WO2000013910A1 - Recording sheet having phosphorescence and sign - Google Patents

Recording sheet having phosphorescence and sign Download PDF

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Publication number
WO2000013910A1
WO2000013910A1 PCT/JP1999/002344 JP9902344W WO0013910A1 WO 2000013910 A1 WO2000013910 A1 WO 2000013910A1 JP 9902344 W JP9902344 W JP 9902344W WO 0013910 A1 WO0013910 A1 WO 0013910A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
luminous
resin
recording
phosphorescent
Prior art date
Application number
PCT/JP1999/002344
Other languages
French (fr)
Japanese (ja)
Inventor
Shigeru Mashima
Torao Hayashi
Nozomi Nagase
Original Assignee
Somar Corporation
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
Application filed by Somar Corporation filed Critical Somar Corporation
Priority to EP99918305A priority Critical patent/EP1031432A4/en
Publication of WO2000013910A1 publication Critical patent/WO2000013910A1/en

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006Substrates for image-receiving members; Image-receiving members comprising only one layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/0013Inorganic components thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • G03G7/0026Organic components thereof being macromolecular
    • G03G7/0033Natural products or derivatives thereof, e.g. cellulose, proteins
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • G03G7/0026Organic components thereof being macromolecular
    • G03G7/0046Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/02Dye diffusion thermal transfer printing (D2T2)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/06Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/32Thermal receivers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36Backcoats; Back layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38Intermediate layers; Layers between substrate and imaging layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/426Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/504Backcoats
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings

