WO2015068292A1 - Article imprimé - Google Patents

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Publication number
WO2015068292A1
WO2015068292A1 PCT/JP2013/080349 JP2013080349W WO2015068292A1 WO 2015068292 A1 WO2015068292 A1 WO 2015068292A1 JP 2013080349 W JP2013080349 W JP 2013080349W WO 2015068292 A1 WO2015068292 A1 WO 2015068292A1
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WO
WIPO (PCT)
Prior art keywords
printing
antimony
layer
tin oxide
ink
Prior art date
Application number
PCT/JP2013/080349
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English (en)
Japanese (ja)
Inventor
文人 小林
芝岡　良昭
博昭 島根
渉 吉住
正太 川▲崎▼
Original Assignee
共同印刷株式会社
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Publication date
Application filed by 共同印刷株式会社 filed Critical 共同印刷株式会社
Priority to PCT/JP2013/080349 priority Critical patent/WO2015068292A1/fr
Publication of WO2015068292A1 publication Critical patent/WO2015068292A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/382—Special inks absorbing or reflecting infrared light
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention relates to a printed matter, and particularly to an infrared absorbing printed matter for preventing counterfeiting.
  • the area of the infrared absorbing ink is visually observed in the same manner as the area of the general ink (infrared non-absorbing ink).
  • the region of the infrared absorbing ink can be confirmed while the region of the general ink is not observed.
  • part of the print design is formed with infrared absorbing ink and the remaining part is formed with infrared non-absorbing ink to obtain a printed matter
  • only the infrared absorbing ink portion is confirmed by checking the printed matter with an infrared detector. Can be confirmed.
  • infrared absorbers infrared absorbing organic materials such as cyanine compounds and phthalocyanine compounds; or infrared absorbing inorganic materials such as carbon black, tungsten oxide, and lead oxide are known.
  • Patent Document 1 describes that a printed matter is obtained using an infrared absorbing ink containing carbon black as an infrared absorbing material.
  • Patent Document 2 describes a forgery-preventing printed matter obtained by superimposing an infrared-absorbing printing layer containing an infrared-absorbing organic material such as a cyanine compound and an infrared-reflecting printing layer.
  • Patent Document 3 describes a forgery-preventing printed matter obtained by overlaying or arranging an infrared absorbing printed layer and an infrared reflecting printed layer on a printed matter.
  • an infrared absorbing printing layer containing an infrared absorbing organic material as an infrared absorber can exhibit various colors because of the variety of colors of this material, but the problem of low weather resistance has been pointed out. .
  • the infrared absorbing printing layer formed with an infrared absorbing ink containing carbon black as an infrared absorbing inorganic material is superior to the ink containing the infrared absorbing organic material in weather resistance, but the carbon black has a dark color tone. Since it is a pigment which has, the color of the printing layer was restricted to the thing of a black type or a low brightness. For this reason, when carbon black was used as the infrared absorbing inorganic material, it was not possible to obtain an infrared absorbing printing layer having a variety of colors by mixing with pigments or dyes having other colors. In particular, it was impossible to obtain a light-colored, particularly light-colored, light-colored infrared absorbing printing layer.
  • the white pigment has the property of reflecting infrared rays, so the printing layer Infrared absorptivity is inhibited, and the function as a printed matter for preventing counterfeiting is adversely affected.
  • an infrared absorbing printing layer containing a metal oxide such as tungsten oxide or lead oxide as an infrared absorbing inorganic material has a problem that the infrared absorbing effect is low although the transparency is high.
  • ITO indium tin oxide
  • antimony tin oxide is excellent in transparency and weather resistance, but regulations of each industry (for example, chemical substance release and transfer notification system (PRTR), toy safety standards, etc.) Therefore, it has been desired to reduce the amount of antimony. Moreover, since antimony is also a rare metal, it has been desired to reduce the production cost of ATO-containing ink by reducing the amount of antimony contained in ATO.
  • PRTR chemical substance release and transfer notification system
  • an object of the present invention is to provide a printed matter that is excellent in infrared absorptivity, transparency, weather resistance, safety and cost, and can exhibit a variety of colors by including colorants of various colors. To do.
  • the degree of crystallinity is 58427 or more.
  • Printed matter [2] The printed matter according to [1], which is for forgery prevention. [3] The printed matter according to [1] or [2], wherein, in (a), the full width at half maximum ( ⁇ 2 ⁇ ) is 0.21 or less. [4] In (b), the content of the antimony oxide is 2.8 to 9.3 wt% based on the weight of the antimony-doped tin oxide, according to [1] or [2] Printed matter. [5] The printed material according to [1] or [2], wherein the crystallinity is 78020 or more.
  • [6] The printed matter according to any one of [1] to [5], wherein the antimony-doped tin oxide has an average particle size of 200 ⁇ m or less.
