WO2018211979A1 - Écran auto-émetteur - Google Patents

Écran auto-émetteur Download PDF

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Publication number
WO2018211979A1
WO2018211979A1 PCT/JP2018/017461 JP2018017461W WO2018211979A1 WO 2018211979 A1 WO2018211979 A1 WO 2018211979A1 JP 2018017461 W JP2018017461 W JP 2018017461W WO 2018211979 A1 WO2018211979 A1 WO 2018211979A1
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WO
WIPO (PCT)
Prior art keywords
resin
layer
self
phosphor
ultraviolet
Prior art date
Application number
PCT/JP2018/017461
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English (en)
Japanese (ja)
Inventor
暢子 満居
幸宏 垰
海田　由里子
玲美 川上
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017245579A external-priority patent/JP2020118701A/ja
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Publication of WO2018211979A1 publication Critical patent/WO2018211979A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10651—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising colorants, e.g. dyes or pigments
    • B32B17/10669—Luminescent agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B21/00—Projectors or projection-type viewers; Accessories therefor
    • G03B21/54—Accessories
    • G03B21/56—Projection screens
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/01—Head-up displays

Definitions

  • the present invention relates to a self-luminous screen that includes a phosphor and can display an image when a portion on which the excitation light is projected emits light.
  • Laminated glass obtained by bonding two glass plates with an intermediate film is used as a window glass for vehicles such as automobiles and window glass for buildings.
  • the intermediate film a film containing a resin such as polyvinyl butyral resin is generally used.
  • a phosphor is contained in an interlayer film of laminated glass and used as a self-luminous screen for a screen of a head-up display device such as an automobile.
  • the excitation light is projected from the projector onto the self-luminous screen, the portion where the excitation light is projected emits light and an image is displayed.
  • the above self-luminous screen has a problem that it emits light or deteriorates due to light from a light source other than the projector, for example, sunlight.
  • a layer that shields excitation light specifically, a layer that contains an ultraviolet absorber, in at least one of the layers that contain a phosphor in the intermediate film
  • Patent Documents 1 and 2 By the layer that blocks the excitation light, it is possible to suppress sunlight and the like from being incident on the layer containing the phosphor, and to suppress unexpected light emission.
  • the layer containing the phosphor and the layer containing the UV absorber are adjacent to each other, the UV absorber moves to the layer containing the phosphor by diffusion, or conversely, the phosphor changes to the layer containing the UV absorber. Easy to migrate.
  • the ultraviolet absorber and the phosphor are mixed in the same layer, the excitation light is absorbed by the ultraviolet absorber, the phosphor emits insufficient light, and the visibility of the image is lowered.
  • Patent Document 1 in order to suppress the above diffusion, it is proposed to arrange the PET film as a diffusion block. However, in this case, a perspective distortion occurs, so that the screen is not suitable.
  • Patent Document 2 in order to suppress the diffusion as described above, it is proposed to use a polyvinyl acetal resin having a different hydroxyl amount for each of the layer containing a phosphor and the layer containing an ultraviolet absorber. However, the effect of suppressing diffusion is not sufficient.
  • An object of the present invention is to provide a self-luminous screen excellent in image visibility and durability.
  • the self-luminous screen in which at least one of the phosphor layer and the ultraviolet absorbing layer contains an inorganic material, an organic material having a water absorption lower than that of the resin and 0.8% by mass or less, or a mixture thereof.
  • % of the resin layer and a third transparent substrate containing an ultraviolet absorber capable of absorbing ultraviolet light having a wavelength of 400 nm, and a laminated structure in which the resin layers are laminated in this order The self-luminous screen in which the matrix of the phosphor layer contains an inorganic material, an organic material having a water absorption of 0.8% by mass or less, or a mixture thereof.
  • a first transparent substrate or a second transparent substrate an ultraviolet absorbing layer containing a matrix and an ultraviolet absorber capable of absorbing ultraviolet light having a wavelength of 400 nm, and a phosphor capable of being excited by the matrix and ultraviolet light having a wavelength of 400 nm
  • a phosphor layer including the layered structure laminated in this order A self-luminous screen in which at least one of the phosphor layer and the ultraviolet absorbing layer contains an inorganic material, an organic material having a water absorption of 0.8% by mass or less, or a mixture thereof.
  • a laminated structure laminated in this order The self-luminous type screen in which the matrix contains an inorganic material, an organic material having a water absorption rate of 0.8% by mass or less, or a mixture thereof.
  • the organic material contained in the matrix is an acrylic resin, polyester resin, polyurethane resin, polyurethane acrylate resin, polycarbonate resin, polyvinyl butyral resin, cycloolefin resin, ethylene / vinyl acetate copolymer resin, or fluorene ring-containing resin.
  • the self-luminous screen according to any one of [1] to [6].
  • the phosphor layer contains at least one phosphor selected from the group consisting of a fluorescent pigment, a fluorescent dye, and semiconductor nanoparticles.
  • the ultraviolet absorbing layer contains at least one ultraviolet absorber selected from the group consisting of organic ultraviolet absorbers or metal oxides and the matrix [1], [3], [5] A self-luminous screen according to any one of [9].
  • the first transparent substrate and the second transparent substrate are each independently glass or transparent resin, and any one of [1], [2], [5] to [10] Luminescent screen.
  • the self-luminous screen of the present invention emits light with sufficient emission intensity at the portion where the excitation light is projected, and the portion where the excitation light is not projected from the projector is suppressed, so that the image can be visually recognized. Excellent in properties. In addition, deterioration of image visibility over time is suppressed, excellent visibility can be maintained over a long period of time, and durability and light resistance are also excellent.
  • FIG. 1 is a schematic configuration diagram schematically illustrating an example of a head-up display device to which a self-luminous screen according to a first embodiment of the present invention is applied. It is a schematic cross section of the self-luminous type screen of a third embodiment of the present invention. It is a schematic cross section of the self-light-emitting screen of the fourth embodiment of the present invention. It is a schematic block diagram which shows typically an example of the rear glass for motor vehicles which applied the self-light-emitting screen of 3rd embodiment of this invention.
  • FIG. 1 is a schematic cross-sectional view of a self-luminous screen 10 according to the first embodiment of the present invention.
  • the self-luminous screen 10 has a laminated structure in which a first transparent base material 11, a phosphor layer 13, a resin layer 15, an ultraviolet absorption layer 17, and a second transparent base material 19 are laminated in this order. Including.
  • the phosphor layer 13 includes a matrix and a phosphor that can be excited by ultraviolet rays having a wavelength of 400 nm (hereinafter also referred to as phosphor (1)).
  • the resin layer 15 contains a resin, does not contain the phosphor (1), and has an ultraviolet transmittance at a wavelength of 400 nm (hereinafter also referred to as ultraviolet transmittance (400 nm)) of 20% or more.
  • the ultraviolet absorbing layer 17 includes a matrix and an ultraviolet absorber that can absorb ultraviolet rays having a wavelength of 400 nm (hereinafter also referred to as an ultraviolet absorber (1)).
  • the ultraviolet transmittance (400 nm) of the resin layer 15 is measured by measuring the transmittance of the resin layer 15 at 400 nm using a spectrophotometer.
  • At least one matrix of the phosphor layer 13 and the ultraviolet absorption layer 17 is an inorganic material, an organic material having a water absorption rate lower than that of the resin of the resin layer 15 and 0.8% by mass or less (hereinafter referred to as “low water absorption organic material”). Or a mixture thereof.
  • the inorganic material, the low water-absorbing organic material, and the mixture thereof are collectively referred to as “material (I)”.
  • the matrix of the phosphor layer 13 and the matrix of the ultraviolet absorption layer 17 either one or both may be made of the material (I). It is preferable that both the matrix of the phosphor layer 13 and the matrix of the ultraviolet absorption layer 17 are the material (I) because more excellent durability can be obtained.
  • the other matrix is the resin of the resin layer 15. Are preferably different resins.