Definitions

  • the present invention relates to a recording sheet having luminous properties and excellent luminosity, which can be suitably used as a guide plate, a poster and the like in a place, and a display material having luminous properties.
  • a sheet with good visibility in a dark place (1) a sheet made by including a retroreflective agent ⁇ phosphorescent pigment in a resin (especially a vinyl chloride resin), or
  • the luminous agent absorbs sunlight and light from indoor lighting, emits its energy at night or in a dark place, and emits light to provide visibility in dark places.
  • the obtained sheet can still satisfy the mechanical properties, productivity and price. Not something.
  • the sheet (2) since the sheet is of a single-wafer type, productivity is low. Further, in order to obtain a certain level of luminance, it is necessary to apply a plurality of coatings. There is a disadvantage that the surface properties and productivity are reduced. Furthermore, in this case, since it is necessary to perform screen printing to form an ink image, a screen printing plate must be prepared, which is not suitable for producing a small number of products of various types. This
  • the present invention provides a luminous recording sheet that can easily produce a display having luminous properties from printing and image patterns created using a personal computer or the like, and that does not require attachment of a luminous sheet and an output sheet. And providing a display object. Disclosure of the invention The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
  • a luminous layer composed of a resin and a luminous pigment is provided on at least one surface of the base film, and a recording layer recordable with toner or ink is further provided on the luminous layer or on the opposite surface.
  • the present invention provides a recording sheet having a luminous property characterized by laminating a plurality of layers.
  • a luminous layer composed of a resin and a luminous pigment is provided on at least one surface of the base film, and a resolution of 200 to 140 is further provided thereon or on the opposite surface.
  • a display object characterized by forming an image layer of 0 dpi is provided.
  • the recording sheet having luminous properties of the present invention is provided with a luminous layer composed of a resin and a luminous pigment on at least one surface of the base sheet, and recording with toner or ink on the surface or on the surface on the opposite side.
  • a possible recording layer is provided.
  • paper, synthetic paper, plastic sheet, and the like are usually used for thermal transfer printers (sublimation transfer printers, thermal melt transfer printers, etc.), ink jet printers, laser printers, and the like.
  • a base sheet can be used.
  • the substrate sheet that blocks light include a plastic sheet made of a thermoplastic resin or the like to which a white pigment such as titanium oxide, calcium carbonate, or synthetic silica is added.
  • the thermoplastic resin include known resins such as a polyester resin, an acrylic resin, a polycarbonate resin, a polyethersulfone resin, and a polyolefin resin. Among them, a biaxially stretched polyethylene terephthalate sheet is preferable in terms of dimensional stability, flatness, and heat resistance. Also, a laminate of a plastic sheet and paper can be used.
  • the substrate sheet When the recording layer and the luminous layer are provided on opposite surfaces, the substrate sheet needs to have transparency, and a transparent plastic sheet is preferable.
  • transparent plastic sheets include polyester resin, acrylic resin, Examples include known plastic materials such as carbonate resins, polyethersulfone resins, and polyolefin resins.
  • the thickness of the substrate sheet is usually from 25 to 250 ⁇ , and preferably from 38 to 100 m from the viewpoint of workability and printer suitability.
  • the luminous layer in the recording sheet of the present invention comprises a resin and a luminous pigment.
  • a luminous pigment used in the luminous layer in the present invention for example, metal sulfides such as barium, strontium, cadmium, calcium, and zinc and a fluorescent dye are dissolved together with an initial condensate of a condensable synthetic resin to promote condensation.
  • MA 1 2 0 4 (1) (wherein, M is made of at least one selected from the group consisting of calcium, strontium and barium)
  • a magnesium-added oxide compound obtained by using a mother crystal of a compound obtained by adding magnesium to this oxide-based compound, or a compound obtained by adding magnesium to this oxide-based compound, or an oxide-based compound or a magnesium-added oxide thereof Activating phosphor compounds to which palladium, dyspronium, and neodymium are added as an activator for the base compound. Specific examples include N Nightlight G-300M manufactured by Nemoto Special Science Co., Ltd.
  • Q is at least one selected from B i, C a, Mg, and Mn, a is 0.0005 ⁇ a ⁇ 0.002, and b is 0.000 1 ⁇ b ⁇ 0. 35 and n is 1 ⁇ n ⁇ 7)
  • the use of the N luminous G-300M or the like is preferable for obtaining a clear image as a display. Further, in order to obtain a clearer image as a display material, it is preferable to use, as the phosphorescent agent, one that looks white under ordinary visible light.
  • S r A l 2 0 4 E u, the phosphorescent phosphors consisting of D y, that the addition of E u 2 0 3 (JP-A-9 one 1 3 0 2 8 JP) and, phosphorescent Examples include pigments having calcium carbonate or silica adhered to the surface of the pigment, and are available as “WA-300” manufactured by Nemoto Special Chemical Co., Ltd.
  • the resin used for the light storage layer of the present invention conventionally known various resins are used. Such materials include thermoplastic resins, curable resins, rubbers and the like. In the present invention, it is particularly preferable to use a curable resin.
  • the curable resin various conventionally known resins having thermosetting properties and photocuring properties can be used.
  • the thermosetting resin includes various types such as urethane type, epoxy type, polyester (alkyd type), silicon type, and thermosetting type acrylic type.
  • the photocurable resin include conventionally known resins such as acryl-based resins.
  • thermosetting resin is preferably used as a two-component composition comprising a main component comprising a thermosetting resin component and a curing agent thereof.
  • an aliphatic (non-aromatic) thermosetting resin containing no aromatic component as the resin binder.
  • aliphatic urethane resins and thermosetting acrylic resins are particularly preferred because of their excellent weather resistance, heat resistance, and adhesion to the base film.
  • the aliphatic urethane resin in this case it is preferable to use a two-part composition in which a main agent composed of aliphatic acrylic polyol and an auxiliary composed of non-yellowing aliphatic isocyanate (hardener) are combined.
  • the aliphatic acryl polyol is a polymer in which a hydroxyl group has been introduced into an acryl polymer or copolymer.
  • the introduction of the hydroxyl group is achieved by copolymerizing an acryl-based ester monomer having a hydroxyl group such as j3-hydroxyshethyl methacrylate with a non-aromatic acryl-based monomer such as acrylic acid / methyl methacrylate. Can be achieved.
  • Non-yellowing aliphatic isocyanates include water additives such as hexamethylene diisocyanate, isophorone diisocyanate, and metaxylene diisocyanate, and non-aromatics such as norvonenedisocyanate.
  • water additives such as hexamethylene diisocyanate, isophorone diisocyanate, and metaxylene diisocyanate
  • non-aromatics such as norvonenedisocyanate.
  • Trimethylo It is made by reacting polyols such as lepropane, glycerin, and glycol to form adducts, and removing excess isocyanate.
  • composition comprising the aliphatic acrylic polyol and the non-yellowing isocyanate
  • a resin binder when it is used as a cured resin film, it is easy to adjust the glass transition point and elongation of the obtained film.
  • a luminous layer coating film having good durability, heat resistance and mechanical strength can be obtained.
  • the mixing ratio of the luminous pigment and the resin is in the range of 5:95 to 95: 5 by weight.
  • the resin solid content is less than 5 parts by weight, the light-storing layer strength cannot be obtained, and when the light-storing pigment is less than 5 parts by weight, sufficient night vision cannot be obtained.
  • the mixing ratio of the light-storing pigment and the resin is more preferably in the range of 15:85 to 85:15 by weight.
  • the glass transition temperature (hereinafter, also referred to as Tg) of the phosphorescent layer of the present invention is preferably from 10 to 60 ° C. in consideration of winding a sheet into a roll at the time of production. Ding 8 blocking can not be avoided at the time and storage time of 1 0 ° Certificates up is less than C, cracks occur in the coating film when Ri ⁇ When it is or 6 0 ° C or higher.
  • the thickness of the luminous layer is in the range of 20 to 200 m, preferably in the range of 30 to 150 ⁇ m. When the thickness of the luminous layer is less than 20 / m, sufficient night vision cannot be obtained, and when it exceeds 200 m, it is not preferable in terms of cost and workability.
  • the preferred thickness of the light-storing layer is in the range of 30 to 70 ⁇ from the viewpoint of light-storing performance, in particular, night vision and workability.
  • the resin binder is a liquid resin at the time of forming the film
  • the use of a solvent is not always necessary. It becomes a coating liquid of 5 to 85%, and a luminous layer is formed by coating and drying according to a conventional method.
  • various additives conventionally used for example, a surfactant, an antifoaming agent, a stabilizer and the like can be added to the coating liquid.
  • the base sheet and the light-storing layer or between the light-storing layer and the recording layer may be used.
  • a primer layer may be provided.
  • the primer layer a saturated polyester resin or a urethane resin is usually used. Alternatively, a urethane resin is preferable because of good adhesion between the light storage layer and the recording layer.
  • the coating amount of this primer layer is usually in the range of 0.5 to 20 g Zm 2 , but preferably 0.5 to 10 g Zin 2 . When the coating amount is less than 0.5 g Zm 2 , uniform adhesion cannot be obtained, and when the coating amount is larger than 20 g Zm 2 , it is not preferable in terms of cost and workability.
  • chemical etching treatment such as chromic acid treatment, ionizing radiation treatment such as corona treatment or plasma treatment, ozone exposure, Surface treatment such as chemical or physical treatment that oxidizes the surface by fire exposure or high-voltage exposure may be applied.
  • a toner or an ink particularly an ink such as an ink for ink jet, an aqueous ballpoint pen, an aqueous pen and the like, and a sublimable dye ink and a sublimable pigment ink are provided on the phosphorescent layer or on the surface opposite to the phosphorescent layer.
  • a recording layer having the property of retaining ink such as is provided. Examples of the recording layer include a layer conventionally used as an ink receiving layer of a recording sheet for an ink jet, a toner receiving layer used for a PPC recording material and the like, which has transparency, and in particular, a phosphorescent layer. A material having transparency that can be visually confirmed is used.
  • the ink receiving layer is formed from at least one layer containing, for example, a water-soluble or water-absorbing polymer compound or a water-resistant water-soluble polymer compound as a binder and optionally containing a pigment or dye fixing agent, organic or inorganic fine particles, and the like.
  • a water-soluble or water-absorbing polymer compound or a water-resistant water-soluble polymer compound as a binder and optionally containing a pigment or dye fixing agent, organic or inorganic fine particles, and the like.
  • water-soluble and water-absorbing polymer compounds examples include polybutyl alcohol and derivatives thereof, polybiercetal, polybutylpyrrolidone, starch, latetus, acrylic resin, melamine resin, cellulose, tannin, and alginic acid.
  • the water-resistant polymer compound is obtained by insolubilizing the water-soluble polymer compound through a reaction such as a salt bond, a coordination bond, a covalent bond, and a hydrogen bond.
  • crosslinking agent for the water-soluble polymer examples include a fibrin reaction crosslinking agent such as a urea resin, a water-soluble melamine, an isocyanate resin, and an aziridine compound. By using this crosslinking agent, water resistance can be imparted to the coating film.
  • the pigment or dye fixing agent examples include pseudo-boehmite, colloidal silica, anionic surfactant, and porous silica.
  • pseudo-boehmite and colloidal silica are water-resistant, dye-pigment-fixed. It is preferable because it has excellent properties and has transparency.
  • the material used for the toner receiving layer includes an acrylic resin, a polyolefin resin, for example, a polyethylene resin, a polypropylene resin, and the like. Is preferably used.
  • the toner receiving layer having a temperature equal to or lower than the melting point of the toner, it is possible to further improve the toner receptivity, the color development of the image, and the sharpness of the image. It is particularly preferable that the ink receiving layer has toner adhesion because it can be used for both purposes.
  • the recording layer of the present invention may contain organic or inorganic fine particles to such an extent that the light storage properties of the light storage layer are not impaired.
  • organic or inorganic fine particles include fine powders of synthetic silica, natural silica, kaolin, talc, sauce, calcium carbonate, titania, alumina, zirconia, zeolite, barium sulfate, magnesium hydroxide, calcium phosphate, glass, etc.
  • inorganic resins such as acrylic resin, urethane resin, butyl chloride resin, benzoguanamine resin, and synthetic resin powder such as benzoguanamine / melamine formaldehyde condensate.
  • silica and carbonic acid calcium are preferred among the inorganic fine particles because they are excellent in ink absorption and blocking resistance.
  • organic fine particles acrylic resin and benzoguanamine resin are preferable because they do not impair transparency and have excellent blocking resistance and printer transportability.
  • the shape of the particles is preferably spherical for excellent workability in preparing the coating solution and excellent ink permeability.
  • a particle-form surface-roughening agent can be used, and the particle size of the surface-roughening agent particles is in the range of 0.5 to 30 rn in weight average particle diameter. is there. If the particle size of the surface-forming agent particles is smaller than this range, no convex portion is formed on the surface of the recording layer, and the effect of surface roughening does not appear, and the fixability of the pigment ink does not improve. If the diameter of the particles is larger than this range, the particles on the surface of the recording layer become large, and the transfer of the toner image becomes poor.
  • the particle size of the surface-roughening agent is preferably in the range of 2 to 25 ⁇ m from the viewpoints of forming convex portions on the surface, fixing the pigment, preventing transfer unevenness, and obtaining a clear image.
  • the surface-roughening agent When the surface-roughening agent is contained in the recording layer, its content can be appropriately selected within a range that does not impair the transparency of the recording layer and the luminous property of the luminous layer.
  • the content is in the range of 0.1 to 20% by weight in the recording layer.
  • the content of the surface-forming agent is less than 0.1% by weight, blocking occurs, and when the content is more than 20% by weight, image reproducibility, transparency and luminous efficiency are undesirably reduced.
  • the recording layer of the present invention is prepared, for example, by dissolving or decomposing the above-mentioned polymer compound and, if desired, a surface-roughening agent in a solvent at a predetermined ratio, respectively, to obtain a solid content concentration of about 10 to 15% by weight.
  • After preparing the coating liquid it can be formed by applying it on a substrate sheet, on a primer layer provided as required, or on a luminous layer according to a conventional method, and then drying it.
  • various additives conventionally used for example, a surfactant, a lubricant, a stabilizer and the like can be added to the coating liquid.
  • the thickness of the recording layer of the present invention is in the range of 5 to 30 / im, preferably 7 to 20. If the thickness of the recording layer is less than 5 ⁇ , the ink absorption and toner receptivity will be insufficient, and if it exceeds 30 ⁇ , curl of the sheet will occur, making it difficult to prevent this and cost. It is not preferable from the viewpoint.
  • an adhesive layer may be provided on a surface opposite to the surface on which the luminous layer is provided.
  • a white paint layer is provided on the luminous layer.
  • the observation surface of the print / image pattern can appear more white.
  • This white paint layer mainly comprises a binder and a white pigment, and the binder can be appropriately selected from thermosetting and thermoplastic resins. For example, phosphorescent from the point of adhesion with the phosphorescent layer It is preferable to use the same type of binder used for the layer.
  • inorganic pigments such as titanium oxide, zinc oxide, talc, clay, calcium carbonate, silica, aluminum hydroxide, aluminum oxide, and organic pigments such as white acryl resin particles may be used as the white pigment. It can. Among them, titanium oxide is preferable because of its excellent concealing property.
  • the particle size of the white pigment is in the range of 0.1 to 50 ⁇ m in weight average particle size. Outside of this range, the adhesion to the phosphorescent layer and the whiteness will be reduced.
  • the particle size of the white pigment is preferably in the range of 2 to 30 m from the viewpoint of the adhesion to the phosphorescent layer and the decrease in luminance due to the decrease in whiteness.
  • the mixing ratio of the white pigment and the binder may be appropriately selected depending on the degree of whiteness to be obtained. For example, the total light transmittance is preferably 30% or less.
  • the white paint layer is coated with organic fine particles such as synthetic resin powder such as acrylic resin, benzoguanamine resin, and benzoguanamine Z melamine / formaldehyde condensate in order to prevent the printer from being transported or blocking. May be included.
  • synthetic resin powder such as acrylic resin, benzoguanamine resin, and benzoguanamine Z melamine / formaldehyde condensate
  • the printer resolution in a range of 200 to 1,400 dpi (Dots Per Inch). is there. If the printer resolution is less than 200 dpi, the printed image will be printed '' The resolution of the image pattern will be low, resulting in reduced image clarity and impact.If it exceeds 1400 dpi, clear images will be obtained during the day.
  • the output print ⁇ The image pattern impairs the luminous properties, the luminous efficiency and the luminous efficiency of the luminous pigment are reduced, and printing in a dark place ⁇
  • the image pattern can be observed without a light source, so-called night vision Is undesirably reduced. This is to prevent the phenomenon that light from the phosphorescent layer appears on the pattern surface between dots or through a translucent part, and it is desirable to select the printer resolution appropriately according to the output sheet size. Better. For example, when the sheet size exceeds A3, a clear image can be obtained even with a relatively low resolution of the printer, and visibility at a place can be secured.
  • the display material of the present invention is a recording sheet in which, in the recording layer, an image having a resolution of 200 to 1,400 dpi, preferably 300 to 1,200 dpi is formed. Become.
  • the image formation can be performed using various printers as described above, or can be performed using various printing methods.
  • the display object of the present invention is displayed at a predetermined location as an advertisement medium or the like according to the type of the image.
  • the physical properties of the recording sheet and the display were evaluated according to the following methods.
  • EPSON Prospurt '' Photo Mach Color Printer PM Print at 180, 360, 720, and 1440 dpi using a 2000C printer, and its image quality was visually inspected at a distance of 1 m during the day and night. evaluated.
  • the image can be recognized without any problem during the day or at night.
  • Images can be recognized during the day, but not at night.
  • X Images cannot be recognized during the day or night.
  • the adhesion between the luminous layer and the recording layer was evaluated by a grid test (JISK-5400).
  • Printing was performed using a Matsuha jet printer PM700C manufactured by EPSON and evaluated by the following indices.
  • the appearance of the coating film surface was visually observed at the time of winding up the mouth.
  • Acrylic polyol (hydroxyl value 17.5) 43.5 parts by weight, phosphorescent pigment (G-300M, manufactured by Nemoto Special Chemical Co., Ltd.) 47.8 parts by weight, additive 4.4 parts by weight, curing agent (N CO% 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution.
  • phosphorescent pigment G-300M, manufactured by Nemoto Special Chemical Co., Ltd. 47.8 parts by weight
  • additive 4.4 parts by weight curing agent (N CO% 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution.
  • Example 2 After providing an easy-adhesion layer of urethane resin having a thickness of 1 ⁇ m on the phosphorescent layer, the above-mentioned coating liquid for forming a recording layer is applied on the easy-adhesion layer with a wire bar, and dried to a thickness of 10 ⁇ m. A recording layer (ink receiving layer) having a thickness of ⁇ m was formed, and a recording sheet having a luminous property according to the present invention was prepared.
  • Example 2 Example 2
  • a recording sheet was manufactured in the same manner as in Example 1 except that the coating liquid for forming a recording layer was changed as follows.
  • Acrylic polyol (hydroxyl value 17.5) 43.5 parts by weight, phosphorescent pigment (G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.) 47.8 parts by weight, additives 4.4 parts by weight, curing agent (NCO % 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution.
  • phosphorescent pigment G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.
  • additives 4.4 parts by weight curing agent (NCO % 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution.
  • the above-mentioned coating solution is applied on the easy adhesion layer with an applicator, and dried to a thickness of 50 / m, Tg 35 A phosphorescent layer at ° C was formed.
  • Example 1 was repeated in the same manner as in Example 1 except that the phosphorescent layer according to the present invention was replaced by a sheet (trade name: Luminova, manufactured by Nemoto Special Chemicals Co., Ltd.) in which a phosphorescent pigment was kneaded with a vinyl chloride resin.
  • the recording layer forming solution having the composition shown in (1) was applied to obtain a recording sheet.
  • Example 4
  • Example 3 all except that the phosphorescent agent (Nemoto Special Chemical Co., WA-300) was used instead of the phosphorescent agent (Nemoto Specialty Chemical Co., G-300M) used in the coating solution for forming the phosphorescent layer.
  • a recording sheet was manufactured in the same manner as in Example 3.
  • the brightness (mc d / m 2 ) of this recording sheet was 200 (one minute value).
  • EPSON Machjet Printer PM-700C it was performed under normal visible light. The images were clearer than in Examples 1-3.
  • the physical properties of this product were evaluated by the above-mentioned evaluation methods.
  • Example 4 The same procedure as in Example 4 was performed except that a white layer forming coating liquid having the following composition was applied on the phosphorescent layer of Example 4 and dried to form a 20 // thick white layer. Then, a recording sheet was manufactured. At this time, the total light transmittance of the white layer was 25%, the brightness (mc d / m 2 ) of the recording sheet was 300 (one minute value), and the EP SON Matsuhajit Printer PM-700C was used on the recording layer. When an image pattern is formed on a Under visual light, the image was clearer than in Example 4. The physical properties of this product were evaluated by the above evaluation methods.
  • Acrylic polyol (hydroxyl value 17.5) 60 parts by weight, white pigment (Taipeta R_680, manufactured by Ishihara Sangyo) 12 parts by weight, additives 1.2 parts by weight, curing agent (NCO% 12.6) 3. 8 parts by weight, 14 parts by weight of toluene and 9 parts by weight of methyl sorbate acetate were mixed to prepare a white layer forming coating solution.
  • white pigment Tipeta R_680, manufactured by Ishihara Sangyo
  • additives 1.2 parts by weight
  • curing agent NCO% 12.6
  • Example 3 instead of the ink receiving layer, an ink fixing layer forming coating liquid consisting of 30 parts by weight of a polyester resin, 20 parts by weight of toluene, 20 parts by weight of methyl ethyl ketone, and 30 parts by weight of an additive was applied and dried.
  • a recording sheet was prepared in the same manner as in Example 3 except that an ink fixing layer was provided.
  • a thermal transfer printer MD-2300, manufactured by Alps
  • “1” indicates that the ink receiving layer could not be formed and could not be evaluated.
  • the luminous recording sheet of the present invention was printed with a personal computer or the like. Hard output can be easily performed with a plotter, thermal transfer printer (sublimation transfer printer, thermal melt transfer printer, etc.), laser printer, and so on. Further, since the recording sheet having the luminous property of the present invention has the luminous layer and the recording layer laminated, the work of bonding the luminous sheet and the recording sheet is unnecessary, and the working efficiency is good.
  • a white paint layer on the luminous layer, it is possible to improve the luminance of the luminous layer, and when a white luminous agent is used, it looks more white under normal visible light. The pattern of the layer can be clearly reproduced.