  • [7] The printed matter according to any one of [1] to [6], wherein the printed layer (A) and the printed layer (B) have the same or different infrared absorption rates.
  • [8] The printed matter according to any one of [1] to [7], wherein the printed layer (A) is formed on or below the printed layer (B).
  • [9] The printed matter according to any one of [1] to [8], wherein the print layer (A) and the print layer (B) are formed by full-surface printing or partial printing.
  • the printing layer (A) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. ] To [9].
  • the printing layer (B) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. ] To [10].
  • the printing layer (A) and / or the printing layer (B) further includes at least one selected from the group consisting of a chromic material, a magnetic pigment, an ultraviolet absorber, an optical variable material, and a pearl pigment.
  • the degree of crystallinity is 58427 or more.
  • Manufacturing method of printed matter [14] The method for producing a printed material according to [13], wherein the printed layer (A) and the printed layer (B) have the same or different infrared absorption rates. [15] The method for producing a printed material according to [13] or [14], wherein the printed layer (B) is formed before or after the printed layer (A) is formed.
  • the antimony-doped tin oxide pigment used in the present invention is an inorganic pigment and hardly deteriorates due to light such as ultraviolet rays. Therefore, according to the present invention, the antimony-doped tin oxide pigment includes an infrared absorption printing layer having high weather resistance and infrared absorption. A printed matter is obtained.
  • the printed matter of the present invention has a lightness and a light white color of the antimony-doped tin oxide pigment, various colors, particularly bright colors, are provided by mixing the antimony-doped tin oxide pigment with other colorants. can do. Therefore, according to the present invention, it is possible to provide printed matter such as banknotes, securities, and cards that are excellent in forgery prevention effect and design.
  • the production cost of antimony-doped tin oxide pigments is lower than that of tin-doped indium oxide pigments.
  • an antimony-doped tin oxide pigment having a lower content of antimony oxide than a conventional antimony-doped tin oxide pigment can be used in a printed matter. Therefore, according to the present invention, it is possible to provide an anti-counterfeit printed matter excellent in economy while complying with safety regulations regarding the amount of antimony used in a wide range of industries.
  • FIG. 1 is a process diagram showing one embodiment of a method for producing antimony-doped tin oxide.
  • FIG. 2 (A) is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Example 1 (antimony oxide content: 0.7% by weight, with aerated firing / cooling), and
  • FIG. 4 is a graph showing the results of X-ray diffraction of antimony-doped tin oxide of Example 2 (antimony oxide content: 2.8% by weight, with aerated firing / cooling).
  • FIG. 2 (A) is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Example 1 (antimony oxide content: 0.7% by weight, with aerated firing / cooling)
  • FIG. 4 is a graph showing the results of X-ray diffraction of antimony-doped tin oxide of Example 2 (antimony oxide content: 2.8% by weight, with aerated
  • FIG. 3 (A) is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Example 3 (antimony oxide content: 5.3% by weight, with aerated firing / cooling), and FIG. FIG. 6 is a graph showing the results of X-ray diffraction by antimony-doped tin oxide of Example 4 (antimony oxide content: 9.3 wt%, with aerated firing / cooling).
  • FIG. 4 (A) shows the X-ray diffraction pattern of antimony-doped tin oxide of Example 5 (ventilated and cooled by commercial cooling, cooling rate of 200 [° C./hour] or more, antimony oxide content 2.7% by weight).
  • FIG. 4 (B) shows the results, and FIG.
  • FIG. 4 shows antimony-doped tin oxide of Example 6 (commercially manufactured product by air firing and cooling, cooling rate of less than 200 [° C./hour], antimony oxide content 2.7 wt. %) Shows the result of X-ray diffraction.
  • FIG. 5 is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Example 7 (aerated firing / cooling of a mixture of metastannic acid and antimony trioxide, antimony oxide content 4.2% by weight).
  • 6A is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Comparative Example 1 (antimony oxide content: 9.9% by weight, commercially available product), and FIG.
  • FIG. 6B is a comparative example. It is a figure which shows the result of the X-ray diffraction of antimony dope tin oxide 2 (antimony oxide content rate 2.8 weight%, aeration baking and no cooling).
  • FIG. 7 is a conceptual diagram schematically showing a method for calculating the crystallinity.
  • FIG. 8 is a graph showing the influence of the antimony oxide content rate on the reflectance at a wavelength of 200 nm to 2500 nm.
  • FIG. 9 is a graph showing the influence of the ventilation firing process on the reflectance at a wavelength of 200 nm to 2500 nm and an antimony oxide content of 2.7 to 2.8% by weight.
  • FIG. 10 is a graph showing the influence of the air-fired process on the reflectance and antimony content of a commercially available antimony-doped tin oxide material at a wavelength of 200 nm to 2500 nm.