  • the matrix of the phosphor layer 13 is made of the material (I)
  • the matrix of both the phosphor layer 13 and the ultraviolet absorbing layer 17 is made of the material (I).
  • the first surface 10a (outermost surface on the first transparent substrate 11 side) of the self-luminous screen 10 is a surface on the side where excitation light for exciting the phosphor (1) is projected from the projector. Also, typically, the first surface 10a is an indoor surface, and the second surface 10b opposite to the first surface 10a (the outermost surface on the second transparent base material 19 side) is a yaw. The outer surface.
  • Examples of the material of the first transparent substrate 11 and the second transparent substrate 19 include glass and transparent resin.
  • the material of each transparent substrate may be the same or different.
  • the glass constituting the transparent substrate is not particularly limited, and examples thereof include soda lime glass, alkali-free glass, borosilicate glass, and aluminosilicate glass.
  • the transparent substrate may be subjected to chemical strengthening, physical strengthening, hard coating or the like in order to improve durability.
  • a chemically strengthened glass plate is preferable from the viewpoint of achieving both lightness and strength.
  • thermoplastic resin As transparent resin which comprises a transparent base material, the hardened
  • the thermoplastic resin include polycarbonate, thermoplastic polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polymethyl methacrylate and the like.
  • the material of the transparent substrate is preferably glass from the viewpoint of ultraviolet transmittance.
  • the transparent substrate those having no birefringence are preferable from the viewpoint of the visibility of the image displayed on the screen and the visibility of the scene on the other side of the screen.
  • the transparent substrate may have a flat plate shape or a shape having a curved portion.
  • the thickness of the transparent substrate may be a thickness that can maintain the durability of the substrate.
  • the thickness of the transparent substrate may be, for example, 0.5 mm or more, 1 mm or more, and 2 mm or more.
  • the thickness of a transparent base material may be 10 mm or less, for example, and may be 5 mm or less.
  • the arithmetic average roughness Ra of the surface of the first transparent substrate 11 (first surface 10a) and the surface of the second transparent substrate 19 (second surface 10b) is preferably 0.3 ⁇ m or less, 0 .05 ⁇ m or less is more preferable. If Ra is 0.3 ⁇ m or less, the excitation light projected from the projector is unlikely to be scattered on each surface.
  • the Ra of each of the surface of the first transparent substrate 11 (first surface 10a) and the surface of the second transparent substrate 19 (second surface 10b) is 0 from the viewpoint of ease of production and cost. 0.001 ⁇ m or more is preferable.
  • the arithmetic average roughness (Ra) is an arithmetic average roughness measured based on JIS B 0601: 2013 (ISO 4287: 1997, Amd. 1: 2009).
  • the reference length lr (cut-off value ⁇ c) for the roughness curve is 0.8 mm. Even when the outermost layer of the self-luminous screen 10 is not a transparent substrate (for example, a transparent film or a light scattering layer), the first surface 10a and the second surface 10a of the self-luminous screen 10 are provided.
  • a preferable arithmetic average roughness Ra on the surface 10b is the same as that when the outermost layer is a transparent substrate.
  • the ultraviolet transmittance (400 nm) of the first transparent substrate 11 is preferably 70% or more, and more preferably 75% or more. If the ultraviolet transmittance (400 nm) is equal to or greater than the lower limit, the intensity of the fluorescence generated from the phosphor layer 13 is sufficiently strong when the excitation light is projected from the first surface 10a side to the phosphor layer 13. , Video visibility is better.
  • the ultraviolet transmittance (400 nm) of the transparent substrate is measured by measuring the transmittance of the transparent substrate at 400 nm using a spectrophotometer.
  • the visible light transmittance of the first transparent substrate 11 is preferably 80% or more, and more preferably 85% or more. If the visible light transmittance is equal to or higher than the lower limit, the visibility of the image is more excellent.
  • the visible light transmittance of the transparent substrate is determined by the following method. A spectrophotometer is used to measure the spectral transmittance at a wavelength of 380 nm to 780 nm of the total transmitted light transmitted to the other surface with respect to the incident light incident at an incident angle of 0 °. By multiplying this measured value by the weighting coefficient obtained from the spectrum of CIE daylight D65 and the wavelength distribution of the visibility, the visible light transmittance is obtained.
  • the phosphor layer 13 includes a matrix and the phosphor (1).
  • the matrix of the phosphor layer 13 is preferably made of the material (I).
  • the phosphor (1) is not particularly limited as long as it can be excited by an ultraviolet ray having a wavelength of 400 nm, and can be appropriately selected from various known phosphors. Examples of the phosphor include a fluorescent pigment, a fluorescent dye, and semiconductor nanoparticles.
  • fluorescent pigment examples include Y 2 O 2 S: Eu, BaMg 2 Al 16 O 27 : Eu, Mn, (SrCaBaMg) 5 (PO 4 ) 3 Cl: Eu, BaMg 2 Al 16 O 27 : Eu, BaMg 2.
  • fluorescent dye examples include (carbazole-naphthalimide) dye, (acetonitrile-triphenyleneamine) dye, aryl sulfonate cyanine dye, perylene dye, coumarin dye, tris (4,4,4-trifluoro-1- (2- Thienyl) -1,3-butanedionate-O, O ′) bis (triphenylphosphine oxide-O—) europium.
  • a compound having a naphthalimide skeleton or a compound having a coumarin skeleton is preferable because of high durability against ultraviolet rays and excellent weather resistance of the phosphor layer 13 using the fluorescent dye.
  • the compound having a naphthalimide skeleton include 4-bromo-1,8-naphthalimide, 4-amino-1,8-naphthalimide, 4-methoxy-N-methylnaphthalimide, naphthalimide, and 4-amino.
  • Naphthalimide N-methyl-4-aminonaphthalimide, N-ethyl-4-aminonaphthalimide, N-propyl-4-aminonaphthalimide, Nn-butyl-4-aminonaphthalimide, 4-acetylamino Phthalimide, N-methyl-4-acetylaminonaphthalimide, N-ethyl-4-acetylaminonaphthalimide, N-propyl-4-acetylaminonaphthalimide, Nn-butyl-4-acetylaminonaphthalimide, N- Methyl-4-methoxynaphthalimide, N-ethyl-4-methoxynaphthalene N-propyl-4-methoxynaphthalimide, Nn-butyl-4-methoxynaphthalimide, N-methyl-4-ethoxynaphthalimide, N-ethyl-4-ethoxynaphthalimide, N-propyl-4-meth
  • Examples of the compound having a coumarin skeleton include derivatives having an electron-donating substituent at the 7-position of the coumarin ring. More specifically, 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2′-benzoimidazolyl)-, which is a derivative characterized by having an amino group at the 7-position of the coumarin ring.
  • a semiconductor nanoparticle is a particle of a predetermined size that is composed of a crystal of a semiconductor material and has a quantum confinement effect, and is a fine particle having a particle size of about several nanometers to several tens of nanometers, and has a quantum dot effect. Point to.
  • the fine particle material that can obtain such an effect include ZnO, Si, and ZnS.
  • grains which have a structure called a core / shell structure may be sufficient.
  • a long-period type periodic table such as carbon, silicon, germanium, tin or the like (hereinafter, the “long-period type periodic table” may be omitted) a group 14 element simple substance Elemental group 15 elements such as phosphorus (black phosphorus); elemental group 16 elements such as selenium and tellurium; compounds composed of a plurality of group 14 elements such as silicon carbide (SiC); tin (IV) oxide ( SnO 2 ), tin sulfide (II, IV) (Sn (II) Sn (IV) S 3 ), tin sulfide (IV) (SnS 2 ), tin sulfide (II) (SnS), tin selenide (II) ( Group 14 elements such as SnSe), tin (II) telluride (SnTe), lead (II) sulfide (PbS), lead (I
  • Group 11 and Group 16 elements copper chloride (I) (CuCl), copper bromide (I) (CuBr), copper iodide (I) (CuI), silver chloride (AgCl), silver bromide Group 11 elements such as (AgBr) and 17 A compound with a group element; a compound of a group 10 element and a group 16 element such as nickel oxide (II) (NiO); a ninth compound such as cobalt oxide (II) (CoO) and cobalt sulfide (II) (CoS) the compounds of the group element and a group 16 element, triiron tetraoxide (Fe 3 O 4), the compounds of the group VIII element and a group 16 element such as iron sulfide (II) (FeS); manganese (II) oxide A compound of a Group 7 element such as (MnO) and a Group 16 element; a group 6 element such as molybdenum sulfide (IV) (Mo
  • the shell part of the semiconductor nanoparticles any material can be used as long as it is a material that functions as a protective film for the core part.