Abstract

A recording sheet having a phosphorescent layer made of resin and phosphorescent pigment and provided at least on one side of a base film and a recording layer recordable with toner or ink and provided over the phosphorescent layer or on the other side of the base film and a sign having such a phosphorescent layer and an image layer having a resolution of 200 to 1400 dpi and provided over the phosphorescent layer or on the other side of the base film are disclosed. They are preferably applied to guideboards and posters and excellent in visibility.

Description

明 細 書  Specification
蓄光性を有する記録用シート及び表示物 技術分野  Recording sheet and display having luminous properties
本発明は、 喑所における案内板、 ポスター等として好適に用いることができる 視認性に優れた蓄光性を有する記録用シート及び蓄光性を有する表示物に関する ものである。 背景技術  The present invention relates to a recording sheet having luminous properties and excellent luminosity, which can be suitably used as a guide plate, a poster and the like in a place, and a display material having luminous properties. Background art
従来、 暗所において視認性のよいシートとして、 (1 ) 再帰反射剤ゃ蓄光顔料 を樹脂 (特に塩化ビュル樹脂) 中に含有させシート状にしたもの、 あるいは Conventionally, as a sheet with good visibility in a dark place, (1) a sheet made by including a retroreflective agent ゃ phosphorescent pigment in a resin (especially a vinyl chloride resin), or
( 2 ) 通常のシート状に、 蓄光剤を含有させたインキで画像を形成したものがあ る。 これらはいずれも、 蓄光剤が太陽光や室内照明の光を吸収し夜間あるいは暗 所にてそのエネルギーを放出し、 発光することを利用し、 暗い場所における視認 性を持たせたものである。 (2) There is an image formed on a normal sheet using an ink containing a luminous agent. In each of these methods, the luminous agent absorbs sunlight and light from indoor lighting, emits its energy at night or in a dark place, and emits light to provide visibility in dark places.
しかしながら、 上記 (1 ) のシートでは、 蓄光顔料当を樹脂中に練り込み、 こ れをフィルム化していることから、 得られるシートは機械的物性、 生産性及び価 格の点で未だ満足し得るものではない。  However, in the sheet of the above (1), since the phosphorescent pigment is kneaded into the resin and this is formed into a film, the obtained sheet can still satisfy the mechanical properties, productivity and price. Not something.
また、 上記 (2 ) のシートの場合、 枚葉式であるため、 生産性が低く、 また、 ある程度の輝度を得るためには重ね塗りをする必要があり、 これが原因となって、 製品シートの表面特性及び生産性が低くなるという欠点があった。 さらに、 この 場合、 インク画像を形成するのにスク リーン印刷を行う必要があるため、 スクリ 一ン印刷版を作成しなければならず、 少量多品種の製品を作成するには不向きで めつ 7こ  In the case of the sheet (2), since the sheet is of a single-wafer type, productivity is low. Further, in order to obtain a certain level of luminance, it is necessary to apply a plurality of coatings. There is a disadvantage that the surface properties and productivity are reduced. Furthermore, in this case, since it is necessary to perform screen printing to form an ink image, a screen printing plate must be prepared, which is not suitable for producing a small number of products of various types. This
本発明は、 パソコン等を用いて作成した印字 ·画像パターンから簡単に蓄光性 を有する表示物を作製でき、 かつ、 蓄光シートと出力シートとの貼り付けが不要 である蓄光性を有する記録用シート及び表示物を提供することをその課題とする。 発明の開示 本発明者らは、 上記課題を解決すべく鋭意研究を重ねた結果、 本発明を完成す るに至った。 The present invention provides a luminous recording sheet that can easily produce a display having luminous properties from printing and image patterns created using a personal computer or the like, and that does not require attachment of a luminous sheet and an output sheet. And providing a display object. Disclosure of the invention The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
即ち、 本発明によれば、 基材フィルムの少なくとも一方の面上に樹脂と蓄光顔 料からなる蓄光層を設け、 さらにその上もしくはその反対側の面上にトナー又は インクで記録可能な記録層を積層したことを特徴とする蓄光性を有する記録用シ ートが提供される。  That is, according to the present invention, a luminous layer composed of a resin and a luminous pigment is provided on at least one surface of the base film, and a recording layer recordable with toner or ink is further provided on the luminous layer or on the opposite surface. The present invention provides a recording sheet having a luminous property characterized by laminating a plurality of layers.
また、 本発明によれば、 基材フィルムの少なくとも一方の面上に樹脂と蓄光顔 料からなる蓄光層を設け、 さらにその上にもしくはその反対側の面上に解像度 2 0 0〜 1 4 0 0 d p iの画像層を形成したことを特徴とする表示物が提供される。 以下本発明について詳述する。  Further, according to the present invention, a luminous layer composed of a resin and a luminous pigment is provided on at least one surface of the base film, and a resolution of 200 to 140 is further provided thereon or on the opposite surface. A display object characterized by forming an image layer of 0 dpi is provided. Hereinafter, the present invention will be described in detail.
本発明の蓄光性を有する記録用シートは、 基材シートの少なくとも一方の面上 に榭脂と蓄光顔料からなる蓄光層を設け、 さらにその上またはその反対側の面上 にトナー又はインクで記録可能な記録層を設けたことを特徴とする。  The recording sheet having luminous properties of the present invention is provided with a luminous layer composed of a resin and a luminous pigment on at least one surface of the base sheet, and recording with toner or ink on the surface or on the surface on the opposite side. A possible recording layer is provided.
本発明で用いる基材シートとしては、 紙、 合成紙、 プラスチックシート等、 通 常、 熱転写プリンター (昇華転写プリンター、 熱溶融転写プリンタ一等) 、 イン クジエツトプリンターやレーザ一プリンターなどに使用される基材シートを使用 することができる。  As the base sheet used in the present invention, paper, synthetic paper, plastic sheet, and the like are usually used for thermal transfer printers (sublimation transfer printers, thermal melt transfer printers, etc.), ink jet printers, laser printers, and the like. A base sheet can be used.
この基材シートは、 記録層を蓄光層上に設ける場合には、 光を遮断する基材シ ートを用いることが輝度の点で有利である。 光遮断する基材シートとしては、 酸 化チタン、 炭酸カルシウム、 合成シリカ等の白色顔料を添加した熱可塑性樹脂等 のプラスチックシートがある。 熱可塑性樹脂としては、 ポリエステル樹脂、 ァク リル樹脂、 ポリカーボネート榭脂、 ポリエーテルサルホン樹脂、 ポリオレフイン 榭脂等の公知のものを挙げることができる。 中でも 2軸延伸ポリエチレンテレフ タレートシートが寸法安定性、 平面性、 耐熱性の点から好適である。 また、 ブラ スチックシ一トと紙を積層したものも使用可能である。  In the case where the recording layer is provided on the luminous layer, it is advantageous to use a substrate sheet that blocks light in terms of luminance. Examples of the substrate sheet that blocks light include a plastic sheet made of a thermoplastic resin or the like to which a white pigment such as titanium oxide, calcium carbonate, or synthetic silica is added. Examples of the thermoplastic resin include known resins such as a polyester resin, an acrylic resin, a polycarbonate resin, a polyethersulfone resin, and a polyolefin resin. Among them, a biaxially stretched polyethylene terephthalate sheet is preferable in terms of dimensional stability, flatness, and heat resistance. Also, a laminate of a plastic sheet and paper can be used.
また、 記録層と蓄光層とは、 反対側の面に設ける場合には、 基材シートは透明 性を有することが必要であり、 透明プラスチックシートが好適である。 このよう な透明プラスチックシ一トとしては、 ポリエステル榭脂、 アクリル榭脂、 ポリ力 ーボネート榭脂、 ポリエーテルサルホン樹脂、 ポリオレフイン樹脂などの公知の プラスチック材料からなるものが挙げられる。 When the recording layer and the luminous layer are provided on opposite surfaces, the substrate sheet needs to have transparency, and a transparent plastic sheet is preferable. Such transparent plastic sheets include polyester resin, acrylic resin, Examples include known plastic materials such as carbonate resins, polyethersulfone resins, and polyolefin resins.
基材シートの厚さは、 通常 25〜250 μπιであり、 作業性、 プリンター適性 の観点から好ましくは 38〜100 mの範囲である。  The thickness of the substrate sheet is usually from 25 to 250 μπι, and preferably from 38 to 100 m from the viewpoint of workability and printer suitability.
本発明の記録用シートにおける蓄光層は、 樹脂と蓄光顔料とからなる。 本発明 において蓄光層に用いられる蓄光顔料としては、 例えばバリウム、 ス トロンチウ ム、 カドミウム、 カルシウム、 亜鉛などの金属硫化物や蛍光染料を縮合性合成樹 脂の初期縮合物とともに溶解し、 縮合を進めて樹脂中に色素を固定させるなどし て得られる顔料や、 下記一般式 (1)  The luminous layer in the recording sheet of the present invention comprises a resin and a luminous pigment. As the luminous pigment used in the luminous layer in the present invention, for example, metal sulfides such as barium, strontium, cadmium, calcium, and zinc and a fluorescent dye are dissolved together with an initial condensate of a condensable synthetic resin to promote condensation. A pigment obtained by fixing a dye in a resin by using the following general formula (1)
MA 1204 (1) (式中、 Mはカルシウム、 ストロンチウム及びバリウムからなる群より選択され た少なくとも 1つからなる) MA 1 2 0 4 (1) ( wherein, M is made of at least one selected from the group consisting of calcium, strontium and barium)
で表わされる酸化物系化合物を母結晶にした化合物、 又はこの酸化物系化合物に マグネシゥムを添加した化合物を母結晶にしたマグネシゥム添加酸化物系化合物、 或いはこれらの酸化物系化合物もしくはマグネシゥム添加酸化物系化合物に対し て賦活剤として、 ユウ口ピウム、 ジスプロニゥム、 ネオジゥムを添加した賦活蛍 光体化合物などが挙げられる。 具体的には根本特殊科学株式会社製 N夜光 G— 3 00M等を挙げることができる。 Or a magnesium-added oxide compound obtained by using a mother crystal of a compound obtained by adding magnesium to this oxide-based compound, or a compound obtained by adding magnesium to this oxide-based compound, or an oxide-based compound or a magnesium-added oxide thereof. Activating phosphor compounds to which palladium, dyspronium, and neodymium are added as an activator for the base compound. Specific examples include N Nightlight G-300M manufactured by Nemoto Special Science Co., Ltd.
また、 下記一般式 (2)  The following general formula (2)
(S r E u) A 1204 · [ (S r E u) O · n (A 1 ^bBbQ 203 (OH) ] (S r E u) A 1 2 0 4 · [(S r E u) O · n (A 1 ^ b B b Q 2 0 3 (OH)]
(2) (2)
(式中、 Qは B i、 C a、 Mg、 Mnから選択される少なくとも 1種であり、 a は 0. 0005≤ a≤0. 002であり、 bは 0. 00 1≤b≤0. 35であり、 nは 1≤n≤ 7である) (In the formula, Q is at least one selected from B i, C a, Mg, and Mn, a is 0.0005≤a≤0.002, and b is 0.000 1≤b≤0. 35 and n is 1≤n≤7)
で表される化合物を挙げることができる。 Can be mentioned.
上記一般式 (1) や一般式 (2) で表される化合物の使用に比べて、 上記 N夜 光 G— 300M等の使用が、 表示物として鮮明な画像を得るために好ましい。 また、 表示物として、 より鮮明な画像を得るためには前記蓄光剤として、 通常 の可視光下では白色に見えるものを使用することが好ましい。 このようなものと しては、 S r A l 2 0 4 : E u , D yからなる蓄光性蛍光体に、 E u 2 0 3を添加 したもの (特開平 9一 1 3 0 2 8号公報) や、 蓄光顔料の表面に炭酸カルシウム やシリカなどを付着させたものなどが挙げられ、 根本特殊化学社製 「WA— 3 0 0」 として入手可能である。 As compared with the use of the compound represented by the general formula (1) or the general formula (2), the use of the N luminous G-300M or the like is preferable for obtaining a clear image as a display. Further, in order to obtain a clearer image as a display material, it is preferable to use, as the phosphorescent agent, one that looks white under ordinary visible light. With something like this Is then, S r A l 2 0 4 : E u, the phosphorescent phosphors consisting of D y, that the addition of E u 2 0 3 (JP-A-9 one 1 3 0 2 8 JP) and, phosphorescent Examples include pigments having calcium carbonate or silica adhered to the surface of the pigment, and are available as “WA-300” manufactured by Nemoto Special Chemical Co., Ltd.
