and the desirable upper limit is 15000 cd / m 2. When the emission luminance is within this range, irradiation can be more reliably detected when laser light is irradiated.
- the laser beam detector of the present invention can detect irradiation easily and reliably when the laser beam is irradiated.
- the aspect of the laser beam detection tool of the present invention is not particularly limited, it preferably has a laminated structure of a transparent plate and a light emitting sheet. By using the above laminate structure, the handleability is improved and application to various uses becomes possible. Especially, it is preferable to have a structure (laminated glass structure) in which the light emitting sheet is laminated between a pair of transparent plates.
- the transparent plate a commonly used transparent plate glass can be used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass.
- inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass.
- the ultraviolet shielding glass in which the ultraviolet shielding coating layer was formed in the glass surface can be used, it is preferable to use as a glass plate opposite to the side irradiated with the light ray of a specific wavelength.
- an organic plastics plate such as polyethylene terephthalate, polycarbonate, polyacrylate or the like can be used as the transparent plate. Two or more types of transparent plates may be used as the transparent plate. Moreover, you may use the transparent plate from which 2 or more types of thickness differs as said transparent plate.
- the laser beam detector of the present invention has a laminated structure or a laminated glass structure, for example, a window glass for a vehicle such as a car, a motorcycle, an airplane, etc. Irradiation can be detected while reducing the irradiation intensity. It can also be used for goggles and eyeglass lenses.
- the laser beam detector of the present invention further includes a detector that detects that the laser beam has been irradiated.
- a detection unit By including such a detection unit, it is possible to detect irradiation of laser light more easily and reliably.
- the detection unit is not particularly limited, and examples thereof include a device that emits a signal when an image of the entire surface of the light emitting sheet is taken and light emission is recognized on the light emitting sheet on the obtained image. At this time, it is preferable that the apparatus detects only the laser light emitted from one side of the laser light detector and does not detect the laser light emitted from the other side.
- the laser beam detector of the present invention when used as a laminated glass structure and as a window glass for vehicles such as cars, motorcycles, airplanes, etc., the laser beam irradiated from the outside is detected. On the other hand, it is possible to prevent detection of laser light emitted from the inside for display on a head-up display or the like.
- the laser beam detector of the present invention further includes a notification unit that performs notification when the detection unit detects a laser.
- a notification unit that performs notification when the detection unit detects a laser.
- the notification unit When the detection unit detects a laser, the notification unit receives the signal and performs notification.
- the notification method is not particularly limited, and examples thereof include sound, vibration, image, and video.
- the notification unit preferably stops the notification when the detection unit stops detecting the laser beam. Thereby, it can be detected while the laser beam irradiation continues, and can be detected when the irradiation stops.
- the laser beam detector which can detect irradiation simply can be provided.
- Example 1 (1) Preparation of Eu (TFA) 3 phen 12.5 mmol of europium acetate (Eu (CH 3 COO) 3 ) was dissolved in 50 mL of distilled water, and 33.6 mmol of trifluoroacetylacetone (TFA, CH 3 COCH 2 COCF 3 ) was dissolved. The mixture was further stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized with methanol and distilled water to obtain Eu (TFA) 3 (H 2 O) 2 .
- the total amount of the obtained plasticizer solution and 100 parts by weight of polyvinyl butyral (PVB, polymerization degree 1700) were sufficiently kneaded with a mixing roll to prepare a resin composition.
- the obtained resin composition was extruded using an extruder to obtain a light emitting sheet having a thickness of 760 ⁇ m.
- Example 2 12.5 mmol of terbium acetate (Tb (CH 3 COO) 3 ) was dissolved in 50 mL of distilled water, 33.6 mmol of trifluoroacetylacetone (TFA, CH 3 COCH 2 COCF 3 ) was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized with methanol and distilled water to obtain Tb (TFA) 3 (H 2 O) 2 . The obtained complex Tb (TFA) 3 (H 2 O) 2 (5.77 g) and 1,10-phenanthroline (phen) (2.5 g) were dissolved in 100 mL of methanol and heated under reflux for 12 hours.
- Tb (TFA) 3 (H 2 O) 2 5.77 g
- 1,10-phenanthroline (phen) 2.5 g
- Tb (TFA) 3 phene was obtained by recrystallization from a mixed solvent of toluene and hexane.
- a light emitting sheet and a laser beam detector were manufactured in the same manner as in Example 1 except that Tb (TFA) 3 phen was used instead of Eu (TFA) 3 phen.