  • the shell part preferably includes a semiconductor having a band gap (forbidden band width) larger than that of the core part. By using such a semiconductor for the shell portion, an energy barrier is formed in the semiconductor nanoparticles, and good light emission performance can be obtained.
  • the semiconductor material preferably used for the shell depends on the band gap of the core used, but for example, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaAs
  • One or more semiconductors selected from the group consisting of GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, and AlSb, or alloys or mixed crystals thereof are preferable.
  • ZnS, ZnSe, ZnTe, and CdSe are preferable from the viewpoint of improving luminance.
  • a phosphor having a terephthalate structure is preferable. Such a phosphor can be easily excited by excitation light having a wavelength near 400 nm.
  • Examples of the phosphor having a terephthalic acid ester structure include a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).
  • R 11 to R 14 each independently represents an organic group
  • Ph 1 represents a phenylene group having 1 to 4 hydroxyl groups
  • Ph 2 represents a phenylene group having 1 to 4 amino groups.
  • the organic group of R 11 to R 14 is preferably a hydrocarbon group, and the hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the hydrocarbon group is preferably an alkyl group.
  • the number of hydroxyl groups possessed by Ph 1 is preferably 1 or 2.
  • the bonding position of the hydroxyl group is preferably either the 2-position or 5-position of the benzene ring.
  • the amino group in Ph 2 include groups represented by e.g. -NR 15 R 16.
  • R 15 and R 16 each independently represent a hydrogen atom or an organic group. Examples of the organic group are the same as those described above.
  • R 15 and R 16 are each preferably a hydrogen atom.
  • Examples of the compound represented by the formula (1-1) include diethyl-2,5-dihydroxyterephthalate, dimethyl-2,5-dihydroxyterephthalate, and the like. Of these, diethyl-2,5-dihydroxyterephthalate is preferable because an image with higher contrast can be displayed. As the compound represented by the formula (1-2), diethyl-2,5-diaminoterephthalate is preferable. Any one of these phosphors may be used alone, or two or more thereof may be used in combination.
  • the phosphor layer 13 may further include a component other than the matrix and the phosphor (1).
  • a component other than the matrix and the phosphor (1) examples include a silane coupling agent, a dispersant, a leveling agent, an antifoaming agent, and a plasticizer. It is preferable that the phosphor layer 13 does not contain the ultraviolet absorber (1).
  • the content of the phosphor (1) in the phosphor layer 13 is preferably 0.1 to 50 parts by mass, more preferably 1.0 to 35 parts by mass with respect to 100 parts by mass of the matrix.
  • the content is not less than the lower limit of the above range, the intensity of the fluorescence generated from the phosphor layer 13 is sufficiently strong and the visibility of the image is more excellent.
  • the content is not more than the upper limit of the above range, the dispersibility of the phosphor (1) in the matrix is more excellent.
  • the total content of the matrix and the phosphor (1) in the phosphor layer 13 is preferably 90% by mass or more, and more preferably 95% by mass or more with respect to the total mass of the phosphor layer 13.
  • An upper limit is not specifically limited, 100 mass% may be sufficient.
  • the thickness of the phosphor layer 13 is preferably 0.5 to 50 ⁇ m, and more preferably 1.0 to 30 ⁇ m. If the thickness is not less than the lower limit of the above range, the intensity of the fluorescence generated from the phosphor layer 13 is sufficiently strong, and the visibility of the image is more excellent. If the thickness is not more than the upper limit of the above range, the film has better crack resistance.
  • the resin layer 15 contains a resin.
  • the resin layer 15 typically functions as an adhesive layer that bonds the phosphor layer 13 and the ultraviolet absorption layer 17 together.
  • a known resin can be used as a resin used for an interlayer film of laminated glass. Examples thereof include thermoplastic resins such as polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ionomer, ethylene-acrylic copolymer resin, polyurethane resin, sulfur-containing polyurethane resin, polyvinyl alcohol resin, vinyl chloride resin, polyethylene terephthalate resin. . Any one of these resins may be used alone, or two or more thereof may be used in combination. Among the above, the resin is preferably a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, or an ionomer.
  • the polyvinyl acetal resin is a resin obtained by acetalizing polyvinyl alcohol with an aldehyde.
  • a polyvinyl butyral resin is preferable.
  • the degree of acetalization of the polyvinyl acetal resin is preferably 40 to 85 mol%, more preferably 60 to 75 mol%.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is preferably 15 to 35 mol%.
  • the degree of acetalization and the amount of hydroxyl groups can be measured according to JIS K6728 “Testing methods for polyvinyl butyral”.
  • the water absorption rate of the resin is preferably 0.06 to 5% by mass, and more preferably 0.1 to 3% by mass. If the water absorption is not less than the lower limit of the above range, the adhesiveness is excellent. If the water absorption is not more than the upper limit of the above range, the durability of the resin is excellent.
  • the resin layer 15 does not contain the phosphor (1).
  • the ultraviolet transmittance (400 nm) of the resin layer 15 is 20% or more, preferably 25% or more, and more preferably 30% or more. The upper limit is not particularly limited. The ultraviolet transmittance (400 nm) of 20% or more indicates that the resin layer 15 does not contain the ultraviolet absorber (1) or the content of the ultraviolet absorber (1) is small.
  • the ultraviolet absorber (1) the thing similar to what is mentioned in the ultraviolet absorption layer 17 mentioned later is mentioned.
  • the resin layer 15 does not contain the phosphor (1) and the ultraviolet transmittance (400 nm) is not less than the lower limit, the ultraviolet absorber (1) is transferred from the resin layer 15 to the phosphor layer 13, It is possible to prevent the phosphor (1) from being transferred from the resin layer 15 to the ultraviolet absorption layer 17.
  • the resin layer 15 may contain a plasticizer.
  • the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers.
  • organic ester plasticizer examples include 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-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylsurexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di
  • polybasic organic acid esters include esters of polybasic organic acids such as adipic acid, sebacic acid, and azelaic acid with alcohols having a linear or branched structure having 4 to 8 carbon atoms. Compounds are preferred.
  • organic phosphate plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.
  • the resin layer 15 may further include other components other than the resin, the phosphor, the ultraviolet absorber (1), and the plasticizer.
  • other components that may be included in the resin layer 15 include other ultraviolet absorbents other than the ultraviolet absorbent (1), an adhesive force adjusting agent, and an antioxidant.
  • the content of the ultraviolet absorber (1) in the resin layer 15 varies depending on the type of the ultraviolet absorber (1), but is typically 0 to 20 parts by mass with respect to 100 parts by mass of the resin.
  • the content of the plasticizer is preferably 30 to 90 parts by mass with respect to 100 parts by mass of the resin.
  • the thickness of the resin layer 15 is preferably 0.1 to 3.0 mm, and more preferably 0.1 to 1.0 mm. When the thickness is equal to or greater than the lower limit of the above range, the strength of the self-luminous screen 10 is more excellent. When the thickness is not more than the upper limit of the above range, the adhesion between the transparent substrates is more excellent.
  • the ultraviolet absorption layer 17 includes a matrix and an ultraviolet absorber (1).
  • the matrix of the ultraviolet absorbing layer 17 is preferably made of the material (I).