本発明の蓄光層に用いる樹脂としては、 従来公知の各種のものが用いられる。 このようなものには、 熱可塑性樹脂、 硬化性榭脂、 ゴム等が包含される。 本発明 においては、 特に、 硬化性樹脂の使用が好ましい。 硬化性樹脂としては、 熱硬化 性や光硬化性を有する従来公知の各種のものを用いることができる。 熱硬化性樹 脂には、 ウレタン系、 エポキシ系、 ポリエステル (アルキッド系) 、 シリコン系、 熱硬化型アク リル系等の各種のものが包含される。 また、 光硬化性榭脂としては、 ァクリル系樹脂等の従来公知のものを挙げることができる。 樹脂バインダーとし て、 このような硬化性樹脂を用いることにより、 耐熱性及び耐久性の優れた蓄光 性フィルムを得ることができる。  As the resin used for the light storage layer of the present invention, conventionally known various resins are used. Such materials include thermoplastic resins, curable resins, rubbers and the like. In the present invention, it is particularly preferable to use a curable resin. As the curable resin, various conventionally known resins having thermosetting properties and photocuring properties can be used. The thermosetting resin includes various types such as urethane type, epoxy type, polyester (alkyd type), silicon type, and thermosetting type acrylic type. Examples of the photocurable resin include conventionally known resins such as acryl-based resins. By using such a curable resin as a resin binder, a luminous film excellent in heat resistance and durability can be obtained.
前記熱硬化性樹脂は、 熱硬化性樹脂成分からなる主剤と、 その硬化剤とからな る 2液性組成物として用いるのが好ましい。  The thermosetting resin is preferably used as a two-component composition comprising a main component comprising a thermosetting resin component and a curing agent thereof.
本発明においては、 樹脂バインダーとしては、 特に、 芳香族成分を含まない脂 肪族系 (非芳香族系) の熱硬化性樹脂の使用が好ましい。 その中でも、 特に、 脂 肪族ウレタン系樹脂及び熱硬化性アク リル系樹脂が、 耐候性、 耐熱性、 基材フィ ルムとの接着性に優れるので好ましい。 この場合の脂肪族ウレタン系榭脂として は、 脂肪族アクリルポリオールからなる主剤と無黄変脂肪族イソシァネート (硬 化剤) からなる助剤とを組合わせた 2液性組成物の使用が好ましい。  In the present invention, it is particularly preferable to use an aliphatic (non-aromatic) thermosetting resin containing no aromatic component as the resin binder. Among them, aliphatic urethane resins and thermosetting acrylic resins are particularly preferred because of their excellent weather resistance, heat resistance, and adhesion to the base film. As the aliphatic urethane resin in this case, it is preferable to use a two-part composition in which a main agent composed of aliphatic acrylic polyol and an auxiliary composed of non-yellowing aliphatic isocyanate (hardener) are combined.
脂肪族ァクリルポリオールは、 ァクリル系重合体又は共重合体に水酸基を導入 したポリマーである。 その水酸基の導入は、 j3—ヒ ドロキシェチルメタクリ レー トなどの水酸基を含有するァクリル系エステルモノマーを、 ァクリル酸ゃメタク リル酸メチルなどの非芳香族系ァクリル系モノマーと共重合させることにより達 成することができる。  The aliphatic acryl polyol is a polymer in which a hydroxyl group has been introduced into an acryl polymer or copolymer. The introduction of the hydroxyl group is achieved by copolymerizing an acryl-based ester monomer having a hydroxyl group such as j3-hydroxyshethyl methacrylate with a non-aromatic acryl-based monomer such as acrylic acid / methyl methacrylate. Can be achieved.
また、 無黄変の脂肪族イソシァネートは、 へキサメチレンジイソシァネート、 イソホロンジイソシァネート、 メタキシレンジイソシァネート等の水添加物、 ノ ルボネンジィソシァネートなどの非芳香族系ジィソシァネ一トに、 トリメチロー ルプロパン、 グリセリン、 グリコールなどのポリオールを反応させてァダク トを 作り、 過剰のイソシァネート除去させたものである。 Non-yellowing aliphatic isocyanates include water additives such as hexamethylene diisocyanate, isophorone diisocyanate, and metaxylene diisocyanate, and non-aromatics such as norvonenedisocyanate. To the Gissocinet, Trimethylo It is made by reacting polyols such as lepropane, glycerin, and glycol to form adducts, and removing excess isocyanate.
前記脂肪族系のアクリルポリオールと無黄変イソシァネートとからなる組成物 を榭脂バインダ一として用いるときには、 それを硬化樹脂フィルムとするときに、 得られるフィルムのガラス転移点及び伸長率の調節が容易である上、 耐久性、 耐 熱性及び機械的強度の良好な蓄光層被膜フィルムを得ることができる。  When the composition comprising the aliphatic acrylic polyol and the non-yellowing isocyanate is used as a resin binder, when it is used as a cured resin film, it is easy to adjust the glass transition point and elongation of the obtained film. In addition, a luminous layer coating film having good durability, heat resistance and mechanical strength can be obtained.
前記蓄光顔料と前記樹脂との配合割合は、 重量比で 5 : 9 5〜9 5 : 5の範囲 である。 樹脂固形分が 5重量部未満の場合は蓄光層の強度が得られず、 蓄光顔料 が 5重量部未満の場合は十分な暗視性が得られない。 蓄光層の塗膜強度及び蓄光 性能、 特に暗視性の点から、 蓄光顔料と樹脂との配合割合は、 重量比で 1 5 : 8 5〜8 5 : 1 5の範囲がより好ましい。  The mixing ratio of the luminous pigment and the resin is in the range of 5:95 to 95: 5 by weight. When the resin solid content is less than 5 parts by weight, the light-storing layer strength cannot be obtained, and when the light-storing pigment is less than 5 parts by weight, sufficient night vision cannot be obtained. From the viewpoint of the coating strength of the light-storing layer and the light-storing performance, particularly from the viewpoint of night vision, the mixing ratio of the light-storing pigment and the resin is more preferably in the range of 15:85 to 85:15 by weight.
本発明の蓄光層は、 製造の際にシートをロール状に巻取ることを考慮すると、 そのガラス転移温度 (以下 T gとも記す) は 1 0〜6 0 °Cであるのが好ましい。 丁 8が 1 0 °C未満であると卷取りの際や保存時にブロッキングが避けられず、 ま た 6 0 °C以上であると卷取り時に塗膜にクラックが発生する。 The glass transition temperature (hereinafter, also referred to as Tg) of the phosphorescent layer of the present invention is preferably from 10 to 60 ° C. in consideration of winding a sheet into a roll at the time of production. Ding 8 blocking can not be avoided at the time and storage time of 1 0 ° Certificates up is less than C, cracks occur in the coating film when Ri卷取When it is or 6 0 ° C or higher.
また、 蓄光層の厚みは 2 0〜2 0 0 mの範囲、 好ましくは 3 0〜 1 5 0 μ mの 範囲である。 蓄光層の厚みが 2 0 / m未満であると十分な暗視性が得られず、 ま た 2 0 0 mを越えるとコストの面や作業性の面から好ましくない。 蓄光性能、 特に暗視性及び作業性の点から蓄光層の好ましい厚さは 3 0〜7 0 μ ηαの範囲で ある。 The thickness of the luminous layer is in the range of 20 to 200 m, preferably in the range of 30 to 150 μm. When the thickness of the luminous layer is less than 20 / m, sufficient night vision cannot be obtained, and when it exceeds 200 m, it is not preferable in terms of cost and workability. The preferred thickness of the light-storing layer is in the range of 30 to 70 μηα from the viewpoint of light-storing performance, in particular, night vision and workability.
本発明の蓄光層は、 その成膜の際に、 樹脂バインダーが液状樹脂である場合に は、 必ずしも溶剤の使用は必要とされず、 その液状樹脂に蓄光顔料を配合するこ とによって固形分 4 5〜8 5 %の塗布液となり、 常法に従って塗布乾燥すること により蓄光層が形成される。 この際、 該塗工液には従来使用されている各種添加 剤、 例えば界面活性剤、 消泡剤、 安定剤などを添加することができる。  In the case where the resin binder is a liquid resin at the time of forming the film, the use of a solvent is not always necessary. It becomes a coating liquid of 5 to 85%, and a luminous layer is formed by coating and drying according to a conventional method. At this time, various additives conventionally used, for example, a surfactant, an antifoaming agent, a stabilizer and the like can be added to the coating liquid.
本発明の記録用シートにおいては、 前記基材シートと蓄光層又は記録層との密 着性を向上させるために、 必要に応じて、 基材と蓄光層、 或いは蓄光層と記録層 の間にプライマー層を設けてもよい。 このプライマー層としては、 通常飽和ポリ エステル樹脂やウレタン樹脂などが利用されるが、 特に、 基材シートと蓄光層、 或いは蓄光層と記録層との良好な密着性のためウレタン樹脂が好ましい。 このプ ライマー層の塗布量は、 通常 0 . 5〜 2 0 g Zm2の範囲であるが、 好ましくは 0 . 5〜1 0 g Zin2である。 塗布量が 0 . 5 g Zm2より少ない場合は均一な密 着性が得られず、 塗布量が 2 0 g Zm2より大きいと、 コスト上、 作業性の観点 から好ましくない。 In the recording sheet of the present invention, in order to improve the adhesion between the base sheet and the light-storing layer or the recording layer, if necessary, the base sheet and the light-storing layer or between the light-storing layer and the recording layer may be used. A primer layer may be provided. As the primer layer, a saturated polyester resin or a urethane resin is usually used. Alternatively, a urethane resin is preferable because of good adhesion between the light storage layer and the recording layer. The coating amount of this primer layer is usually in the range of 0.5 to 20 g Zm 2 , but preferably 0.5 to 10 g Zin 2 . When the coating amount is less than 0.5 g Zm 2 , uniform adhesion cannot be obtained, and when the coating amount is larger than 20 g Zm 2 , it is not preferable in terms of cost and workability.
また、 基材シートと蓄光層、 或いは基材シートと記録層の密着力を向上させる ために、 例えばクロム酸処理等のケミカルエッチング処理、 コロナ処理やプラズ マ処理等のイオン化放射線処理、 オゾン暴露、 火災暴露や高圧電撃暴露等により 表面を酸化させる化学的又は物理的処理などの表面処理を施してもよい。  In order to improve the adhesion between the substrate sheet and the phosphorescent layer, or between the substrate sheet and the recording layer, for example, chemical etching treatment such as chromic acid treatment, ionizing radiation treatment such as corona treatment or plasma treatment, ozone exposure, Surface treatment such as chemical or physical treatment that oxidizes the surface by fire exposure or high-voltage exposure may be applied.
本発明においては、 蓄光層の上又は蓄光層とは反対側の面上に、 トナー又はィ ンク、 特にインクジェッ ト用インクや水性ボールペン、 水性ペン等のインク及び 昇華性染料ィンク、 昇華性顔料ィンクなどのインクを保持する性質を有する記録 層を設ける。 この記録層としては、 従来インクジェッ ト用記録シートのインク受 容層として用いられているものや、 P P C用記録材料などで用いられているトナ 一受容層で透明性を有するもの、 特に蓄光層を目視確認できる程度の透明性を有 するものが用いられる。  In the present invention, a toner or an ink, particularly an ink such as an ink for ink jet, an aqueous ballpoint pen, an aqueous pen and the like, and a sublimable dye ink and a sublimable pigment ink are provided on the phosphorescent layer or on the surface opposite to the phosphorescent layer. A recording layer having the property of retaining ink such as is provided. Examples of the recording layer include a layer conventionally used as an ink receiving layer of a recording sheet for an ink jet, a toner receiving layer used for a PPC recording material and the like, which has transparency, and in particular, a phosphorescent layer. A material having transparency that can be visually confirmed is used.