  • FIG. 11 is a graph showing the influence of the aeration firing process on the reflectance of a mixture of metastannic acid and antimony trioxide at a wavelength of 200 nm to 2500 nm.
  • FIG. 12 is a graph showing the reflectance of indigo / red / yellow (CMY) process ink at wavelengths of 350 nm to 1500 nm.
  • CY indigo / red / yellow
  • FIG. 13 is a diagram showing an aspect in which the infrared absorbing printing layer and the infrared non-absorbing printing layer overlap in the printed matter according to the embodiment of the present invention
  • FIG. 13 (A) shows the infrared non-absorbing printing layer as the infrared absorbing printing layer.
  • FIG. 13B shows an embodiment in which an infrared non-absorbing printing layer is formed on an infrared absorbing printing layer without hiding the infrared absorbing printing layer.
  • FIG. 13C shows an embodiment in which an infrared absorbing printing layer is formed on the infrared non-absorbing printing layer.
  • FIG. 14 is a schematic diagram showing a detection pattern when the printed matter according to the embodiment of the present invention is observed visually or with a visible light detector or with an infrared light detector
  • FIG. 14A is a printed matter
  • 14B shows a detection pattern when the printed material is observed visually or with a visible light detector
  • FIG. 14C shows the printed material when observed with an infrared light detector. The detection pattern is shown.
  • the printed matter of the present invention includes a substrate, a printed layer (A), and a printed layer (B). Further, on the substrate, the print layer (A) at least partially overlaps the print layer (B).
  • At least one of the printing layer (A) and the printing layer (B) contains antimony-doped tin oxide. Since antimony-doped tin oxide has infrared absorptivity, at least one of the printed layer (A) and the printed layer (B) is an infrared absorbing printed layer.
  • the printed matter of the present invention can be for anti-counterfeit due to the infrared absorptivity of the infrared absorbing printing layer.
  • the antimony dope tin oxide used by embodiment of this invention is mentioned later.
  • the substrate, the printing layer (A) and the printing layer (B) will be described below.
  • a base material is a component holding a printing layer (A) and a printing layer (B). Further, the substrate may be a substrate to be printed on the printing layer (A) and the printing layer (B).
  • the substrate may be planar or three-dimensional.
  • the base material may be in the form of a sheet, a film, a sphere, a rectangular parallelepiped, a cube, or the like. Therefore, the substrate may have a flat surface, a curved surface, or irregularities depending on the desired form of the printed material.
  • Examples of the substrate include paper, carton board, metal plate, resin film, fabric, clothing, glass, wallpaper, flooring, card, label, and seal.
  • one of the printing layer (A) and the printing layer (B) may not contain antimony-doped tin oxide.
  • the layer not containing antimony-doped tin oxide becomes an infrared non-absorbing print layer if it does not contain other infrared absorbing materials.
  • At least one of the printing layer (A) and the printing layer (B) is an infrared absorption printing layer
  • at least one of the infrared absorption rate of the printing layer (A) and the infrared absorption rate of the printing layer (B) is: It is a positive number.
  • the infrared absorptivity of the printing layer (A) and the printing layer (B) may be the same or different.
  • one of the print layer (A) and the print layer (B) has a positive infrared absorption rate, while the other has the same infrared absorption rate as the infrared absorption rate, or the infrared absorption rate. It may have a different positive number of infrared absorption, or the other infrared absorption may be zero.
  • the printed layer (A) and the printed layer (B) may have the same color tone when observed visually or with a visible light detector. Therefore, the printing layer (A) and the printing layer (B) can be formed in a color-matched state.
  • the printing layer (A) is disposed on the substrate so as to at least partially overlap the printing layer (B). Therefore, when the printed material is observed from a direction perpendicular to the printing surface of the printed material, the range in which the printed layer (A) is arranged and the range in which the printed layer (B) are arranged overlap at least partially. Further, when the print layer (A) and the print layer (B) overlap, any layer may be an upper layer.
  • the printed material is observed with an infrared light detector such as an infrared camera from the direction perpendicular to the printed surface of the printed material. Then, in the range where only the print layer (A) is arranged, the range where only the print layer (B) is arranged, and the range where the print layer (A) and the print layer (B) overlap each other, infrared rays having different densities are provided. Absorption pattern can be detected.
  • the overlapping range of the printing layer (A) and the printing layer (B) absorbs more infrared rays than the range where only the printing layer (A) is arranged, the range where only the printing layer (B) is arranged, It can be detected as a corresponding concentration.
  • the printed material is observed with an infrared light detector such as an infrared camera from the direction perpendicular to the printed surface of the printed material. Then, infrared absorption patterns having different densities can be detected in a range where the print layer (A) and the print layer (B) overlap and in a range where the print layer (A) and the print layer (B) do not overlap.