  • the ultraviolet absorber (1) is not particularly limited as long as it can absorb ultraviolet rays having a wavelength of 400 nm, and can be appropriately selected from various known ultraviolet absorbers.
  • the ultraviolet absorber (1) may be capable of absorbing ultraviolet rays other than the wavelength of 400 nm, for example, ultraviolet rays having a wavelength of less than 400 nm.
  • Examples of the ultraviolet absorber (1) include organic ultraviolet absorbers and metal oxides.
  • Organic UV absorbers include compounds having a malonic ester structure, compounds having an oxalate anilide structure, compounds having a benzotriazole structure, compounds having a benzophenone structure, compounds having a triazine structure, compounds having a benzoate structure, hindered amines Examples thereof include compounds having a structure.
  • the metal oxide include Fe 2 O 3 , TiO 2 , CeO 2 , WO 3 , Nb 2 O 5 , Ta 2 O 5 , Bi 2 O 3 , Eu 2 O 3 , Sb 2 O 3 , ZrO 2 and the like. It is done.
  • the ultraviolet absorbing layer 17 may further contain other components other than the matrix and the ultraviolet absorber (1).
  • examples of other components that may be included in the ultraviolet absorbing layer 17 include ultraviolet absorbers other than the ultraviolet absorber (1), silane coupling agents, dispersants, leveling agents, antifoaming agents, and plasticizers.
  • the ultraviolet absorbing layer 17 preferably does not contain the phosphor (1).
  • the content of the ultraviolet absorber (1) in the ultraviolet absorbing layer 17 is such that the ultraviolet transmittance (400 nm) of the laminate comprising the second transparent substrate 19 and the ultraviolet absorbing layer 17 laminated on one side thereof is 10%.
  • the amount of the following is preferable, and the amount of 3% or less is more preferable. If the ultraviolet transmittance (400 nm) is equal to or less than the upper limit, it is possible to effectively prevent ultraviolet rays having a wavelength of 400 nm from entering the phosphor layer 13 from the second surface 10b side, and image visibility and light resistance. Is better.
  • the lower limit of the ultraviolet transmittance (400 nm) is not particularly limited, and may be 0%.
  • the 2nd transparent base material 19 may contain a ultraviolet absorber (1).
  • the content of the ultraviolet absorber (1) in the ultraviolet absorbing layer 17 can be appropriately set according to the ultraviolet transmittance (400 nm) of the laminate, the type of the ultraviolet absorber (1), etc.
  • the amount is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to parts. If the content is not less than the lower limit of the above range, there is a tendency that ultraviolet rays having a wavelength of 400 nm can be effectively suppressed from entering the phosphor layer 13 from the second surface 10b side. When the content is not less than the lower limit of the above range, a decrease in the luminous efficiency of the phosphor when installed in a super xenon weather meter (for example, Suga tester) is suppressed.
  • a super xenon weather meter for example, Suga tester
  • 90 mass% or more is preferable with respect to the total mass of the ultraviolet absorption layer 17, and, as for the total content of the matrix in the ultraviolet absorption layer 17, and an ultraviolet absorber (1), 95 mass% or more is more preferable.
  • An upper limit is not specifically limited, 100 mass% may be sufficient.
  • the thickness of the ultraviolet absorbing layer 17 is preferably 0.5 to 50 ⁇ m, more preferably 1.0 to 30 ⁇ m. When the thickness is equal to or greater than the lower limit of the above range, it is possible to effectively suppress the ultraviolet light having a wavelength of 400 nm from entering the phosphor layer 13 from the second surface 10b side. If the said thickness is below the upper limit of the said range, the crack resistance of a film
  • Material (I) is an inorganic material, a low water-absorbing organic material, or a mixture thereof.
  • the resin layer 15 can function as an adhesive layer.
  • the resin of the resin layer 15 (polyvinyl acetal resin or the like) has a relatively large amount of hydrophilic groups such as hydroxyl groups and tends to have high water absorption (hygroscopicity). Since the water absorption of the resin is high, the resin layer 15 contains a predetermined amount of moisture.
  • the phosphor (1) and the ultraviolet absorber (1) are contained in the resin layer 15, the phosphor (1) and the ultraviolet absorber (1) are caused by heat during the production and use of the self-luminous screen 10. It becomes easy to move by dissolving and ionizing in moisture.
  • the intermediate film used for the laminated glass is also made of a highly water-absorbing resin, like the resin layer 15, and contains a predetermined amount of moisture. Therefore, the phosphor (1) and the ultraviolet absorber (1 ) Is a mixed problem.
  • the material (I) since the material (I) has a low water absorption, the phosphor layer or the ultraviolet absorption layer using the material (I) as a matrix does not contain or contains a small amount of moisture. Therefore, the phosphor (1) or the ultraviolet absorber (1) is difficult to move in the layer. Therefore, the phosphor (1) in the phosphor layer or the ultraviolet absorber (1) in the ultraviolet absorbing layer moves out of the layer with time, and the phosphor (1) and the ultraviolet absorber (1) are in the same layer. It can suppress becoming mixed. In particular, when the matrix of the phosphor layer 13 is made of the material (I), the light deterioration of the phosphor (1) can be suppressed and the light resistance can be improved due to the small amount of water.
  • Examples of the inorganic material include a hydrolysis condensate of a hydrolyzable metal compound.
  • the hydrolyzable metal compound is a compound having a metal atom and one or more hydrolyzable groups bonded to the metal atom (hereinafter also referred to as an unhydrolyzed product), and one or two of such compounds. It is a general term for partially hydrolyzed (co) condensates of species or more.
  • the skeleton of this condensate consists of repeating metal atoms and oxygen atoms.
  • the unhydrolyzed product may further have a non-hydrolyzable group bonded to a metal atom.
  • the non-hydrolyzed product has a non-hydrolyzable group
  • the resulting condensate also has a non-hydrolyzable group bonded to a metal atom.
  • the non-hydrolyzable group is an organic group
  • this condensate contains an organic group, but since the skeleton portion is inorganic, it is handled as an inorganic material.
  • Examples of the metal in the metal atom include silicon, tin, titanium, aluminum, zirconium, iron, nickel, copper, magnesium, and antimony. Of these, silicon or titanium is preferable, and silicon is particularly preferable.
  • Examples of hydrolyzable groups include alkoxy groups, alkenyloxy groups, acyl groups, acyloxy groups, oxime groups, amide groups, amino groups, iminoxy groups, aminoxy groups, alkyl-substituted amino groups, isocyanate groups, and chlorine atoms.
  • Examples of non-hydrolyzable groups include hydrocarbon groups such as alkyl groups and aryl groups, halogenated alkyl groups, and halogenated aryl groups.
  • Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and a phenethyl group.
  • hydrolyzable metal compound examples include alkoxides, carboxylates, organosiloxides, acetylacetonate complexes, sulfates, nitrates or partial condensates thereof, or a mixture of two or more of these metals.
  • tetramethoxysilane tetraethoxysilane
  • dibutyltin diethoxide tetraisopropoxy titanate
  • tetrabutyl titanate tetra (2-ethylhexyl) titanate
  • aluminum triethoxide and the like
  • dibutyl-bis (triethoxysiloxy) Organosiloxides such as tin
  • carboxylates such as dibutyltin diacetate, butyltin triacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, and ethylaluminum diacetate
  • Any one of these hydrolyzable metal compounds may be used alone, or two or more thereof may be used in combination.
  • the hydrolyzable metal compound preferably contains a tetrafunctional hydrolyzable silicon compound in that it forms a dense SiO 2 structure.
  • the tetrafunctional hydrolyzable silicon compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetra n-propoxysilane, and tetra n-butyloxysilane.
  • the four alkoxy groups in the tetraalkoxysilane may be the same or different.
  • the number of carbon atoms of the alkoxy group is preferably 1 to 4, for example.
  • the low water absorption organic material has a water absorption of 0.8% by mass or less.