インク受容層は、 例えば水溶性、 吸水性高分子化合物又は耐水化された水溶性 高分子化合物をバインダーとし、 所望により顔料又は染料定着剤、 有機もしくは 無機微粒子などを含有する少なく とも 1つの層からなることが好ましい。  The ink receiving layer is formed from at least one layer containing, for example, a water-soluble or water-absorbing polymer compound or a water-resistant water-soluble polymer compound as a binder and optionally containing a pigment or dye fixing agent, organic or inorganic fine particles, and the like. Preferably,
前記水溶性、 吸水性高分子化合物としては、 例えば、 ポリビュルアルコール及び その誘導体、 ポリ ビエルァセタール、 ポリ ビュルピロリ ドン、 デンプン、 ラテツ タス、 アクリル系樹脂、 メラミン樹脂、 セルロース、 タンニン、 アルギン酸等が 挙げられる。 Examples of the water-soluble and water-absorbing polymer compounds include polybutyl alcohol and derivatives thereof, polybiercetal, polybutylpyrrolidone, starch, latetus, acrylic resin, melamine resin, cellulose, tannin, and alginic acid.
また、 前記耐水化された水溶性高分子化合物は、 前記水溶性高分子化合物を塩 結合、 配位結合、 共有結合、 水素結合等の反応により不溶化することにより得ら れる。  Further, the water-resistant polymer compound is obtained by insolubilizing the water-soluble polymer compound through a reaction such as a salt bond, a coordination bond, a covalent bond, and a hydrogen bond.
前記水溶性高分子の架橋剤としては、 例えば、 繊維素反応架橋剤、 例えば尿素 樹脂、 水溶性メラミン等や、 イソシァネート樹脂、 アジリジン化合物が挙げられ る。 この架橋剤を用いることにより塗膜に耐水性を付与することができる。 また、 前記顔料又は染料定着剤としては、 例えば、 擬ベーマイ ト、 コロイダル シリカ、 ァニオン性界面活性剤、 多孔性シリカ等が挙げられ、 特に、 擬ベーマイ ト、 コロイダルシリカが耐水性、 染 ·顔料定着性にすぐれ、 かつ透明性を有する ので好ましい。 Examples of the crosslinking agent for the water-soluble polymer include a fibrin reaction crosslinking agent such as a urea resin, a water-soluble melamine, an isocyanate resin, and an aziridine compound. By using this crosslinking agent, water resistance can be imparted to the coating film. Examples of the pigment or dye fixing agent include pseudo-boehmite, colloidal silica, anionic surfactant, and porous silica. In particular, pseudo-boehmite and colloidal silica are water-resistant, dye-pigment-fixed. It is preferable because it has excellent properties and has transparency.
一方、 トナー受容層に用いられる材料としては、 アク リル系樹脂、 ポリオレフ イン系榭脂、 例えばポリエチレン系榭脂、 ポリプロピレン樹脂等からなるものが 挙げられるが、 トナーとの密着性の点からポリエチレン樹脂が好ましく用いられ る。 この時、 トナ一受容層は、 トナーの融点と同等またはそれよりも低いものを 選択することにより、 より トナー受容性、 画像の発色性、 画像の鮮明性向上する ことができる。 また、 前記インク受容層でトナー密着性のある場合は、 両方の用 途に使用できるので特に好ましい。  On the other hand, the material used for the toner receiving layer includes an acrylic resin, a polyolefin resin, for example, a polyethylene resin, a polypropylene resin, and the like. Is preferably used. At this time, by selecting the toner receiving layer having a temperature equal to or lower than the melting point of the toner, it is possible to further improve the toner receptivity, the color development of the image, and the sharpness of the image. It is particularly preferable that the ink receiving layer has toner adhesion because it can be used for both purposes.
さらに、 本発明の記録層においては、 蓄光層の蓄光性を阻害しない程度に有機 または無機微粒子を含有することができる。 これら微粒子を含有させることによ り、 出力時の搬送性や顔料及びトナーの定着性を向上することができる。 無機 - 有機微粒子としては、 例えば合成シリカ、 天然シリカ、 カオリン、 タルク、 タレ 一、 炭酸カルシウム、 チタニア、 アルミナ、 ジルコニァ、 ゼォライ ト、 硫酸バリ ゥム、 水酸化マグネシウム、 燐酸カルシウム、 ガラスなどの微粉末等の無機系の ものや、 アクリル系樹脂、 ウレタン榭脂、 塩化ビュル樹脂、 ベンゾグアナミン樹 脂、 ベンゾグアナミン ζメラミン ホルムアルデヒ ド縮合物などの合成樹脂の粉 末などの有機系のものが挙げられる。 中でも無機系微粒子ではシリカ及び炭酸力 ルシゥムがインク吸収性、 耐ブロッキング性に優れるので好ましい。 また、 有機 系微粒子ではアクリル樹脂、 ベンゾグアナミン樹脂が透明性を損なわず耐ブロッ キング性、 プリンター搬送性に優れるので好ましい。 また、 粒子の形状は塗布液 の調製時の作業性及びインク浸透性に優れるための球形のものが好ましい。  Further, the recording layer of the present invention may contain organic or inorganic fine particles to such an extent that the light storage properties of the light storage layer are not impaired. By incorporating these fine particles, the transportability at the time of output and the fixability of the pigment and the toner can be improved. Examples of inorganic-organic fine particles include fine powders of synthetic silica, natural silica, kaolin, talc, sauce, calcium carbonate, titania, alumina, zirconia, zeolite, barium sulfate, magnesium hydroxide, calcium phosphate, glass, etc. And inorganic resins such as acrylic resin, urethane resin, butyl chloride resin, benzoguanamine resin, and synthetic resin powder such as benzoguanamine / melamine formaldehyde condensate. Among them, silica and carbonic acid calcium are preferred among the inorganic fine particles because they are excellent in ink absorption and blocking resistance. Among organic fine particles, acrylic resin and benzoguanamine resin are preferable because they do not impair transparency and have excellent blocking resistance and printer transportability. In addition, the shape of the particles is preferably spherical for excellent workability in preparing the coating solution and excellent ink permeability.
本発明の記録層においては粒子状の粗面化形成剤を使用することができるが、 その粗面化形成剤粒子の粒径は、 重量平均粒径で 0 . 5〜3 0 rnの範囲である。 粗面化形成剤粒子の粒径がこの範囲より小さいと記録層表面に凸部が形成されず、 粗面化の効果が現れず、 また顔料インクの定着性が向上しない。 また該粒子の粒 径がこの範囲よりも大きいと記録層表面のと粒が大きくなり、 トナー像の転写む らが発生したり、 転写トナー像を定着する際、 ロールによる定着不十分となった り、 インクジェッ トで印字 '画像パターンを形成した際、 ドッ トが変形し、 鮮明 な画像を得ることができなくなる。 表面の凸部形成性、 顔料定着性、 転写むら防 止及び鮮明な画像を得るという点から、 好ましい粗面化形成剤の粒径は 2〜 2 5 μ mの範囲である。 In the recording layer of the present invention, a particle-form surface-roughening agent can be used, and the particle size of the surface-roughening agent particles is in the range of 0.5 to 30 rn in weight average particle diameter. is there. If the particle size of the surface-forming agent particles is smaller than this range, no convex portion is formed on the surface of the recording layer, and the effect of surface roughening does not appear, and the fixability of the pigment ink does not improve. If the diameter of the particles is larger than this range, the particles on the surface of the recording layer become large, and the transfer of the toner image becomes poor. When the transfer toner image is fixed, the roll is insufficiently fixed by the roll, or when the ink jet prints the image pattern, the dot is deformed and a clear image can be obtained. Disappears. The particle size of the surface-roughening agent is preferably in the range of 2 to 25 μm from the viewpoints of forming convex portions on the surface, fixing the pigment, preventing transfer unevenness, and obtaining a clear image.
また、 前記粗面化形成剤を記録層中に含有させる場合、 その含有量は記録層の 透明性と蓄光層の蓄光性を阻害しなレ、範囲で適宜選択することができるが、 通常 その含有量は、 記録層中 0 . 1〜2 0重量%の範囲である。 粗面化形成剤の含有 量が 0 . 1重量%未満の場合ブロッキングが発生し、 また 2 0重量%よりも多い 場合は画像再現性、 透明性、 蓄光効率が低下するので好ましくない。  When the surface-roughening agent is contained in the recording layer, its content can be appropriately selected within a range that does not impair the transparency of the recording layer and the luminous property of the luminous layer. The content is in the range of 0.1 to 20% by weight in the recording layer. When the content of the surface-forming agent is less than 0.1% by weight, blocking occurs, and when the content is more than 20% by weight, image reproducibility, transparency and luminous efficiency are undesirably reduced.
本発明の記録層は、 例えば前記高分子化合物及び所望により粗面化形成剤をそ れぞれ所定の割合で溶媒中に溶解又は分解させて、 固形分濃度 1 0〜1 5重量% 程度の塗工液を調製した後、 基材シート上に、 所望により設けられるプライマー 層上に、 または蓄光層上に、 常法に従って塗布した後、 乾燥させることによって 形成することができる。 この際、 該塗工液には従来使用されている各種添加剤、 例えば界面活十生剤、 潤滑剤、 安定剤などを添加するすることができる。  The recording layer of the present invention is prepared, for example, by dissolving or decomposing the above-mentioned polymer compound and, if desired, a surface-roughening agent in a solvent at a predetermined ratio, respectively, to obtain a solid content concentration of about 10 to 15% by weight. After preparing the coating liquid, it can be formed by applying it on a substrate sheet, on a primer layer provided as required, or on a luminous layer according to a conventional method, and then drying it. At this time, various additives conventionally used, for example, a surfactant, a lubricant, a stabilizer and the like can be added to the coating liquid.
本発明の記録層の膜厚は、 5〜3 0 /i m、 好ましくは 7〜2 0 の範囲であ る。 記録層の膜厚が 5 μ πι未満であるとインク吸収性やトナー受容性が不十分と なり、 また 3 0 μ πを越えるとシートのカールが発生し、 これを防止することが 難しく、 コスト面からも好ましくない。  The thickness of the recording layer of the present invention is in the range of 5 to 30 / im, preferably 7 to 20. If the thickness of the recording layer is less than 5 μπι, the ink absorption and toner receptivity will be insufficient, and if it exceeds 30 μπ, curl of the sheet will occur, making it difficult to prevent this and cost. It is not preferable from the viewpoint.
また、 本発明における記録用シートは、 基材シート、 蓄光層及び記録層を順次 積層した場合、 蓄光層が設けられている面とは反対側の面に粘着層を設けてもよ い。  In the recording sheet of the present invention, when a base sheet, a luminous layer and a recording layer are sequentially laminated, an adhesive layer may be provided on a surface opposite to the surface on which the luminous layer is provided.
さらに、 本発明における記録用シートは、 基材シート上に蓄光層を積層し、 蓄 光層とは反対側の面に記録層を形成する場合、 蓄光層上に白色塗料層を設けるこ とによりより高い輝度を得ることができ、 かつ、 白色蓄光剤を用いた場合、 印 字 ·画像パターンの観察面をより白色に見せることができる。 この白色塗料層は、 主に、 バインダーと白色顔料からなり、 バインダーは、 熱硬化性及び熱可塑性樹 脂の中から適宜選択することができる。 例えば、 蓄光層との密着性の点から蓄光 層に使用しているのと同種のバインダーを用いることが好ましい。 また、 白色顔 料としては、 酸化チタン、 亜鉛華、 タルク、 クレー、 炭酸カルシウム、 シリカ、 水酸化アルミニウム、 酸化アルミ二ゥム等の無機顔料や白色ァクリル樹脂粒子、 などの有機顔料を用いることができる。 なかでも酸化チタンが隠ぺぃ性にすぐれ ているので好ましい。 また、 白色顔料の粒径は、 重量平均粒径で 0. 1〜50 μ mの範囲である。 この範囲を逸脱すると、 蓄光層との密着性、 白色度が低下する。 蓄光層との密着性及び白色度低下による輝度低下の面から好ましい白色顔料の粒 径は◦. 2〜30 mの範囲である。 また、 白色顔料とバインダーとの配合割合 は、 得ようとする白色度により適宜選択すればよく、 例えば、 全光線透過率が 3 0%以下となるようにするのがよい。 Further, in the recording sheet of the present invention, when a luminous layer is laminated on a base sheet and a recording layer is formed on a surface opposite to the luminous layer, a white paint layer is provided on the luminous layer. When a higher luminance can be obtained and a white luminous agent is used, the observation surface of the print / image pattern can appear more white. This white paint layer mainly comprises a binder and a white pigment, and the binder can be appropriately selected from thermosetting and thermoplastic resins. For example, phosphorescent from the point of adhesion with the phosphorescent layer It is preferable to use the same type of binder used for the layer. In addition, inorganic pigments such as titanium oxide, zinc oxide, talc, clay, calcium carbonate, silica, aluminum hydroxide, aluminum oxide, and organic pigments such as white acryl resin particles may be used as the white pigment. it can. Among them, titanium oxide is preferable because of its excellent concealing property. The particle size of the white pigment is in the range of 0.1 to 50 μm in weight average particle size. Outside of this range, the adhesion to the phosphorescent layer and the whiteness will be reduced. The particle size of the white pigment is preferably in the range of 2 to 30 m from the viewpoint of the adhesion to the phosphorescent layer and the decrease in luminance due to the decrease in whiteness. The mixing ratio of the white pigment and the binder may be appropriately selected depending on the degree of whiteness to be obtained. For example, the total light transmittance is preferably 30% or less.