  • the range in which the print layer (A) and the print layer (B) overlap absorbs more infrared rays than the range in which the print layer (A) and the print layer (B) do not overlap, and can therefore be detected as a corresponding density.
  • the printing layer having a positive infrared absorption rate is A printing layer that is an infrared absorbing printing layer and has an infrared absorption rate of 0 is an infrared non-absorbing printing layer.
  • an infrared light detector such as an infrared camera from a direction perpendicular to the printing surface of the printed matter, an infrared absorption pattern can be detected in a range where the infrared absorbing layer is disposed.
  • one of the printing layer (A) and the printing layer (B) is an infrared absorbing printing layer
  • the other is an infrared non-absorbing printing layer
  • an infrared non-absorbing printing layer on the infrared absorbing printing layer may or may not hide the infrared absorbing print layer.
  • the infrared non-absorbing print layer does not cover the infrared absorbing print layer
  • the infrared non-absorbing print layer can be realized by being formed on the infrared absorbing print layer by partial printing.
  • the infrared absorbing printing layer and the infrared non-absorbing printing layer may be overlapped in any of the modes shown in FIGS. 13 (A) to (C).
  • the infrared non-absorbing print layer is formed on the infrared absorbing print layer so as to conceal the infrared absorbing print layer.
  • the infrared non-absorbing print layer is formed on the infrared absorbing print layer so as not to conceal the infrared absorbing print layer and overlap the infrared absorbing print layer as at least one design.
  • an infrared absorbing printing layer is formed on the infrared non-absorbing printing layer.
  • the printing layer (A) and the printing layer (B) are obtained by printing the entire surface or partial printing of the ink on the substrate.
  • full surface printing means printing so that the entire surface of the substrate is covered with ink (solid)
  • partial printing is a character, picture, pattern, background pattern, It is printed as a pattern such as a line drawing or is printed so that a part of the substrate is covered with ink (solid).
  • the printing layer (A) and the printing layer (B) are both formed by full-surface printing, or both are formed as patterns of characters, pictures, patterns, background patterns, line drawings, etc., or one of them is printed entirely. And the other can be formed as a pattern.
  • the printing layer (A) becomes the infrared absorption printing layer (A) and the printing layer.
  • (B) becomes an infrared absorption printing layer (B).
  • the infrared ray absorbing printing layer (A) is printed on the entire surface and the infrared ray absorbing printing layer (B) is partially printed because the density of the infrared ray absorbing pattern of the printed matter can be easily distinguished.
  • the infrared absorption printing layer (A) and the infrared absorption printing layer (B) are partially printed and the two layers partially overlap, because the density of the infrared absorption pattern of the printed matter can be easily distinguished.
  • the infrared absorbing printing layer (A) and the infrared absorbing printing layer (B) are partially printed and both layers are completely overlapped, in order to facilitate confirmation of the infrared absorption pattern of the printed matter, It is preferable to further include another print layer having an infrared absorption rate different from the infrared absorption rate of the non-absorption print layer or the print layer in which both layers are overlapped.
  • the printing layer (A) becomes the infrared absorption printing layer (A)
  • the printing layer (B) becomes an infrared non-absorbing printing layer (B).
  • the infrared absorbing print layer (A) is disposed under the infrared non-absorbing print layer (B), or It is preferable to arrange on the infrared non-absorbing print layer (B) so that at least a part of the infrared non-absorbing print layer (B) can be seen when the printed material is observed from a direction perpendicular to the printing surface.
  • the printing layer (A) and the printing layer (B) can be formed by printing ink on a substrate, the ink will be described below.
  • an ink containing antimony-doped tin oxide is used in order to give the printed layer (A) and / or the printed layer (B) infrared absorption.
  • the ink since the antimony-doped tin oxide has infrared absorptivity, the ink is an infrared absorbing ink. This infrared absorbing ink can be used to prevent forgery of printed matter by utilizing the infrared absorbing property of antimony-doped tin oxide.
  • an infrared absorbing material such as antimony-doped tin oxide in the ink is used so that at least one of the printing layer (A) and the printing layer (B) contains antimony-doped tin oxide and has a positive infrared absorptance. It is preferable to determine the content rate or the presence or absence of an infrared absorbing material in the ink.
  • an ink that does not contain an infrared absorbing material such as antimony-doped tin oxide can be used.
  • the ink may be an infrared non-absorbing ink.
  • an ink containing a functional material other than the infrared absorbing material may be used.
  • a chromic material can be included in the ink as a functional material.
  • the ink includes antimony-doped tin oxide and / or a colorant and a vehicle.
  • the ink may also contain adjuvants as well as antimony-doped tin oxide, colorants and vehicles.
  • the ink can be used as an oxidation polymerization ink, an ultraviolet curable ink, an oxidation polymerization / ultraviolet curable ink, or a solvent-containing ink depending on the type of vehicle component.