  • the water absorption rate of the low water absorption organic material is preferably 0.3% by mass or less, and more preferably 0.1% by mass or less. If the water absorption is not more than the above upper limit value, the amount of water in the layer using this as a matrix is small, and the phosphor (1) or the ultraviolet absorber (1) is difficult to diffuse. When the amount of moisture in the layer is large, the phosphor (1) or the ultraviolet absorber (1) is dissolved in the moisture in the layer and ionized, for example, by heat during manufacture or use of the self-luminous screen 10. It becomes easy to diffuse.
  • the minimum of the said water absorption is not specifically limited, For example, it may be 0.05 mass%.
  • the water absorption rate of the low water absorption organic material is lower than that of the resin of the resin layer 15.
  • the phosphor (1) or the ultraviolet absorber (1) is difficult to diffuse.
  • the organic material is typically a resin.
  • the resin may be linear or may not be linear.
  • the resin may or may not contain a crosslinked structure.
  • linear means that the main chain is linear, and does not limit the presence or absence of side chains.
  • the resin include acrylic resin, polyester resin, polyurethane resin, polyurethane acrylate resin, polycarbonate resin, polyvinyl butyral resin, cycloolefin resin, ethylene / vinyl acetate copolymer resin, and fluorene ring-containing resin.
  • each of these resins has various water absorption rates, but the higher the hydrophobicity, the lower the content of hydrophilic groups such as hydroxyl groups, or the higher the crystallinity, the lower the water absorption rate.
  • the water absorption rate is 0.8% by mass or less.
  • the cycloolefin resin include a polymer represented by the following formula a or b.
  • R ⁇ 1 > and R ⁇ 2 > shows the functional group, hydrogen atom, or halogen atom which reacts with either a metal or a metal oxide each independently.
  • the functional group that reacts with either a metal or a metal oxide include an alkoxyl group, an isocyanate group, an epoxy group, a silanol group, a carbonyl group, an amino group, and a hydroxyl group.
  • the compatibility with the resin layer 15 is low, and since the phosphor (1) or the ultraviolet absorber (1) is excellent in the effect of suppressing the migration outside the layer, it is an inorganic material or low water absorption. Organic materials are preferred.
  • the visible light transmittance of the entire self-luminous screen 10 is preferably 70% or more, and more preferably 80% or more. When the visible light transmittance is equal to or higher than the lower limit, transparency and background visibility are more excellent.
  • the “visible light transmittance” of the entire self-luminous screen 10 is obtained by the following method. First, using a spectrophotometer, a second light is incident on incident light incident at an incident angle of 0 ° from the first surface 10a side (or the second surface 10b side) of the self-luminous screen 10 (measurement target). Of the total transmitted light transmitted to the surface 10b side (or the first surface 10a side), the spectral transmittance at a wavelength of 380 nm to 780 nm is measured. By multiplying this measured value by the weighting coefficient obtained from the spectrum of CIE daylight D65 and the wavelength distribution of the visibility, the visible light transmittance is obtained.
  • Manufacturing method of self-luminous type screen 10 examples include the following manufacturing method ( ⁇ ) and manufacturing method ( ⁇ ).
  • the liquid medium in the first coating liquid and the second coating liquid may be any medium that can dissolve the matrix or its precursor, such as water, an organic solvent, A mixture thereof may be mentioned.
  • the organic solvent include methyl ethyl ketone and cyclopentanone.
  • the method for applying the coating liquid include spray coating, die coating, and bar coating.
  • a second coating liquid containing a matrix or a precursor thereof, an ultraviolet absorber (1), and a liquid medium is applied to one side of the second transparent substrate 19 and dried to form an ultraviolet absorbing layer 17.
  • Obtaining a second laminate A step of laminating and bonding the first transparent base material 11, the film that becomes the phosphor layer 13, the resin layer 15, and the surface of the second laminate on the side of the ultraviolet absorbing layer 17 in this order.
  • the production method, wherein at least one of the first matrix and the second coating liquid or a precursor thereof is material (I) or a precursor thereof.
  • Bonding of the first laminated body and the second laminated body can be performed in the same manner as in the production of a known laminated glass.
  • the first laminate, the resin layer 15 (for example, the thermoplastic resin sheet), and the second laminate are stacked so as to have a desired layer structure, and the laminate is reduced in pressure.
  • the temporary bonding conditions may be, for example, a pressure of 0.07 to 0.10 MPa and a temperature of 70 to 130 ° C.
  • the conditions for the main adhesion may be, for example, a pressure of 0.5 to 1.5 MPa and a temperature of 80 to 150 ° C.
  • the self-luminous screen 10 has the phosphor layer 13 containing the phosphor (1), excitation light having an arbitrary pattern is projected from the projector such as a projector to the first surface 10a side of the self-luminous screen 10.
  • the portion of the phosphor (1) on which the excitation light is projected emits light, and an image corresponding to the projected pattern is displayed.
  • the wavelength of the excitation light only needs to excite the phosphor (1) and is typically 405 nm.
  • the self-luminous screen 10 has the ultraviolet absorption layer 17 containing the ultraviolet absorber (1) on the second surface 10b side of the phosphor layer 13, the phosphor (1) can be excited. Light (sunlight or the like) is prevented from entering the phosphor layer 13 from the second surface 10b side. Therefore, it can suppress that the part in which excitation light is not projected from a projector emits light, and the visibility of an image
  • the resin layer 15 is interposed between the phosphor layer 13 and the ultraviolet absorption layer 17 and at least one of the matrix of the phosphor layer 13 and the matrix of the ultraviolet absorption layer 17 is made of the material (I), the phosphor layer
  • the migration of the phosphor (1) from 13 to the ultraviolet absorption layer 17 and the migration of the ultraviolet absorber (1) from the ultraviolet absorption layer 17 to the phosphor layer 13 are suppressed. Therefore, over time, the phosphor (1) and the ultraviolet absorber (1) are mixed in the phosphor layer 13 and the ultraviolet absorbing layer 17, or the content of the phosphor (1) in the phosphor layer 13 decreases. Can be suppressed.
  • the phosphor (1) When the phosphor (1) is transferred to the ultraviolet absorption layer 17, there is a possibility that a portion where excitation light is not projected from the projector emits light, or the phosphor (1) is deteriorated by sunlight or the like.
  • the ultraviolet absorber (1) moves to the phosphor layer 13, the excitation light is absorbed by the ultraviolet absorber (1), and the phosphor (1) may be insufficiently emitted. Therefore, in the self-luminous screen 10, the portion where the excitation light is projected emits light with sufficient emission intensity, and the portion where the excitation light is not projected from the projector is suppressed from emitting light.
  • the visibility of the image is excellent. In addition, deterioration of image visibility over time is suppressed, and excellent visibility can be maintained over a long period of time.
  • the matrix of the phosphor layer 13 is made of the material (I)
  • the light degradation of the phosphor (1) is suppressed and the light resistance is excellent.
  • FIG. 2 is a schematic cross-sectional view of the self-luminous screen 20 according to the second embodiment of the present invention.
  • the self-luminous screen 20 includes a laminated structure in which a first transparent base material 11, a phosphor layer 13, a resin layer 15, and a third transparent base material 21 are laminated in this order.
  • the self-luminous screen 20 is the same as that of the first embodiment except that a third transparent substrate 21 is provided instead of the ultraviolet absorbing layer 17 and the second transparent substrate 19.
  • the first surface 20a (outermost surface on the first transparent substrate 11 side) of the self-luminous screen 20 is a surface on the side where excitation light for exciting the phosphor (1) is projected from the projector. Also, typically, the first surface 20a is a surface on the indoor side, and the second surface 20b opposite to the first surface 20a (the outermost surface on the third transparent base material 21 side) is a yaw. The outer surface.
  • the 3rd transparent base material 21 contains a ultraviolet absorber (1).