さらに、 白色塗料層には、 プリンター搬送性やブロッキングを防止するために、 アク リル系樹脂、 ベンゾグアナミン榭脂、 ベンゾグアナミン Zメラミン/ホルム アルデヒ ド縮合物などの合成樹脂の粉末などの有機系の微粒子を含有させてもよ レ、。  Furthermore, the white paint layer is coated with organic fine particles such as synthetic resin powder such as acrylic resin, benzoguanamine resin, and benzoguanamine Z melamine / formaldehyde condensate in order to prevent the printer from being transported or blocking. May be included.
本発明による記録用シートを用いて、 プリンタ一等の各種出力装置により記録 層上にパターンを形成する場合、 プリンター解像度を 200〜1 400 d p i (Dots Per Inch)の範囲で出力することが必要である。 プリンター解像度が 20 0 d p i未満であると、 出力した印字 '画像パターンの解像度が低いため画像の 鮮明性、 インパク トが低下するし、 1 400 d p iを越えると、 日中では鮮明な 画像が得られるが、 出力した印字 ·画像パターンが蓄光性を阻害し、 蓄光効率及 び蓄光顔料の発光効率が低下し、 暗所における印字 ·画像パターンを光源が無く ても観察できるという特徴、 いわゆる暗視性が低下するので好ましくない。 これ は、 蓄光層からの光がドッ ト間や、 半透明部を通過してパターン表面に現れると いう現象を妨げるためであり、 このプリンター解像度は出力するシートサイズに より適宜選択することが望まし。 例えば、 シートサイズが A 3を越える場合は、 比較的低めのプリンタ一解像度であっても鮮明な画像を得ることができ、 かつ喑 所での視認性を確保できる。  When a pattern is formed on a recording layer by various output devices such as a printer using the recording sheet according to the present invention, it is necessary to output the printer resolution in a range of 200 to 1,400 dpi (Dots Per Inch). is there. If the printer resolution is less than 200 dpi, the printed image will be printed '' The resolution of the image pattern will be low, resulting in reduced image clarity and impact.If it exceeds 1400 dpi, clear images will be obtained during the day. However, the output print · The image pattern impairs the luminous properties, the luminous efficiency and the luminous efficiency of the luminous pigment are reduced, and printing in a dark place · The image pattern can be observed without a light source, so-called night vision Is undesirably reduced. This is to prevent the phenomenon that light from the phosphorescent layer appears on the pattern surface between dots or through a translucent part, and it is desirable to select the printer resolution appropriately according to the output sheet size. Better. For example, when the sheet size exceeds A3, a clear image can be obtained even with a relatively low resolution of the printer, and visibility at a place can be secured.
本発明の表示物は、 前記記録用シートにおいて、 その記録層に、 解像度 200 〜1 400 d p i、 好ましくは 300〜1 200 d p iの画像を形成したものか らなる。 この場合の画像の形成は、 前記した如き各種のプリンターを用いて実施 し得る他、 各種の印刷方式で行うことができる。 The display material of the present invention is a recording sheet in which, in the recording layer, an image having a resolution of 200 to 1,400 dpi, preferably 300 to 1,200 dpi is formed. Become. In this case, the image formation can be performed using various printers as described above, or can be performed using various printing methods.
本発明の表示物は、 その画像の種類に応じて、 広告媒体等として所定個所に展 示される。 実施例  The display object of the present invention is displayed at a predetermined location as an advertisement medium or the like according to the type of the image. Example
次に、 実施例により本発明を更に詳細に説明するが、 本発明はこれらの例によ つてなんら限定されるものではない。  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
なお、 記録用シート及ぴ表示物の物性は次に示す方法に従って評価した。  The physical properties of the recording sheet and the display were evaluated according to the following methods.
[評価方法]  [Evaluation method]
1. 視認性  1. Visibility
E P SON社製プロスパート ' フォトマッハカラープリンター PM— 2000 Cを使用し、 1 80、 360、 720、 1440 d p iで印字し、 その画像性を 日中、 夜間において 1 m離れたところより目視にて評価した。  EPSON Prospurt '' Photo Mach Color Printer PM—Printed at 180, 360, 720, and 1440 dpi using a 2000C printer, and its image quality was visually inspected at a distance of 1 m during the day and night. evaluated.
〇: 日中、 夜間とも画像を問題なく認識できる。  〇: The image can be recognized without any problem during the day or at night.
△ : 日中は画像を認識できるが、 夜間においては認識できない。 X : 日中、 夜間とも画像を認識できない。  Δ: Images can be recognized during the day, but not at night. X: Images cannot be recognized during the day or night.
2. 密着性  2. Adhesion
蓄光層と記録層間の密着性を碁盤目試験法 (J I S k— 5400) により評 価した。  The adhesion between the luminous layer and the recording layer was evaluated by a grid test (JISK-5400).
5 :欠損部が 0  5: No missing part
4 :欠損部が 5 %以内  4: Defective part within 5%
3 :欠損部が 5〜: 1 5 %  3: Defects 5 to: 15%
2 :欠損部が 1 5〜 3 5 %  2: 15 to 35% defect
1 :欠損部が 35 %以上  1: 35% or more of missing part
3. インク乾燥性  3. Ink drying property
E P SON社製マツハジエツ 卜プリンター PM700 Cを用いて印字し、 以下 の指標により評価した。  Printing was performed using a Matsuha jet printer PM700C manufactured by EPSON and evaluated by the following indices.
〇:指触乾燥時間が 60秒未満のもの Δ : 60秒以上 3分未満のもの 〇 : Touch dry time less than 60 seconds Δ: 60 seconds or more and less than 3 minutes
X : 3分以上のもの  X: 3 minutes or more
4. 口一ル卷取り性  4. Easy winding
口一ル卷取り時に塗膜表面の外観を目視にて観察した。  The appearance of the coating film surface was visually observed at the time of winding up the mouth.
〇 : プロッキングもなくクラックも発生しないで卷き取れたもの X : ブロッキングもしくはクラックが発生したもの  :: Unwound without blocking and no cracking X: Blocking or cracking
5. 耐熱性  5. Heat resistance
トナーまたはインク記録層を塗布し、 一定の乾燥条件 (140°C、 3分) で乾 燥したシートの平面性及びプリンター搬送性を評価した。  The flatness and printer transportability of the sheet coated with the toner or ink recording layer and dried under certain drying conditions (140 ° C, 3 minutes) were evaluated.
〇 :波うちもなく、 プリンター搬送性も良好なもの  〇: No wave, good printer transportability
△ :波うちはしているが、 プリンター搬送性の良好なもの  △: Wavy, but good printer transportability
X :波うちがあり、 プリンター搬送性のよくないもの  X: Wavy, poor printer transportability
6. カール性  6. Curlability
ロール品を A 4サイズに裁断後、 蓄光層を有する面を上にして平面台上に置く。 このときの台からシートまでの四隅の高さ平均を測定し、 下記指標で評価した。  After cutting the rolled product into A4 size, place it on a flat table with the luminous layer facing up. At this time, the average of the heights of the four corners from the table to the sheet was measured, and evaluated by the following indices.
〇:高さ 1 0mm以下  〇: Height 10mm or less
△ :高さ 1 0〜2 Omm  △: Height 10 ~ 2 Omm
X :高さ 20 mm以上 実施例 1  X: height 20 mm or more Example 1
アクリルポリオール (水酸基価 1 7. 5) 43. 5重量部、 蓄光顔料 (G— 3 00M、 根本特殊化学社製) 47. 8重量部、 添加剤 4. 4重量部、 硬化剤 (N CO% 1 2. 6) 4. 3重量部を混合して、 蓄光層形成塗工液を調製した。 厚さ 50 /xmの白色ポリエチレンテレフタレートシ一トの片面にウレタン樹脂 からなる厚さ 1 μηιの易接着層を設けた後、 前記塗工液をアプリケ一ターにて易 接着層上に塗布、 乾燥し、 厚さ 50 / m、 T g 3 5°Cの蓄光層を形成した。  Acrylic polyol (hydroxyl value 17.5) 43.5 parts by weight, phosphorescent pigment (G-300M, manufactured by Nemoto Special Chemical Co., Ltd.) 47.8 parts by weight, additive 4.4 parts by weight, curing agent (N CO% 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution. After providing an easy-adhesion layer of urethane resin on one side of a 50 / xm-thick white polyethylene terephthalate sheet, apply the coating solution on the easy-adhesion layer with an applicator and dry. Then, a luminous layer having a thickness of 50 / m and a Tg of 35 ° C was formed.
次に、 ァセトァセチル化ポリビュルアルコール (けん化度 99モル%、 重合度 1 , 000) 6. 4重量部、 ポリ ビニルピロリ ドン (重量平均分子量 630, 0 00) 2重量部、 コロイダルシリカ酸性液 (スノーテックス S T— AK、 日産化 学工業社製) 8重量部、 エタノール 1 0重量部、 水 73. 6重量部を混合して、 記録層形成塗工液を調製した。 Next, 6.4 parts by weight of acetoacetylated polybutyl alcohol (degree of saponification: 99 mol%, degree of polymerization: 1,000), 2 parts by weight of polyvinyl pyrrolidone (weight average molecular weight: 630, 000), acidic colloidal silica (Snowtex ST—AK, Nissan 8 parts by weight, 10 parts by weight of ethanol and 73.6 parts by weight of water were mixed to prepare a coating liquid for forming a recording layer.
前記蓄光層の上にウレタン樹脂からなる厚さ 1; umの易接着層を設けた後、 前 記記録層形成塗工液をワイヤーバーにて易接着層上に塗布、 乾燥し、 厚さ 10 μ mの記録層 (インク受容層) を形成し、 本発明による蓄光性を有する記録用シー トを作成した。 実施例 2  After providing an easy-adhesion layer of urethane resin having a thickness of 1 μm on the phosphorescent layer, the above-mentioned coating liquid for forming a recording layer is applied on the easy-adhesion layer with a wire bar, and dried to a thickness of 10 μm. A recording layer (ink receiving layer) having a thickness of μm was formed, and a recording sheet having a luminous property according to the present invention was prepared. Example 2
実施例 1において、 記録層形成塗工液を以下のように変更した以外は同様にし て記録用シートを製造した。  A recording sheet was manufactured in the same manner as in Example 1 except that the coating liquid for forming a recording layer was changed as follows.
ポリ ビニルアルコール (重合度 1 700、 けん化度 88モル。 /0) 7重量部、 ポ リビニルピロリ ドン (重量平均分子量 630, 000) 1重量部、 ポリスチレン スルホン酸塩 (三洋化成社製、 ケミスタツト 6 1 20) 2重量部、 繊維素反応型 架橋剤であるジメチロールダリオキザールモノウレイン 0. 2重量部、 水 69. 66重量部、 合成シリカ (平均粒径 6 μηι) 0. 04重量部を混合して記録層形 成塗工液を調製した。 記録層形成塗工液をワイヤーバーにて易接着層上に塗布、 乾燥し、 厚さ 25 mの記録層 (インク受容層) を形成した。 実施例 3 Polyvinyl alcohol (polymerization degree 1,700, saponification degree: 88 mol. / 0) 7 parts by weight, Po Ribinirupirori pyrrolidone (weight average molecular weight 630, 000), 1 part by weight of polystyrene sulfonate (manufactured by Sanyo Chemical Industries, Ltd., Kemisutatsuto 6 1 20 ) 2 parts by weight, 0.2 part by weight of dimethylol dalioxal monourein, a cellulose-reactive crosslinking agent, 69.66 parts by weight of water, and 0.04 parts by weight of synthetic silica (average particle size: 6 μηι) Thus, a recording layer forming composition coating solution was prepared. The coating liquid for forming a recording layer was applied onto the easy-adhesion layer with a wire bar and dried to form a recording layer (ink receiving layer) having a thickness of 25 m. Example 3