  • oil-based ink is an ink that can be cured by oxidative polymerization of a vehicle component.
  • oil-based inks contain a resin, a crosslinking agent or a gelling agent, a drying oil or a semi-drying oil, a solvent and the like as a vehicle component.
  • UV curable ink is an ink that can be cured by photopolymerization of a vehicle component.
  • a UV ink contains a photopolymerizable resin, a photopolymerization initiator, and the like as a vehicle component, but may not contain a volatile component such as a solvent.
  • oil-based / ultraviolet-curing combined ink (hereinafter abbreviated as “oil-based / UV combined ink”) is an ink having curing characteristics of both oil-based ink and UV ink.
  • the solvent-containing ink is an ink containing a solvent and antimony-doped tin oxide and / or a colorant.
  • the solvent-containing ink can fix the antimony-doped tin oxide and / or the colorant to the substrate by evaporation of the solvent or penetration of the solvent into the printing medium.
  • the solvent-containing ink is preferably used as an aqueous ink containing water as a main solvent or an organic solvent-containing ink containing an organic solvent as a main solvent.
  • the water-based ink is an ink containing water as a main solvent, but may contain an organic solvent. Furthermore, the water-based ink is preferable because it can contain various resins such as a water-soluble resin, a colloidal dispersion resin, and an emulsion resin in addition to water.
  • the organic solvent-containing ink is an ink containing an organic solvent as a main solvent, but does not need to contain water substantially. “Substantially free of water” means that the content of water in the ink is 0% by mass, or that the ink inevitably contains 1% by mass or less of water.
  • Antimony-doped tin oxide, vehicle, auxiliary agent and coloring agent will be described below.
  • Antimony-doped tin oxide is a substance in which tin oxide is doped with antimony.
  • the antimony-doped tin oxide may be in the form of a pigment containing tin oxide and antimony oxide.
  • the antimony-doped tin oxide used in the present invention contains tin oxide and antimony oxide.
  • the content of antimony oxide is about 0.5% by weight or more, about 1.0% by weight or more, about 1.5% by weight or more, about 2.0% by weight or more based on the weight of antimony-doped tin oxide.
  • the content is preferably 2.5% by weight or more, or about 2.8% by weight or more, and the content thereof is about 10.0% by weight or less, about 9.5% by weight or less, and about 9.3% by weight. Or less, about 8.0% or less, about 7.0% or less, about 6.0% or less, about 5.5% or less, about 5.0% or less, about 4.0% or less, It is preferably about 3.5% by weight or less, or about 3.0% by weight or less.
  • the content of antimony oxide is about 2.5 to about 9.3 wt%, about 2.8 to about 9.3 wt%, and about 2.8 to about 5 based on the weight of antimony-doped tin oxide. More preferably, it is 0.5 wt%, or about 2.8 to about 3.5 wt%.
  • Conventional antimony-doped tin oxide needs to contain more than 10% by weight of antimony oxide in order to obtain a transparent conductive material having sufficient conductivity.
  • the antimony dope tin oxide used for this invention can reduce the usage-amount of antimony oxide compared with the conventional antimony dope tin oxide as above-mentioned.
  • antimony oxide is considered to play a role of absorbing infrared rays by entering into the crystal lattice of tin oxide, so if the amount used is simply reduced, the infrared absorption effect is reduced accordingly. Will do.
  • the infrared absorption effect is an effect that occurs when antimony oxide is dissolved (enters) into the crystal lattice of tin oxide, which is the main component. That is, when manufacturing antimony-doped tin oxide, antimony oxide is contained in tin oxide as the main component.
  • antimony oxide not dissolved in the tin oxide crystal lattice is present as an impurity as in conventional antimony-doped tin oxide, it is considered that the impurity did not contribute to the infrared absorption effect.
  • the portion of antimony oxide that does not contribute to the infrared absorption effect remains as a waste material (impurity).
  • the usage-amount of antimony oxide has increased more than necessary. Therefore, the inventors of the present invention have conducted research on this impurity, and as a result, the half-value width ( ⁇ 2 ⁇ ) of antimony-doped tin oxide is wide and / or the crystallinity (the crystallization of the whole material when the material is crystallized).
  • the ratio of the portion is low, antimony oxide as an impurity increases.
  • the half width ( ⁇ 2 ⁇ ) is narrow and / or the degree of crystallinity is high, antimony oxide as an impurity decreases. I found it.
  • examples of means for improving the crystallinity of antimony-doped tin oxide while removing antimony oxide as an impurity include aeration firing described later and vaporization purification described later.
  • the present invention provides an antimony-doped tin oxide having a narrowed half width ( ⁇ 2 ⁇ ) and / or an increased crystallinity in order to minimize the amount of antimony oxide used.