  • the third transparent substrate 21 is the same as the transparent substrate of the first embodiment except that it is essential that the third transparent substrate 21 contains the ultraviolet absorber (1). Specifically, it includes a matrix and an ultraviolet absorber (1), and examples of the matrix include the same materials as those described above for the transparent substrate. Examples of the ultraviolet absorber (1) include the same as those described above.
  • the third transparent substrate 21 has an ultraviolet transmittance (400 nm) of 10% or less, preferably 3% or less. If the ultraviolet transmittance (400 nm) is equal to or less than the upper limit, it is possible to effectively prevent ultraviolet rays having a wavelength of 400 nm from entering the phosphor layer 13 from the second surface 20b side, and image visibility and light resistance. Is better.
  • the lower limit of the ultraviolet transmittance (400 nm) is not particularly limited, and may be 0%.
  • the third transparent substrate 21 contains an ultraviolet absorber (1) and glass as a matrix, and has an ultraviolet transmittance (400 nm) of 90% or less (preferably 50% or less).
  • the ultraviolet absorber (1) is preferably a metal oxide.
  • the ultraviolet absorber (1) when the matrix of the third transparent substrate 21 is a transparent resin is preferably an organic ultraviolet absorber.
  • the 3rd transparent base material 21 may contain 1 or more types of ultraviolet absorbers (1).
  • the content of the ultraviolet absorber (1) in the third transparent substrate 21 is determined by the desired ultraviolet transmittance (400 nm) of the third transparent substrate 21, the type of the ultraviolet absorber (1), and the third transparency. Although it can be appropriately set according to the matrix of the base material, etc., when the matrix of the third transparent base material is a transparent resin, for example, 0.1 to 50 parts by weight is preferable with respect to 100 parts by weight of the matrix. 30 parts by mass is more preferable. When the matrix of the third transparent substrate is glass, the content of the ultraviolet absorber (1) is preferably 0.01 to 5.0 parts by mass, and 0.02 to 3. 0 parts by mass is more preferable.
  • the content is not less than the lower limit of the above range, there is a tendency that ultraviolet rays can be effectively suppressed from entering the phosphor layer 13 from the second surface 20b side. If the said content is below the upper limit of the said range, there will be little coloring and there exists a tendency which can manufacture glass stably.
  • the self-luminous screen 20 is manufactured by using the third transparent substrate 21 instead of the second stacked body without performing the step of obtaining the second stacked body.
  • a self-luminous screen 20 is obtained.
  • the 3rd transparent base material 21 containing a ultraviolet absorber (1) can be manufactured by adding a ultraviolet absorber to a glass composition, for example. If the transparent base material containing a ultraviolet absorber (1) is marketed, you may use this transparent base material as the 3rd transparent base material 21.
  • the self-luminous screen 20 has the phosphor layer 13 containing the phosphor (1), as in the self-luminous screen 10 of the first embodiment, the first self-luminous screen 20 is projected from the projector.
  • the excitation light (image light) of an arbitrary pattern is projected on the surface 20a side
  • the phosphor (1) of the portion where the excitation light is projected emits light, and an image corresponding to the projected pattern is displayed.
  • the self-luminous screen 20 has the third transparent substrate 21 containing the ultraviolet absorber (1) on the second surface 20b side of the phosphor layer 13, the phosphor (1) is provided.
  • Excitable light (sunlight or the like) is prevented from entering the phosphor layer 13 from the second surface 20b side. Therefore, it can suppress that the part in which excitation light is not projected from a projector emits light, and the visibility of an image
  • the resin layer 15 is interposed between the phosphor layer 13 and the third transparent base material 21 and the matrix of the third transparent base material 21 is glass that is an inorganic material, it occurs in the first embodiment.
  • the possible transfer of the phosphor (1) from the phosphor layer 13 to the ultraviolet absorption layer 17 and the transfer of the ultraviolet absorber (1) from the ultraviolet absorption layer 17 to the phosphor layer 13 are suppressed. Therefore, over time, the phosphor (1) and the ultraviolet absorber (1) are mixed in the phosphor layer 13, or the content of the phosphor (1) in the phosphor layer 13 is decreased. Can be suppressed.
  • the portion where the excitation light is projected emits light with sufficient emission intensity, and the portion where the excitation light is not projected from the projector is suppressed from emitting light.
  • the visibility of the image is excellent.
  • deterioration of image visibility over time is suppressed, and excellent visibility can be maintained over a long period of time. If the matrix of the phosphor layer 13 is made of the material (I), the light deterioration of the phosphor (1) is suppressed, and the light resistance is excellent.
  • FIG. 4 is a schematic cross-sectional view of the self-luminous screen 30 according to the third embodiment of the present invention.
  • the self-luminous screen 30 includes a laminated structure in which the first transparent substrate 11 or the second transparent substrate 19, the ultraviolet absorbing layer 17, and the phosphor layer 13 are laminated in this order.
  • an arbitrary protective layer 25 may be laminated on the phosphor layer 13 (on the first surface 30a side of the phosphor layer 13).
  • the self-luminous screen 30 is the same as that of the first embodiment except that the resin layer 15 is not provided and only one of the first transparent substrate 11 and the second transparent substrate 19 is provided. .
  • the surface on the side where the excitation light for exciting the phosphor (1) is projected from the projector is the first surface 30a (the outermost surface on the arbitrary protective layer 25 side) and the second surface. Any of 30b (the 1st transparent substrate 11 or the 2nd transparent substrate 19 side outermost surface) may be sufficient.
  • the first surface 30a is an indoor surface
  • the second surface 30b is an outdoor surface.
  • the self-luminous screen 30 may further include layers other than the first transparent substrate 11, the second transparent substrate 19, the ultraviolet absorption layer 17, and the phosphor layer 13. Examples of other layers include a protective layer 25 and an adhesive layer (not shown). Typically, the protective layer 25 is preferably a hard coat layer.
  • At least one of the matrix of the phosphor layer 13 and the ultraviolet absorbing layer 17 is made of a material (I) having a low water absorption, so that the phosphor layer 13 and / or the ultraviolet absorbing layer 17 contains moisture. There is little to no. Therefore, the phosphor (1) and / or the ultraviolet absorber (1) is difficult to move within the layer. Therefore, even if the phosphor layer 13 and the ultraviolet absorbing layer 17 are adjacent to each other, the phosphor (1) or the ultraviolet absorber (1) of the phosphor layer moves out of the layer with time, and the phosphor (1). And the ultraviolet absorber (1) can be prevented from being mixed in the same layer.
  • the matrix of the phosphor layer 13 is made of the material (I)
  • the amount of water is small, so that the light deterioration of the phosphor (1) can be suppressed.
  • both the matrix of the fluorescent substance layer 13 and the ultraviolet absorption layer 17 consists of material (I)
  • mixing with a fluorescent substance (1) and an ultraviolet absorber (1) can be suppressed lightly, and it is preferable.
  • the self-luminous screen 30 is manufactured by, for example, applying the second coating liquid to one side of the first transparent base material 11 or the second transparent base material 19 in the same manner as the manufacturing method ( ⁇ ). The steps of drying and forming the ultraviolet absorbing layer 17 and applying the first coating liquid onto the ultraviolet absorbing layer 17 and drying to form the phosphor layer 13 are sequentially performed.
  • the light emitting screen 30 can be manufactured.
  • a self-luminous screen 30 can be manufactured by laminating a film that becomes the phosphor layer 13 on the adhesive layer.
  • the self-luminous screen 30 can be manufactured without performing the step of laminating and laminating the first laminated body and the second laminated body. For this reason, since it can suppress that a fluorescent substance (1) and a ultraviolet absorber (1) melt
  • the self-luminous screen 30 has the phosphor layer 13 including the phosphor (1), as in the self-luminous screen of the first embodiment and / or the second embodiment, the projector emits light from the projector.
  • the phosphor (1) in the portion where the excitation light is projected emits light, and an image corresponding to the projected pattern is displayed.