アク リルポリオール (水酸基価 1 7. 5) 43. 5重量部、 蓄光顔料 (G— 3 00M、 根本特殊化学社製) 47. 8重量部、 添加剤 4. 4重量部、 硬化剤 (N CO% 1 2. 6) 4. 3重量部を混合して、 蓄光層形成塗工液を調製した。 両面に易接着処理を施した厚さ 50 i mの透明ポリエチレンテレフタレートシ 一卜の片面に、 前記塗工液をアプリケーターにて易接着層上に塗布、 乾燥し、 厚 さ 50 /m、 T g 35°Cの蓄光層を形成した。  Acrylic polyol (hydroxyl value 17.5) 43.5 parts by weight, phosphorescent pigment (G-300M, manufactured by Nemoto Special Chemicals Co., Ltd.) 47.8 parts by weight, additives 4.4 parts by weight, curing agent (NCO % 1 2. 6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution. On one side of a transparent polyethylene terephthalate sheet having a thickness of 50 im having both sides subjected to an easy adhesion treatment, the above-mentioned coating solution is applied on the easy adhesion layer with an applicator, and dried to a thickness of 50 / m, Tg 35 A phosphorescent layer at ° C was formed.
次に、 ァセトァセチル化ポリビュルアルコール (けん化度 9 9モル%、 重合度 1, 000) 6. 4重量部、 ポリビニルピロリ ドン (重量平均分子量 630, 0 00) 2重量部、 コロイダルシリカ酸性液 (スノーテックス ST— A :、 日産化 学工業社製) 8重量部、 エタノール 1 0重量部、 水 7 3 · 6重量部を混合して、 記録層形成塗工液を調製した。 Next, 6.4 parts by weight of acetoacetylated polybutyl alcohol (degree of saponification: 99 mol%, degree of polymerization: 1,000), 2 parts by weight of polyvinylpyrrolidone (weight average molecular weight: 630, 000), an acid solution of colloidal silica (snow) Tex ST-A: Nissan Kagaku Kogyo) 8 parts by weight, 10 parts by weight of ethanol, 73.6 parts by weight of water A recording layer forming coating liquid was prepared.
前記蓄光層を設けた面とは反対側の面に、 前記記録層形成塗工液をワイヤーバ 一にて易接着層上に塗布、 乾燥し、 厚さ Ι Ο μηιの記録層 (インク受容層) を形 成し、 本発明による蓄光性を有する記録用シートを作成した。 この時の蓄光層を 1 000 LX (ノレタス) で 10分照射後、 トプコン社製輝度計 (製品名 : ΒΜ— 8、 試料設置台の表面は黒色のものを使用) で測定したときの輝度 (m c dZm On the surface opposite to the surface on which the light-storing layer is provided, apply the recording layer-forming coating liquid onto the easy-adhesion layer with a wire bar, and dry the recording layer (ink-receiving layer) with a thickness of Ι μμιι. Was formed to prepare a recording sheet having a luminous property according to the present invention. After illuminating the luminous layer at this time with 1 000 LX (no lettuce) for 10 minutes, the luminance measured with a Topcon luminance meter (product name: ΒΜ-8, the surface of the sample mounting table was black) was used. mc dZm
2) は 400 ( 1分値) であった。 比較例 1 2 ) was 400 (one minute value). Comparative Example 1
実施例 1において、 本発明による蓄光層の代わりに塩化ビュル樹脂に蓄光顔料 を練り込んだシート (商品名ルミノーバ、 根本特殊化学社製) を使用した以外は 実施例 1と同様にして実施例 1に示した配合の記録層形成ェ液を塗布し、 記録用 シートを得た。 実施例 4  Example 1 was repeated in the same manner as in Example 1 except that the phosphorescent layer according to the present invention was replaced by a sheet (trade name: Luminova, manufactured by Nemoto Special Chemicals Co., Ltd.) in which a phosphorescent pigment was kneaded with a vinyl chloride resin. The recording layer forming solution having the composition shown in (1) was applied to obtain a recording sheet. Example 4
実施例 3において、 蓄光層形成塗工液に使用する蓄光剤 (根本特殊化学社製、 G— 300M) にかえ、 蓄光剤 (根本特殊化学社製、 WA— 300) を用いた以 外はすべて実施例 3と同様にして記録用シ一トを製造した。 この記録用シートの 輝度 (mc d/m2) は 200 ( 1分値) であり、 E P S O Nマッハジェッ トプ リンター PM— 700 Cで記録層上に画像パターンを形成した際、 通常の可視光 下では実施例 1〜3より画像が鮮明であった。 またこのものの物性を前記評価方 法にて評価した。 実施例 5 In Example 3, all except that the phosphorescent agent (Nemoto Special Chemical Co., WA-300) was used instead of the phosphorescent agent (Nemoto Specialty Chemical Co., G-300M) used in the coating solution for forming the phosphorescent layer. A recording sheet was manufactured in the same manner as in Example 3. The brightness (mc d / m 2 ) of this recording sheet was 200 (one minute value). When an image pattern was formed on the recording layer using EPSON Machjet Printer PM-700C, it was performed under normal visible light. The images were clearer than in Examples 1-3. The physical properties of this product were evaluated by the above-mentioned evaluation methods. Example 5
実施例 4の蓄光層上に、 次の組成からなる白色層形成塗工液を蓄光層上に塗布、 乾燥し、 厚さ 20 / /の白色層を形成した以外は、 全て実施例 4と同様にして、 記 録用シートを製造した。 このときの白色層の全光線透過率は 25%、 記録用シー トの輝度 (mc d/m2) は 300 ( 1分値) であり、 E P SONマツハジエツ トプリンタ一 PM— 700 Cで記録層上に画像パターンを形成した際、 通常の可 視光下では前記実施例 4よりさらに画像が鮮明であった。 またこのものの物性を 前記の評価方法にて評価した。 The same procedure as in Example 4 was performed except that a white layer forming coating liquid having the following composition was applied on the phosphorescent layer of Example 4 and dried to form a 20 // thick white layer. Then, a recording sheet was manufactured. At this time, the total light transmittance of the white layer was 25%, the brightness (mc d / m 2 ) of the recording sheet was 300 (one minute value), and the EP SON Matsuhajit Printer PM-700C was used on the recording layer. When an image pattern is formed on a Under visual light, the image was clearer than in Example 4. The physical properties of this product were evaluated by the above evaluation methods.
<白色層形成塗工液 > <White layer forming coating liquid>
アクリルポリオール (水酸基価 1 7. 5) 60重量部、 白色顔料 (タイペータ R_680、 石原産業社製) 1 2重量部、 添加剤 1. 2重量部、 硬化剤 (NCO % 1 2. 6) 3. 8重量部、 トルエン 14重量部、 メチルセ口ソルブァセテー ト 9重量部を混合して、 白色層形成塗工液を調製した。 実施例 6  Acrylic polyol (hydroxyl value 17.5) 60 parts by weight, white pigment (Taipeta R_680, manufactured by Ishihara Sangyo) 12 parts by weight, additives 1.2 parts by weight, curing agent (NCO% 12.6) 3. 8 parts by weight, 14 parts by weight of toluene and 9 parts by weight of methyl sorbate acetate were mixed to prepare a white layer forming coating solution. Example 6
実施例 3において、 インク受容層にかえ、 ポリエステル系樹脂 30重量部、 ト ルェン 20重量部、 メチルェチルケトン 20重量部、 添加剤 30重量部からなる インク定着層形成塗工液を塗布乾燥し、 インク定着層を設けた以外は、 全て実施 例 3と同様にして記録用シートを作成した。 この記録用シートの蓄光層とは反対 側の面に熱転写プリンター (アルプス社製、 MD— 2300) を用いて、 印字 ' 画像パターン解像度 600 d p iで形成したところ、 日中、 夜間とも画像を問題 なく認識でき、 特に日中に鮮明な画像が認識できる表示物を得ることができた。 前記実施例 1〜 5及び比較例 1で得た各製品の評価結果を表 1にまとめて示す。 In Example 3, instead of the ink receiving layer, an ink fixing layer forming coating liquid consisting of 30 parts by weight of a polyester resin, 20 parts by weight of toluene, 20 parts by weight of methyl ethyl ketone, and 30 parts by weight of an additive was applied and dried. A recording sheet was prepared in the same manner as in Example 3 except that an ink fixing layer was provided. Using a thermal transfer printer (MD-2300, manufactured by Alps) on the surface of the recording sheet opposite to the luminous layer, the image was printed and formed at an image pattern resolution of 600 dpi. A display object that can be recognized, and in particular, a clear image can be recognized during the day. Table 1 summarizes the evaluation results of the products obtained in Examples 1 to 5 and Comparative Example 1.
視 1 g性 密 ロ ーノレ Sight 1 g sex dense
 K
180 360 720 1440 着全 イン  180 360 720 1440 All arrivals Inn
巻取り IW熱 77 ' ノレ 13E 乾燥性  Winding IW heat 77 'Nore 13E Drying
dpi d i d i d i 性 性  dpi d i d i d i sex sex
実施例 X 〇 Example X 〇
1 o o 厶 5 〇 〇 〇 1 o o m 5 〇 〇 〇
実施例 X 〇 〇 Δ 5 〇 〇 〇 〇 Example X 〇 〇 Δ 5 〇 〇 〇 〇
2Two
tf Λ. tal  tf Λ.tal
X 〇 〇 厶 〇 X 〇 〇 〇
3 * 〇 〇 〇 3 * 〇 〇 〇
実施例 X 〇 〇 Δ 〇 4 * 〇 〇 〇  Example X 〇 〇 Δ 〇 4 * 〇 〇 〇
実施例 X 〇 〇 Δ 〇 〇 5 * 〇 〇  Example X 〇 〇 Δ 〇 〇 5 * 〇 〇
比較例 1 X  Comparative Example 1 X
1  1
*評価せず  * Not evaluated
表中の 「一」 は、 インク受容層が形成できず、 評価できなかった < 本発明の蓄光性を有する記録用シートには、 パソコン等で作成された印字 .画 像パターンをインクジェットプリンター、 インクジェットプロッタ一、 熱転写プ リンター (昇華転写プリンター、 熱溶融転写プリンタ一等) 及びレーザープリン ターなどで簡単にハード出力することができる。 また、 本発明の蓄光性を有する 記録用シートは、 蓄光層と記録層とを積層していることから、 蓄光シートと記録 シートを貼り合わせるという作業が不要であり、 作業効率がよい。  In the table, “1” indicates that the ink receiving layer could not be formed and could not be evaluated. <The luminous recording sheet of the present invention was printed with a personal computer or the like. Hard output can be easily performed with a plotter, thermal transfer printer (sublimation transfer printer, thermal melt transfer printer, etc.), laser printer, and so on. Further, since the recording sheet having the luminous property of the present invention has the luminous layer and the recording layer laminated, the work of bonding the luminous sheet and the recording sheet is unnecessary, and the working efficiency is good.
また、 本発明による蓄光性を有する記録用シートに印字 ·画像パターンをプリ ンター解像度 2 0 0〜 1 4 0 0 d p iで形成して表示物を形成すると、 明るい場 所ではもちろんのこと喑所であっても、 蓄光した光が、 印字 '画像パターンを鮮 明に表示するため、 照明器具等を用意する必要がない。 このため、 電気等の化石 燃料を必要としないため、 地球環境にも優しい優れた広告、 看板などの表示物を 得ることができる。  In addition, printing on a recording sheet having a luminous property according to the present invention.When an image pattern is formed at a printer resolution of 200 to 140 dpi to form a display object, it can be used not only in a bright place but also in other places. Even so, the stored light clearly displays the printed image pattern, so there is no need to prepare lighting equipment. For this reason, since fossil fuels such as electricity are not required, it is possible to obtain excellent advertisements and signs such as signboards that are friendly to the global environment.
さらに、 蓄光層上に白色塗料層を設けたことにより、 蓄光層の輝度を向上する ことができ、 かつ、 白色蓄光剤を用いた場合、 通常の可視光下ではより白色に見 えるため、 記録層のパターンを鮮明に再現することができる。  Furthermore, by providing a white paint layer on the luminous layer, it is possible to improve the luminance of the luminous layer, and when a white luminous agent is used, it looks more white under normal visible light. The pattern of the layer can be clearly reproduced.