  • the half width ( ⁇ 2 ⁇ ) is narrowed or the crystallinity is increased, impurities are reduced, and antimony oxide can be effectively dissolved and the infrared absorption effect can be improved.
  • a commercially available X-ray diffractometer may be used to select an arbitrary scan speed, but the number of integrations is set to one.
  • it is preferably 0.25 or less, 0.21 or less, 0.20 or less, or 0.19 or less.
  • the crystallinity of antimony-doped tin oxide is 58427 or more, particularly 78020 or more, impurities can be further reduced, and antimony oxide can be effectively solid-solved to further improve the infrared absorption effect. Therefore, according to the present invention, the infrared absorption effect can be sufficiently exhibited while reducing the amount of antimony oxide used.
  • the antimony-doped tin oxide is dissolved in a varnish containing an acrylic polymer and silicone, applied to a substrate, dried, and a solid content weight ratio of antimony-doped tin oxide having a thickness of 70 ⁇ m and about 11.6% by weight.
  • the solar reflectance of this coating film is measured according to JIS K5602 when a coating film having a thickness of 380 is formed, the average reflectance in the wavelength range of 780 to 1100 nm is subtracted from the average reflectance in the wavelength range of 380 to 780 nm.
  • the obtained value is preferably about 3.00% or more.
  • the antimony-doped tin oxide Visible light absorption is relatively low, that is, the visible light transparency of antimony-doped tin oxide is relatively high. Therefore, antimony-doped tin oxide can be used in a wide range of applications without being restricted by the color exhibited by antimony-doped tin oxide.
  • the value obtained by subtracting the average reflectance in the wavelength range of 780 to 1100 nm from the average reflectance in the wavelength range of 380 to 780 nm is about 4.80% or more, or about 4.85% or more. And more preferably about 99% or less, about 90% or less, or about 80% or less.
  • the infrared absorbing material used in the present invention may be an infrared absorbing pigment made of the above antimony-doped tin oxide.
  • the action and effect of the antimony-doped tin oxide described above can be realized by the infrared absorbing material. For this reason, while reducing the usage-amount of antimony oxide, the infrared absorption effect can fully be exhibited, and the high quality infrared absorption material which followed the predetermined safety standard etc. can be provided.
  • the printed matter of the present invention has a peak reflectance value of 28.776 in the infrared wavelength region of 780 to 1100 nm. % Or less is preferable.
  • infrared absorbing printing layer having a low infrared reflectance
  • antimony oxide contained in the infrared absorbing printing layer can be reduced, and the infrared absorbing effect can be sufficiently exhibited.
  • the antimony-doped tin oxide used in the present invention can be produced, for example, by the following method.
  • the method for producing antimony-doped tin oxide used in the present invention includes an aeration firing step of firing the antimony-doped tin oxide raw material under ventilation.
  • aeration firing or cooling is performed not only by firing or cooling while circulating a firing or cooling atmosphere, but also by firing or cooling in an open space (hereinafter also referred to as “open system”) that does not block outside air. Including.
  • the method for producing antimony-doped tin oxide used in the present invention can make the half-value width of antimony-doped tin oxide narrower than that of the conventional product and / or increase the crystallinity of antimony-doped tin oxide than that of the conventional product.
  • the method for producing antimony-doped tin oxide used in the present invention includes an antimony-doped tin oxide that can sufficiently exhibit an infrared absorption effect while reducing the amount of antimony oxide used by including an aeration firing step. Can be manufactured.
  • the inventors of the present invention have found that the removal of excess antimony oxide can be achieved by performing an aeration firing process and a subsequent cooling process.
  • the antimony dope tin oxide obtained by the said manufacturing method has a narrow half value width and / or a high crystallinity degree, It is thought that this originates in there being few antimony oxides of an impurity.
  • extra antimony oxide is present in the antimony-doped tin oxide, it is considered that X-rays are scattered during measurement by X-ray diffraction and the peak is lowered.
  • a method for producing antimony-doped tin oxide including at least an aeration firing step and a subsequent aeration cooling step is referred to as a “vaporization purification method”.
  • the above-described manufacturing method can maintain the crystal structure appropriately while removing a part thereof by the aeration firing process, so that a high infrared absorption effect Can be maintained. For this reason, a high infrared absorption effect can be obtained while reducing the amount of antimony oxide used by passing through the aeration firing step.
  • tin compound examples include metastannic acid, sodium stannate trihydrate, niobium tritin, fenbutane oxide, tin oxide, and tin hydride.
  • antimony compound examples include antimony oxide, indium antimonide, and stibine.
  • the method for producing antimony-doped tin oxide used in the present invention may include the following steps after the aeration firing step: A ventilation cooling step of cooling the obtained antimony-doped tin oxide under ventilation; and / or a cooling step of cooling the obtained antimony-doped tin oxide at a cooling rate of 200 [° C./hour] or more.