  • the self-luminous screen 30 has the ultraviolet absorption layer 17 containing the ultraviolet absorber (1) on the first surface 30a side of the phosphor layer 13, the phosphor (1) can be excited. Light (sunlight or the like) is prevented from entering the phosphor layer 13 from the first surface 30 side. Therefore, it can suppress that the part in which excitation light is not projected from a projector emits light, and the visibility of an image
  • the phosphor (1) is transferred from the phosphor layer 13 to the ultraviolet absorption layer 17, and the ultraviolet absorption layer 17. Migration of the ultraviolet absorber (1) from the phosphor layer to the phosphor layer 13 is suppressed. Therefore, as with the first embodiment and / or the second embodiment, deterioration of image visibility over time is suppressed, and excellent visibility can be maintained over a long period of time.
  • FIG. 5 is a schematic cross-sectional view of the self-luminous screen 40 according to the fourth embodiment of the present invention.
  • the self-luminous screen 40 includes a laminated structure in which the third transparent substrate 21 and the phosphor layer 13 are laminated in this order. Also in the self-luminous screen 40, an optional protective layer 25 may be laminated on the phosphor layer 13 (on the first surface 40a side of the phosphor layer 13).
  • the surface on the side where the excitation light for exciting the phosphor (1) is projected from the projector is the first surface 40a (the outermost surface on the side of the arbitrary protective layer 25) and the second surface. Any of 40b (the outermost surface on the third transparent substrate 21 side) may be used.
  • the first surface 40a is an indoor surface
  • the second surface 40b is an outdoor surface.
  • the self-luminous screen 40 may further include a layer other than the third transparent substrate 21 and the phosphor layer 13. Examples of other layers include a protective layer 25 and an adhesive layer (not shown).
  • the protective layer 25 is preferably a hard coat layer.
  • the matrix of the phosphor layer 13 is made of the material (I) having a low water absorption, the phosphor layer 13 does not contain water or only contains water. Therefore, it is possible to suppress the light deterioration of the phosphor (1), which is preferable.
  • the method for manufacturing the self-luminous screen 40 is, for example, in the same manner as the manufacturing method ( ⁇ ) described above, applying the first coating liquid to one side of the third transparent substrate 21 and drying to form the phosphor layer 13. Thus, the self-luminous screen 40 can be manufactured.
  • a self-luminous screen 40 made of the first laminate can be manufactured by laminating the film to be the layer 13.
  • the self-luminous screen 40 can be manufactured without performing the step of laminating and laminating the first laminated body and the second laminated body. For this reason, since it can suppress that a fluorescent substance (1) and a ultraviolet absorber (1) melt
  • the projector emits the self-luminous screen 40 from the projector.
  • the phosphor (1) in the portion where the excitation light is projected emits light, and an image corresponding to the projected pattern is displayed.
  • the self-luminous screen 40 has the third transparent substrate 21 containing the ultraviolet absorber (1) on the first surface 40b side of the phosphor layer 13, the phosphor (1) is provided.
  • Excitable light (sunlight or the like) is prevented from entering the phosphor layer 13 from the second surface 40b side. Therefore, it can suppress that the part in which excitation light is not projected from a projector emits light, and the visibility of an image
  • the matrix of the third transparent substrate 21 is glass, the phosphor (1) in the phosphor layer 13 and ultraviolet absorption that may occur with time in the first embodiment and / or the third embodiment. Mixing with the agent (1) and a decrease in the content of the phosphor (1) in the phosphor layer 13 can be suppressed. Therefore, in the self-luminous type screen 40, the deterioration with time of the visibility of the image is suppressed as in the second embodiment, and excellent visibility can be maintained over a long period of time.
  • the self-luminous type screen of the present invention is not limited to the above-mentioned embodiment.
  • layers other than the first to third transparent base materials 11, 19, and 21, the phosphor layer 13, the resin layer 15, and the ultraviolet absorbing layer 17 are included in the laminated structure.
  • a second ultraviolet absorbing layer is further provided on the second surface 10b side of the second transparent base material 19 or on the second surface 20b side of the third transparent base material 21. It may be.
  • the second ultraviolet absorbing layer may be the same as the ultraviolet absorbing layer 17, for example.
  • the laminated structure and other members may be combined.
  • the self-luminous screen of the present invention may be installed alone at any place such as outdoors or indoors, or may be used as a part of a vehicle such as an automobile or a membrane structure building.
  • a membrane structure building is a building in which at least a part of a roof, a wall, and the like is made of a membrane material, and examples thereof include an exercise facility, a greenhouse, and an atrium.
  • An example of a suitable application of the self-luminous screens 10 and 20 of the present invention is an automotive head-up display device (hereinafter also referred to as a HUD device).
  • the self-luminous screen can be applied to an automobile windshield, rear glass, side glass, ceiling glass, and the like. It can also be used as an architectural screen.
  • FIG. 3 is a schematic configuration diagram schematically showing an example of a HUD device to which the self-luminous screen of the present invention is applied.
  • the HUD device 100 includes a self-luminous screen 10 installed as a windshield of an automobile, and a projector 110.
  • the self-luminous screen 10 is arranged with the first surface 10a side facing the vehicle inner side (viewer X side).
  • the projector 110 is installed in a vehicle (for example, a dashboard), and can project image light L (excitation light of an arbitrary pattern) onto the self-luminous screen 10 from the inside of the vehicle.
  • the projector 110 may be any projector that can project the image light L, and a known projector or the like can be used.
  • a near ultraviolet (wavelength: 405 nm) projector is preferably used.
  • FIG. 6 is a schematic configuration diagram schematically showing an example of an automotive rear glass to which the self-luminous screen of the third embodiment is applied.
  • the automobile rear glass 200 includes a self-luminous screen 30 installed as a rear glass of the automobile, and a projector 110.
  • the self-luminous screen 30 is arranged with the second surface 30b side facing the vehicle outer side (viewer X side).
  • the projector 110 is installed in a vehicle (for example, a dashboard), and can project the image light L (an arbitrary pattern of excitation light) onto the self-luminous screen 30 from the inside of the vehicle.
  • the projector 110 may be any projector that can project the image light L, and a known projector or the like can be used. Typically, a near ultraviolet (wavelength: 405 nm) projector is preferably used.
  • the self-luminous screens 30 and 40 can also be suitably used as architectural screens.
  • Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
  • Examples 1, 3, 4 and 6 are examples, and examples 2, 5 are comparative examples.
  • Example 1 The self-luminous screen shown in FIG. 1 was manufactured by the following method. First, 2 mm thick soda lime glass was prepared as a first transparent substrate. Next, a fluorescent dye (Lumogen-F570 manufactured by BASF) is dissolved in a cyclopentanone solvent so as to have a concentration of 2% by mass, and organic material 1 (fluorene ring-containing resin, OKP2 manufactured by Osaka Gas Chemical Company) is used as a matrix. ) was added and mixed so that the ratio of the fluorescent dye to the total mass of the organic material 1 and the fluorescent dye was 15% by mass to prepare a paste. This paste was applied onto the first transparent substrate by a die coating method and dried at 110 ° C. to produce a phosphor layer. As for the thickness of the phosphor layer, an average of 5 ⁇ m measured at any five locations was 5 ⁇ m.
  • a fluorescent dye Liogen-F570 manufactured by BASF
  • organic material 1 fluorene ring-containing resin, OKP2 manufactured by Osaka Gas Chemical Company
  • a glass substrate having an ultraviolet absorption layer on an ultraviolet absorption glass (UVverre made by Asahi Glass Co., Ltd.) having a thickness of 2 mm and having an ultraviolet transmittance of 10% or less at a wavelength of 400 nm is prepared.
  • a first transparent base material, a phosphor layer, a resin layer, an ultraviolet absorbing layer, and a second transparent base material were laminated in this order to form a laminate.
  • this laminate was heated at 120 ° C. for 1 hour in a vacuum-packed state. This produced a transparent screen (hereinafter referred to as the self-luminous screen of Example 1).