- Example 3 A light emitting sheet and laser light in the same manner as in Example 1 except that diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”) was used instead of Eu (TFA) 3 phen. A detector was manufactured.
- Example 1 A light emitting sheet and a laser beam detector were manufactured in the same manner as in Example 1 except that no light emitting material was used.
- the laser light source, the laser light detector, and the observer were installed in a straight line so that the horizontal intervals were 20 m and 1 m, respectively.
- the height of the laser light source and the height of the laser beam detector were matched with the height of the observer's line of sight.
- laser light was irradiated from the laser light source so as not to directly enter the eyes of the observer (targeted at the forehead).
- the case where the observer was able to detect that the laser beam was irradiated by the light emission on the laser beam detector was evaluated as “ ⁇ ”, and the case where the observer was not detected was evaluated as “X”.
- NDV4B16 wavelength 405 nm, output 300 mW
- the position of the laser beam was recorded in order to irradiate the same position with the laser beam.
- Laser detectability indirect observation
- a laser light source, a laser light detector, and an observer were installed.
- the height of the laser light source and the height of the laser beam detector were matched with the height of the observer's line of sight. In this state, a laser beam was irradiated from the laser light source to the same position as the direct observation performed previously.
- the case where the observer was able to detect that the laser beam was irradiated by light emission on the laser beam detector was evaluated as “ ⁇ ”, and the case where the observer was not detected was evaluated as “X”.
- the laser beam detectors obtained in Examples 1 to 3 were able to detect the laser beam even when the observer was not positioned on a straight line of the laser beam.
- the horizontal intervals are 20 m and 1 m, respectively, and the detection part is positioned at a 45 ° angle in the horizontal direction with respect to the glass center part of the laser light detection tool.
- the detection unit takes an image of the entire surface of the laser beam detector (light emitting sheet), and when the laser beam detector (light emitting sheet) emits light on the obtained image, a signal is sent to the notification unit. It was set as the device which transmits. Furthermore, when the said detection part detected the laser, the alerting