  • the aeration cooling process can be performed, for example, by sending air into the furnace (specifically, it is possible to set the number of hours and how many times it is cooled by setting the cooling device).
  • the air cooling process may be performed in an earlier time (for example, about 5 hours). For this reason, the ventilation cooling process is more actively cooling than natural cooling.
  • the cooling rate is preferably 200 [° C./hour] or more, 215 [° C./hour] or more, or 216 [° C./hour] or more.
  • the manufacturing method of the antimony dope tin oxide used for this invention includes the following mixing processes and closed baking processes before a ventilation baking process: A mixing step of mixing a tin compound and an antimony compound to obtain a mixture; and a closed baking step of firing the mixture in a closed system to obtain an antimony-doped tin oxide raw material.
  • the manufacturing method of the antimony dope tin oxide used for this invention includes the closed cooling process which cools an antimony dope tin oxide raw material by a closed system between a closed baking process and an aeration baking process.
  • the antimony-doped tin oxide raw material satisfying the above (i) to (iii) can be obtained by the mixing step, the closed firing step, and the closed cooling step, respectively.
  • the content of antimony trioxide is preferably 10% by weight, but may be about 5 to 20% by weight.
  • Step S102 In this step, the material mixed in the previous raw material mixing step (step S100) is dried at 320 ° C. Thereby, the water used when mixing materials in the previous raw material mixing step (step S100) can be removed.
  • Step S104 the material dried in the first drying step (step S102) is pulverized. Specifically, the dried material is pulverized into a powder by a fine pulverizer.
  • Step S106 the material pulverized in the first pulverization step (step S104) is baked. Specifically, the material pulverized in the first pulverization step (step S104) is fired at 1000 to 1300 ° C. for 1 hour or longer in a closed system. In the closed baking process, since baking is performed in a closed system, the content of antimony oxide (solid solution ratio) is maintained at about 10% by weight.
  • Step S107 the material fired in the previous closed firing step (step S106) is cooled. Specifically, cooling is started simultaneously with the end of the closed firing step, and the fired material is cooled in a closed system. Thereby, an antimony-doped tin oxide raw material in which tin (Sn) and antimony (Sb) are combined is generated. The antimony-doped tin oxide raw material is generated through a closed firing process (step S106) and a closed cooling process (step S107). In addition, although natural cooling may be sufficient as cooling, you may cool the baked material under ventilation similarly to the ventilation cooling process mentioned later.
  • this step may be performed to pulverize the material cooled in the previous closed cooling step (step S107).
  • the fired material can be pulverized using a bead mill while using water as a medium until the particle diameter (median diameter in the laser diffraction scattering method) reaches about 100 nm.
  • the process may be continuously performed in the apparatus used in the process before this process (for example, step S106, step S107, etc.).
  • Step S110 the material pulverized in the first pulverization step (step S108) may be dried by heating to 320 ° C. Thereby, the water used when the material is pulverized in the first fine pulverization step (step S108) can be removed.
  • the process may be continuously performed in the apparatus used in the process before this process (for example, step S106, step S107, etc.).
  • this step may be performed to pulverize the material dried in the second drying step (step S110). Specifically, the dried material can be pulverized with a fine pulverizer. In the case where this process is omitted, the process may be continuously performed in the apparatus used in the process before this process (for example, step S106, step S107, etc.).
  • Step S114 the material pulverized in the second pulverization step (step S112) is baked. Specifically, the material pulverized in the second pulverization step (step S112) is fired in a furnace under ventilation (a state in which ventilation is maintained inside the furnace).
  • the firing temperature may be 1000 ° C. or more, 1050 ° C. or more, 1100 ° C. or more, or 1150 ° C. or more, and the firing temperature may be 1300 ° C. or less, 1250 ° C. or less, or 1200 ° C. or less.
  • the firing time may be 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, 6 hours or more, 7 hours or more, or 8 hours or more. It may be 12 hours or less, 11 hours or less, 10 hours or less, or 9 hours or less.
  • Step S116 In this step, the antimony-doped tin oxide fired in the previous aeration firing step (step S114) is cooled under ventilation.
  • cooling is started simultaneously with the end of the aeration firing process, and the temperature in the firing furnace is set to room temperature (for example, about 20 to 25 ° C.) within 300 minutes. Cooling.
  • the aeration cooling step is performed under aeration.
  • an aeration cooling process (step S116) can be performed after an aeration baking process (step S114).
  • Step S118 the purified material cooled in the previous air cooling process (step S116) is pulverized. Specifically, using water as a medium, the purified material is pulverized using a bead mill until the particle size (median diameter in the laser diffraction scattering method) becomes about 100 nm.
  • Step S120 the impurities of the material whose particle size has been adjusted in the second fine pulverization step (step S118) are removed by washing with water.