  • Example 2 The self-luminous screen of Example 2 was produced in the same manner as in Example 1. However, in Example 2, organic material 2 (PVB, PVB BK1 manufactured by Sekisui Chemical Co., Ltd.) is added as a matrix and mixed so that the ratio of the fluorescent dye to the total mass of organic material 2 and the fluorescent dye is 15% by mass. The paste obtained was used.
  • organic material 2 PVB, PVB BK1 manufactured by Sekisui Chemical Co., Ltd.
  • the water absorption rate of PVB contained in the PVB film used for the resin layer was the same as the above except that the 0.38 mm PVB film used in Example 1 or Example 2 was used instead of producing the self-supporting film by casting. It was 1.0 mass% when measured.
  • Weather resistance evaluation was performed using the self-luminous screens of Examples 1 and 2 as samples.
  • the weather resistance evaluation was carried out by holding each sample for 150 hours in a super xenon weather meter (irradiance 150 W / m 2 ) manufactured by Suga Test Instruments Co., Ltd. Thereafter, a sample was taken out and checked for yellowing. The case where the degree of yellowing was large was rated as x, and the case where almost no yellowing was observed was marked as ⁇ .
  • Table 1 summarizes the specifications and evaluation results of the self-luminous screens of Examples 1 and 2.
  • Example 1 From Table 1, it can be seen that the self-luminous screen of Example 1 is suppressed in yellowing even after 150 hours and has improved weather resistance compared to the self-luminous screen of Example 2. In Example 1, it is considered that the deterioration of the phosphor is suppressed due to the low water absorption rate of the organic material used as the matrix.
  • Example 3 The self-luminous screen of Example 3 was produced in the same manner as in Example 1. However, in Example 3, diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich) was added as the fluorescent dye, and the ratio of the fluorescent dye to the total mass of the organic material 1 and the fluorescent dye was 1% by mass. A paste obtained by mixing was used.
  • Example 4 As a third transparent base material, an ultraviolet absorbing glass (Asahi Glass UVFL) having a thickness of 3 mm is prepared, and the first transparent base material, the phosphor layer, the resin layer, and the third transparent base material are laminated in this order. A self-luminous screen of Example 4 shown in FIG. 2 was produced.
  • Aligni Glass UVFL ultraviolet absorbing glass
  • Example 5 The self-luminous screen of Example 5 was produced in the same manner as in Example 3. However, in Example 5, the organic material 2 is used as the matrix, and the same ultraviolet absorber as in Example 3 is added to the matrix, and the fluorescent dye and the ultraviolet absorber with respect to the total amount of the organic material 2, the fluorescent dye, and the ultraviolet absorber. A paste obtained by mixing so that the ratio was 1% by mass was used.
  • the self-luminous screens of Examples 3 and 4 have a lower fluorescence quantum yield, that is, a lower visibility than the self-luminous screen of Example 5.
  • the organic material used as the matrix of the phosphor layer has a low water absorption rate, so that deterioration of the phosphor due to contact with and / or heating with the ultraviolet absorber is suppressed. It is considered that the decrease in visibility was suppressed.
  • the self-luminous screens of Examples 3 and 4 since the phosphor layer and the ultraviolet absorbing layer are not adjacent to each other, the migration of the phosphor and the ultraviolet absorber to the outside of the layer is suppressed. It is thought that the decline was further suppressed.
  • Example 6 As the second transparent base material, UV absorbing glass (UV verre made by Asahi Glass Co., Ltd.) having a thickness of 3 mm is prepared, and the second transparent base material, the UV absorbing layer, and the phosphor layer are laminated in this order in the same manner as in Example 3. Thus, the self-luminous screen of Example 6 shown in FIG. 4 was produced. However, in Example 6, the organic material 3 (cycloolefin resin, manufactured by Nippon Zeon Co., Ltd., water absorption: 0.01%) is used as the matrix of the phosphor layer, and the fluorescent dye with respect to the total mass of the organic material 3 and the fluorescent dye. The paste obtained by mixing was used so that the ratio was 4% by mass. Using the self-luminous screen of Example 6 as a sample, the visibility was evaluated in the same manner as in Examples 3 to 5. Table 3 below summarizes the specifications and evaluation results of the self-luminous screen of Example 6.
  • the self-luminous screen of Example 6 has a lower fluorescence quantum yield, that is, a lower visibility than the self-luminous screen of Example 5.
  • the organic material used as the matrix of the phosphor layer has a low water absorption rate, the deterioration of the phosphor due to contact with the ultraviolet absorber is suppressed, so that a decrease in visibility is suppressed. It is thought that it was done.
  • the self-luminous screen of Example 6 further suppresses a decrease in visibility as compared with the self-luminous screens of Examples 3 and 4.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un écran auto-émetteur qui est excellent en matière de visibilité des images et de durabilité. Un écran auto-émetteur (10) comprend une structure stratifiée dans laquelle sont stratifiés, dans cet ordre : un premier substrat transparent (11), une couche de luminophore (13) comprenant une matrice et un luminophore pouvant être excité par des rayons UV ayant une longueur d'onde de 400 nm, une couche de résine (15) qui n'inclut pas le luminophore et qui présente un facteur de transmission des rayons UV à une longueur d'onde de 400 nm égal ou supérieur à 20 %, une couche absorbant les rayons UV (17) comprenant une matrice et un agent absorbant les rayons UV capable d'absorber des rayons UV ayant une longueur d'onde de 400 nm, et un deuxième substrat transparent (19). La matrice d'au moins l'une parmi la couche de luminophore (13) et la couche d'absorption de rayons UV (17) contient un matériau inorganique, 0,8 % massique ou moins d'un matériau organique ayant une absorption d'eau inférieure à celle de la résine, ou un mélange de ceux-ci.
PCT/JP2018/017461 2017-05-16 2018-05-01 Écran auto-émetteur WO2018211979A1 (fr)

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JP2017097306 2017-05-16
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CN111019327A (zh) * 2019-12-20 2020-04-17 中国科学院过程工程研究所 一种具有力致变色和自修复双功能的高分子复合材料及其制备方法
JP2022548372A (ja) * 2019-09-18 2022-11-18 キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション バリヤ被覆を含む固体電解キャパシタ
US11926122B2 (en) 2019-04-03 2024-03-12 Acr Ii Glass America Inc. Luminescent glazing

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JP2016069215A (ja) * 2014-09-29 2016-05-09 積水化学工業株式会社 合わせガラス用中間膜、合わせガラス及び車両
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JPH1141548A (ja) * 1997-07-17 1999-02-12 Fuji Photo Film Co Ltd 投射型画像表示装置および蛍光スクリーン
US20050231692A1 (en) * 2004-04-19 2005-10-20 Superimaging, Inc. Excitation light emission apparatus
JP2006091172A (ja) * 2004-09-21 2006-04-06 Nissan Motor Co Ltd 投射型画像表示装置
JP2011085753A (ja) * 2009-10-15 2011-04-28 Seiko Epson Corp スクリーンおよびプロジェクションシステム
WO2014051139A1 (fr) * 2012-09-28 2014-04-03 積水化学工業株式会社 Film intermédiaire pour verre feuilleté et verre feuilleté
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JP2017502322A (ja) * 2013-10-22 2017-01-19 サン−ゴバン グラス フランス ディスプレーシステムのためのガラスパネル
JP2016069215A (ja) * 2014-09-29 2016-05-09 積水化学工業株式会社 合わせガラス用中間膜、合わせガラス及び車両

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11926122B2 (en) 2019-04-03 2024-03-12 Acr Ii Glass America Inc. Luminescent glazing
JP2022548372A (ja) * 2019-09-18 2022-11-18 キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション バリヤ被覆を含む固体電解キャパシタ
JP7417714B2 (ja) 2019-09-18 2024-01-18 キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション バリヤ被覆を含む固体電解キャパシタ
CN111019327A (zh) * 2019-12-20 2020-04-17 中国科学院过程工程研究所 一种具有力致变色和自修复双功能的高分子复合材料及其制备方法

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