- the laser beam detector which can detect irradiation simply can be provided.
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Abstract
Description
特許文献2には、レーザー誘導弾に対して有効な防御手段が可能なレーザー照射検出装置が開示されているが、軍事目的の極めて高価かつ大がかりな装置であり、到底一般の用途に適用できるものではなかった。
以下に本発明を詳述する。
上記熱可塑性樹脂は特に限定されず、例えば、ポリビニルアセタール樹脂、エチレン-酢酸ビニル共重合体樹脂、エチレン-アクリル共重合体樹脂、ポリウレタン樹脂、硫黄元素を含有するポリウレタン樹脂、ポリビニルアルコール樹脂、塩化ビニル樹脂、ポリエチレンテレフタレート樹脂等が挙げられる。なかでも、ガラス等の透明板と積層したときに、可塑剤と併用して透明板に対して優れた接着性を発揮できることからポリビニルアセタール樹脂が好適である。
上記ポリビニルアセタール樹脂のアセタール化度の好ましい下限は40モル%、好ましい上限は85モル%であり、より好ましい下限は60モル%、より好ましい上限は75モル%である。
なお、上記アセタール化度及び水酸基量は、例えば、JIS K6728「ポリビニルブチラール試験方法」に準拠して測定できる。
上記ポリビニルアルコールの重合度の好ましい下限は500、好ましい上限は4000である。上記ポリビニルアルコールの重合度が500以上であると、得られる発光シートを透明板との積層体としたときに耐貫通性が高くなる。上記ポリビニルアルコールの重合度が4000以下であると、発光シートの成形が容易になる。上記ポリビニルアルコールの重合度のより好ましい下限は1000、より好ましい上限は3600である。
ランタノイド錯体のなかでも、ハロゲン原子を含む多座配位子を有するランタノイド錯体はレーザー光を照射することにより高い発光強度で発光する。上記ハロゲン原子を含む多座配位子を有するランタノイド錯体としては、ハロゲン原子を含む二座配位子を有するランタノイド錯体、ハロゲン原子を含む三座配位子を有するランタノイド錯体、ハロゲン原子を含む四座配位子を有するランタノイド錯体、ハロゲン原子を含む五座配位子を有するランタノイド錯体、ハロゲン原子を含む六座配位子を有するランタノイド錯体等が挙げられる。
上記ハロゲン原子を含む三座配位子を有するランタノイド錯体は、例えば、ターピリジントリフルオロアセチルアセトンユーロピウム、ターピリジンヘキサフルオロアセチルアセトンユーロピウム等が挙げられる。
上記ハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体は、例えば、Eu(TFA)3phen、Eu(TFA)3dpphen、Eu(HFA)3phen、[Eu(FOD)3]bpy、[Eu(TFA)3]tmphen、[Eu(FOD)3]phen等が挙げられる。これらのハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体の構造を示す。
上記ハロゲン原子を含む二座配位子を有するランタノイド錯体又はハロゲン原子を含む三座配位子を有するランタノイド錯体が粒子状である場合、ランタノイド錯体の平均粒子径の好ましい下限は0.01μm、好ましい上限は10μmであり、より好ましい下限は0.03μm、より好ましい上限は1μmである。
これらは単独で用いてもよく、2種以上を用いてもよい。
上記発光シートの透明性がより一層高くなることから、xは1又は2であることが好ましく、ベンゼン環の2位又は5位に水酸基を有することがより好ましく、ベンゼン環の2位及び5位に水酸基を有することが更に好ましい。
上記R1の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。
上記炭化水素基の炭素数が10以下であると、上記テレフタル酸エステル構造を有する発光材料を発光シート中に容易に分散させることができる。
上記炭化水素基はアルキル基であることが好ましい。
なかでも、コントラストがより一層高い画像を表示できることから、上記一般式(1)で表される構造を有する化合物はジエチル-2,5-ジヒドロキシルテレフタレート(Aldrich社製「2,5-ジヒドロキシテレフタル酸ジエチル」)であることが好ましい。
上記R2の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。
上記炭化水素基の炭素数が上記上限以下であると、上記テレフタル酸エステル構造を有する発光材料を発光シート中に容易に分散させることができる。
上記炭化水素基はアルキル基であることが好ましい。
上記一般式(2)中、NR3R4はアミノ基である。
R3及びR4は、水素原子であることが好ましい。
上記一般式(2)で表される構造を有する化合物のベンゼン環の水素原子のうち、一つの水素原子が上記アミノ基であってもよく、二つの水素原子が上記アミノ基であってもよく、三つの水素原子が上記アミノ基であってもよく、四つの水素原子が上記アミノ基であってもよい。