Claims

請求の範囲 The scope of the claims
1. 基材フィルムの少なくとも一方の面上に樹脂と蓄光顔料からなる蓄光層を設 け、 さらにその上にもしくはその反対側の面上にトナー又はィンクで記録可能な 記録層を積層したことを特徴とする記録用シート。 1. A luminous layer composed of a resin and a luminous pigment was provided on at least one surface of the base film, and a recording layer recordable with toner or ink was laminated thereon or on the opposite surface. Characteristic recording sheet.
2. 基材フィルムの一方の面上に樹脂と蓄光顔料からなる蓄光層を設け、 該蓄光 層とは反対側の面上にトナー又はインクで記録可能な記録層を積層した記録用シ ートであって、 さらに、 該蓄光層上に、 白色層を積層させたことを特徴とする記 録用シ一ト。 2. A recording sheet in which a phosphorescent layer composed of a resin and a phosphorescent pigment is provided on one surface of a base film, and a recording layer recordable with toner or ink is laminated on the surface opposite to the phosphorescent layer. A recording sheet, further comprising a white layer laminated on the light storage layer.
3. 蓄光層全体に対して蓄光顔料が 5〜95重量%である請求の範囲 1又は 2記 載の記録用フィルム。 3. The recording film according to claim 1, wherein the luminous pigment is 5 to 95% by weight based on the entire luminous layer.
4. 蓄光層の膜厚が 20〜 200 mである請求の範囲 1〜 3のいずれかに記載 の記録用フィルム。 4. The recording film according to any one of claims 1 to 3, wherein the phosphorescent layer has a thickness of 20 to 200 m.
5. 蓄光層のガラス転移温度 (T g) が 10〜60°Cである請求の範囲 1〜4の いずれかに記載の記録用フィルム。 5. The recording film according to any one of claims 1 to 4, wherein the luminous layer has a glass transition temperature (Tg) of 10 to 60 ° C.
6. 白色層の光線透過率が、 30%以下であることを特徴とする請求の範囲 2〜 5のいずれかに記載の記録用フィルム。 6. The recording film according to any one of claims 2 to 5, wherein the light transmittance of the white layer is 30% or less.
7. 基材フィルムの少なくとも一方の面上に樹脂と蓄光顔料からなる蓄光層を設 け、 さらにその上にもしくはその反対側の面上に解像度 200〜1400 d p i の画像層を形成したことを特徴とする表示物。 7. A luminous layer composed of a resin and a luminous pigment is provided on at least one surface of the base film, and an image layer with a resolution of 200 to 1400 dpi is formed on or on the opposite surface. Indications to be made.
8. 蓄光層上に、 白色層を積層させたことを特徴とする請求の範囲 7記載の表示 物。 8. The display according to claim 7, wherein a white layer is laminated on the phosphorescent layer.
9. 蓄光層のガラス転移温度 (Tg) が 10〜60°Cである請求の範囲 7又は 8 記載の表示物。 9. The display according to claim 7, wherein the phosphorescent layer has a glass transition temperature (Tg) of 10 to 60 ° C.
10. 白色層の光線透過率が、 30%以下であることを特徴とする請求の範囲 7 〜 9のいずれかに記載の表示物。 10. The display according to any one of claims 7 to 9, wherein the white layer has a light transmittance of 30% or less.
PCT/JP1999/002344 1998-09-04 1999-04-30 Recording sheet having phosphorescence and sign WO2000013910A1 (en)

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JP10/251608 1998-09-04
JP25160898 1998-09-04
JP11/70823 1999-03-16
JP11070823A JP2000141884A (en) 1998-09-04 1999-03-16 Recording sheet having light storing properties and displayed material

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072532A1 (en) * 2000-03-30 2001-10-04 Celfa Ag Phosphorescent material which can be printed with a transfer system for digital data
WO2002011995A2 (en) * 2000-08-03 2002-02-14 Ramsden Paul A Luminescent image-receptive sheet and its method of preparation

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002086895A (en) * 2000-09-05 2002-03-26 Three M Innovative Properties Co Image recording medium
EP1226958A1 (en) * 2001-01-25 2002-07-31 Celfa AG Image-receiving material having an adhesive layer, method for its' preparation, and its' use
JP2003312136A (en) * 2002-04-25 2003-11-06 Konica Minolta Holdings Inc Recording medium for ink jet printer
NL1029317C2 (en) * 2005-06-22 2006-12-27 Next Generation B V Float glass, has phosphorescent pigment applied to its surface by e.g. screen printing or spray coating
JP2007291269A (en) * 2006-04-26 2007-11-08 Agc Matex Co Ltd Resin composition for fiber-reinforced resin molded article, resin-impregnated reinforcing fiber material and fiber-reinforced resin molded article
JP2008233178A (en) * 2007-03-16 2008-10-02 Kurimoto Kasei Kogyo Kk Luminous sign board
JP2009163022A (en) * 2008-01-08 2009-07-23 Unimatec Co Ltd Phosphorescent signboard and its manufacturing method
CN101875253A (en) * 2009-04-28 2010-11-03 大连路明发光科技股份有限公司 Water-proof self-luminous printing film
JP5749097B2 (en) * 2011-06-29 2015-07-15 日本ダム株式会社 Phosphorescent signs and their manufacturing methods

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02155795A (en) * 1988-12-09 1990-06-14 Nitto Denko Corp Image-receiving body for thermal transfer
US5270100A (en) * 1992-02-05 1993-12-14 Giglio Anthony J Phosphorescent coloring method
JPH06297883A (en) * 1993-04-19 1994-10-25 Dainippon Printing Co Ltd Information pattern print and manufacture thereof
JPH0721362Y2 (en) * 1991-09-21 1995-05-17 小野谷機工株式会社 Safety cover for tire air filling
JPH0825816A (en) * 1994-07-13 1996-01-30 Dainippon Printing Co Ltd Dye acceptor, receiving layer transfer sheet and receiving layer transfer matter
JPH0872389A (en) * 1994-09-01 1996-03-19 Canon Inc Recording medium and recording device using recording medium
JPH0890937A (en) * 1994-09-27 1996-04-09 Sony Corp Photographic paper
JPH08175040A (en) * 1994-12-27 1996-07-09 Casio Electron Mfg Co Ltd Luminous label, luminous printing method and luminous label cassette
JPH10235990A (en) * 1997-02-19 1998-09-08 Eastman Kodak Co Medium and its production

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720480A (en) * 1985-02-28 1988-01-19 Dai Nippon Insatsu Kabushiki Kaisha Sheet for heat transference
US6027210A (en) * 1996-08-02 2000-02-22 Canon Kabushiki Kaisha Ink-jet recording process using liquid formulation and ink in combination

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02155795A (en) * 1988-12-09 1990-06-14 Nitto Denko Corp Image-receiving body for thermal transfer
JPH0721362Y2 (en) * 1991-09-21 1995-05-17 小野谷機工株式会社 Safety cover for tire air filling
US5270100A (en) * 1992-02-05 1993-12-14 Giglio Anthony J Phosphorescent coloring method
JPH06297883A (en) * 1993-04-19 1994-10-25 Dainippon Printing Co Ltd Information pattern print and manufacture thereof
JPH0825816A (en) * 1994-07-13 1996-01-30 Dainippon Printing Co Ltd Dye acceptor, receiving layer transfer sheet and receiving layer transfer matter
JPH0872389A (en) * 1994-09-01 1996-03-19 Canon Inc Recording medium and recording device using recording medium
JPH0890937A (en) * 1994-09-27 1996-04-09 Sony Corp Photographic paper
JPH08175040A (en) * 1994-12-27 1996-07-09 Casio Electron Mfg Co Ltd Luminous label, luminous printing method and luminous label cassette
JPH10235990A (en) * 1997-02-19 1998-09-08 Eastman Kodak Co Medium and its production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1031432A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072532A1 (en) * 2000-03-30 2001-10-04 Celfa Ag Phosphorescent material which can be printed with a transfer system for digital data
EP1138525A1 (en) * 2000-03-30 2001-10-04 Celfa AG Phosphorescent, printable media
WO2002011995A2 (en) * 2000-08-03 2002-02-14 Ramsden Paul A Luminescent image-receptive sheet and its method of preparation
WO2002011995A3 (en) * 2000-08-03 2002-04-11 Paul A Ramsden Luminescent image-receptive sheet and its method of preparation

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