上記可塑剤は特に限定されず、例えば、一塩基性有機酸エステル、多塩基性有機酸エステル等の有機エステル可塑剤、有機リン酸可塑剤、有機亜リン酸可塑剤等のリン酸可塑剤等が挙げられる。上記可塑剤は液状可塑剤であることが好ましい。
上記接着力調整剤としては、例えば、アルカリ金属塩又はアルカリ土類金属塩が好適に用いられる。上記接着力調整剤として、例えば、カリウム、ナトリウム、マグネシウム等の塩が挙げられる。
上記塩を構成する酸としては、例えば、オクチル酸、ヘキシル酸、2-エチル酪酸、酪酸、酢酸、蟻酸等のカルボン酸の有機酸、又は、塩酸、硝酸等の無機酸が挙げられる。
そこで、上記発光シートに含まれるカリウム、ナトリウム及びマグネシウムの合計の含有量は50ppm以下であることが好ましい。カリウム、ナトリウム及びマグネシウムの合計の含有量を50ppm以下とすることにより、発光材料の発光性が低下するのを防止することができる。
上記分散剤は、例えば、直鎖アルキルベンゼンスルホン酸塩等のスルホン酸構造を有する化合物や、ジエステル化合物、リシノール酸アルキルエステル、フタル酸エステル、アジピン酸エステル、セバシン酸エステル、リン酸エステル等のエステル構造を有する化合物や、ポリオキシエチレングリコール、ポリオキシプロピレングリコールやアルキルフェニル-ポリオキシエチレン-エーテル等のエーテル構造を有する化合物や、ポリカルボン酸等のカルボン酸構造を有する化合物や、ラウリルアミン、ジメチルラウリルアミン、オレイルプロピレンジアミン、ポリオキシエチレンの2級アミン、ポリオキシエチレンの3級アミン、ポリオキシエチレンのジアミン等のアミン構造を有する化合物や、ポリアルキレンポリアミンアルキレンオキシド等のポリアミン構造を有する化合物や、オレイン酸ジエタノールアミド、アルカノール脂肪酸アミド等のアミド構造を有する化合物や、ポリビニルピロリドン、ポリエステル酸アマイドアミン塩等の高分子量型アミド構造を有する化合物等の分散剤を用いることができる。また、ポリオキシエチレンアルキルエーテルリン酸(塩)や高分子ポリカルボン酸、縮合リシノール酸エステル等の高分子量分散剤を用いてもよい。なお、高分子量分散剤とは、その分子量が1万以上である分散剤と定義される。
本発明のレーザー光検知具の態様は特に限定されないが、透明板と発光シートとの積層体構造を有することが好ましい。上記積層体構造とすることにより取り扱い性が向上し、種々の用途への適用が可能となる。なかでも、一対の透明板の間に上記発光シートが積層されている構造(合わせガラス構造)を有することが好ましい。
上記透明板として、2種類以上の透明板を用いてもよい。また、上記透明板として、2種以上の厚さの異なる透明板を用いてもよい。
上記検知部としては特に限定されず、例えば、上記発光シートの全面の画像を撮影し、得られた画像上で発光シートに発光が認められた場合に、シグナルを発信する装置等が挙げられる。
この際、レーザー光検知具の一方の側から照射されたレーザー光のみを検知し、他方の側から照射されたレーザー光は検知しない装置とすることが好ましい。このような装置とすることにより、例えば、本発明のレーザー光検知具を合わせガラス構造として、車やバイク、飛行機等の車両用窓ガラスとして用いた場合に、外部から照射されたレーザー光を検知できる一方、ヘッドアップディスプレイ等の表示のために内側から照射されたレーザー光を検知してしまうのを防止することができる。
上記報知部は、検知部がレーザー光を検出しなくなったときに報知を停止することが好ましい。これにより、レーザー光の照射が持続している間はそれを検知することができ、照射が止んだときにはそれを検知することができる。
(1)Eu(TFA)3phenの調製
酢酸ユーロピウム(Eu(CH3COO)3)12.5mmolを50mLの蒸留水へ溶かし、トリフルオロアセチルアセトン(TFA、CH3COCH2COCF3)33.6mmolを加え、室温で3時間撹拌した。沈殿した固体を濾過、水洗後、メタノールと蒸留水で再結晶を行なってEu(TFA)3(H2O)2を得た。得られた錯体Eu(TFA)3(H2O)25.77gと1,10-フェナントロリン(phen)2.5gを100mLのメタノールに溶かし、12時間加熱還流を行なった。12時間後、メタノールを減圧留去により取り除き、白色生成物を得た。この粉末をトルエンで洗浄し、未反応の原料を吸引濾過により取り除いた後、トルエンを減圧留去し、紛体を得た。トルエン、ヘキサンの混合溶媒により再結晶を行なうことにより、Eu(TFA)3phenを得た。
可塑剤であるトリエチレングリコールジ-2-エチルヘキサノエート(3GO)40重量部に、発光材料としてEu(TFA)3phen0.2重量部と、接着力調整剤として最終的な濃度が0.036phrとなるようにアセチルアセトンマグネシウムを加え、発光性の可塑剤溶液を調製した。得られた可塑剤溶液の全量と、ポリビニルブチラール(PVB、重合度1700)100重量部とをミキシングロールで充分に混練して樹脂組成物を調製した。
得られた樹脂組成物を、押出機を用いて押出し、厚み760μmの発光シートを得た。
得られた発光シートを、縦30cm×横30cmの一対のクリアガラス(厚み2.5mm)の間に積層し、積層体を得た。得られた積層体を、真空ラミネーターにて90℃下、30分保持しつつ真空プレスを行い圧着した。圧着後140℃、14MPaの条件でオートクレーブを用いて20分間圧着を行い、合わせガラス構造のレーザー光検知具を得た。
酢酸テリビウム(Tb(CH3COO)3)12.5mmolを50mLの蒸留水へ溶かし、トリフルオロアセチルアセトン(TFA、CH3COCH2COCF3)33.6mmolを加え、室温で3時間撹拌した。沈殿した固体を濾過、水洗後、メタノールと蒸留水で再結晶を行なってTb(TFA)3(H2O)2を得た。得られた錯体Tb(TFA)3(H2O)25.77gと1,10-フェナントロリン(phen)2.5gを100mLのメタノールに溶かし、12時間加熱還流を行なった。12時間後、メタノールを減圧留去により取り除き、白色生成物を得た。この粉末をトルエンで洗浄し、未反応の原料を吸引濾過により取り除いた後、トルエンを減圧留去し、紛体を得た。トルエン、ヘキサンの混合溶媒により再結晶を行なうことにより、Tb(TFA)3phenを得た。
Eu(TFA)3phenに代えてTb(TFA)3phenを用いた以外は実施例1と同様にして発光シート、レーザー光検知具を製造した。
Eu(TFA)3phenに代えてジエチル-2,5-ジヒドロキシテレフタレート(アルドリッチ社製、「2,5-ジヒドロキシテレフタル酸ジエチル」)を用いた以外は実施例1と同様にして発光シート、レーザー光検知具を製造した。
発光材料を用いなかった以外は実施例1と同様にして発光シート、レーザー光検知具を製造した。
実施例及び比較例で得られたレーザー光検知具について、以下の方法でレーザー検知性を評価した。
結果を表1に示した。
レーザー光源、レーザー光検知具及び観察者の順にそれぞれの水平方向間隔が20m、1mとなるように一直線上に設置した。ここで、レーザー光源の高さ、レーザー光検知具の高さを観察者の目線の高さに合わせた。
この状態でレーザー光源よりレーザー光を観察者の目に直接入らないように照射した(額部分を目標とした)。そのとき観察者がレーザー光検知具上の発光によりレーザー光が照射されたことを検知できた場合を「○」と、検知できなかった場合を「×」と評価した。
なお、レーザー光源としては、日亜化学工業社製「NDV4B16」(波長405nm、出力300mW)を用いた。また、下記の間接観察、音による報知の評価に於いても同じ位置へレーザー光を照射するため、レーザー光の位置を記録した。
レーザー光検知具及び観察者の間隔が1m、且つ、レーザー光検知具のガラスの中央部に対して水平方向に45°の角度となる位置に観察者を設置したこと以外は、上記直接観察と同様に、レーザー光源、レーザー光検知具及び観察者を設置した。ここで、レーザー光源の高さ、レーザー光検知具の高さを観察者の目線の高さに合わせた。この状態でレーザー光源よりレーザー光を、先に行った直接観察と同じ位置に照射した。そのとき観察者がレーザー光検知具上の発光によりレーザー光が照射されたことを検知できた場合を「○」と、検知できなかった場合を「×」と評価した。
実施例1~3で得られたレーザー光検知具は、観察者がレーザー光の一直線上に位置しない場合であっても、レーザー光を検知することができた。
レーザー光源、レーザー光検知具及び検知部の順にそれぞれの水平方向間隔が20m、1m、且つ、レーザー光検知具のガラスの中央部に対して水平方向に45°の角度となる位置に検知部を設置した。ここで、検知部は、レーザー光検知具(発光シート)の全面の画像を撮影し、得られた画像上でレーザー光検知具(発光シート)に発光が認められた場合に、報知部にシグナルを発信する装置とした。更に、上記検知部がレーザーを検知したときに、そのシグナルを受けて音による報知を行う報知部を設けた。
この状態でレーザー光源よりレーザー光を、先に行った直接観察と同じ位置に照射した。そのとき報知部の音によりレーザー光が照射されたことを検知できた場合を「○」と、検知できなかった場合を「×」と評価した。
実施例1~3で得られたレーザー光検知具は、報知部が音を発することにより、レーザー光を検知することができた。
Claims (9)
- レーザー光が照射されたときに、照射を検知することができるレーザー光検知具であって、
熱可塑性樹脂と、レーザー光によって励起され可視光を発光する発光材料を含有する発光シートを含む
ことを特徴とするレーザー光検知具。 - 発光材料は、波長380~750nmの可視レーザー光によって発光するものであることを特徴とする請求項1記載のレーザー光検知具。
- 発光材料は、波長380nm以下の紫外線レーザー光によって発光するものであることを特徴とする請求項1記載のレーザー光検知具。
- 発光材料は、波長750nm以上の赤外線レーザー光によって発光するものであることを特徴とする請求項1記載のレーザー光検知具。
- 透明板と発光シートとの積層体構造を有することを特徴とする請求項1、2、3又は4記載のレーザー光検知具。
- 一対の透明板の間に発光シートが積層されている構造を有することを特徴とする請求項1、2、3又は4記載のレーザー光検知具。
- 更に、レーザー光が照射されたことを検知する検知部を含むことを特徴とする請求項1、2、3、4、5又は6記載のレーザー光検知具。
- 更に、検知部がレーザーを検知したときに報知を行う報知部を含むことを特徴とする請求項7記載のレーザー光検知具。
- 報知部は、検知部がレーザー光を検出しなくなったときに報知を停止することを特徴とする請求項8記載のレーザー光検知具。
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EP3604246A1 (en) | 2020-02-05 |
EP3604246A4 (en) | 2020-11-25 |
TW201842374A (zh) | 2018-12-01 |
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