  • Impurities are minute amounts of electrolyte (for example, sodium (Na), potassium (K), etc.) contained in the raw material, and whether or not the impurities are sufficiently removed can be confirmed by conductivity.
  • Step S122 the material cleaned in the previous cleaning step (step S120) is dried by heating to 145 ° C. Thereby, while being able to remove the water used when wash
  • Step S124 the material dried in the third drying step (step S122) is pulverized. Specifically, the dried material is pulverized with a fine pulverizer so that the particle diameter (median diameter by laser diffraction scattering method) is about several tens of nm to 100 ⁇ m.
  • antimony dope tin oxide used for this invention is manufactured by passing through each said process.
  • the vehicle is a medium in which antimony-doped tin oxide and / or colorant is dispersed and adhered to the substrate.
  • the ink may contain known vehicle components used in printing. Since the ink can be formed as oil-based ink, UV ink, oil-based / UV combined ink, or solvent-containing ink, vehicles suitable for each ink will be described below.
  • Vehicle suitable for oil-based ink for example, a resin, an oxidation polymerization catalyst, a solvent, or the like can be used alone or in combination.
  • the resin, the oxidation polymerization catalyst, and the solvent will be described below.
  • Resins contained in oil-based inks include linseed oil, tung oil and other drying oils, soybean oil, rapeseed oil and other semi-drying oils, alkyd resins produced by modification from semi-drying oils, and other modified alkyd resins, especially Use phenol-modified alkyd resin, epoxy-modified alkyd resin, urethane-modified alkyd resin, silicone-modified alkyd resin, acrylic-modified alkyd resin, vinyl-modified alkyd resin, neutralized acid alkyd resin, etc. Can do.
  • oxidation polymerization catalyst As the oxidation polymerization catalyst, a metal compound such as cobalt, vanadium, manganese, zirconium, lead, iron, cerium, or a salt of a long chain fatty acid may be used alone or in combination of two or more.
  • oxidation polymerization catalyst include cobalt borate, cobalt octylate, manganese octylate, zircon octylate, cobalt naphthenate, lead monoxide and the like.
  • a known solvent used for the ink may be selected in consideration of the boiling point of the solvent, the compatibility between the solvent and the resin, the drying property of the ink, the permeability to the printing material, and the like.
  • the solvent include mineral oil; aromatic oil such as toluene and xylene; ester such as ethyl acetate; ketone such as methyl ethyl ketone; alcohol such as isopropyl alcohol; glycol such as ethylene glycol, diethylene glycol and triethylene glycol; cellulose solvent; and high boiling mineral oil such as n-dodecane mineral oil.
  • Vehicle suitable for UV ink examples include photopolymerizable resins such as monomers, oligomers and binder polymers; photopolymerization initiators and the like.
  • photopolymerizable resins such as monomers, oligomers and binder polymers
  • photopolymerization initiators and the like.
  • the photopolymerizable resin and the photopolymerization initiator will be described below.
  • Photopolymerizable resins include epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, acrylated amine, acrylic saturated resin and acrylic acrylate, bisphenol A type epoxy acrylate acid anhydride addition acrylate, phenol novolac epoxy acrylate acid Carboxylic acid acrylates with hydroxyl anhydrides added to hydroxylated acrylates such as anhydride added acrylates, acid anhydride added acrylates of dipentaerythritol pentaacrylate, and carboxyls with acid anhydrides added to urethane acrylates with hydroxyl groups
  • Group-containing acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyglycerin epoxy Relate, water-soluble acrylates such as polyglycerol acrylate, monomers and oligomers such as acryloyl morpholine, may be used in combination either alone or two or more.
  • the oligomer is a resin that governs the basic physical properties of the UV ink, and the monomer mainly acts as a diluent and affects the curability and adhesiveness as well as the viscosity adjustment of the ink.
  • the photopolymerization initiator is a compound that generates radicals such as active oxygen when irradiated with ultraviolet rays.
  • the UV ink may contain a known photopolymerization initiator used for printing.
  • photopolymerization initiator examples include, but are not limited to, acetophenone, ⁇ -aminoacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-methylpropyl) ) Ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1- ON, 2-benzyl-2-dimethylamino-1- (4-mol Acetophenones such as linophenyl) -butanone; bezoin, beizoin methyl ether, be
  • a photopolymerization initiation assistant such as ethyl 4-dimethylaminobenzoate or isoamyl 4-dimethylaminobenzoate may be used in combination with the photopolymerization initiator.
  • an oil-based ink and a UV ink may be used in combination to form an oil-based / UV combined ink.
  • antimony-doped tin oxide is added to a vehicle for oil-based inks other than the solvent, and optionally a solvent comprising a vegetable oil component, a radically polymerizable monomer and / or oligomer, or a pigment dispersant is added to the bead mill or three-roll mill.
  • An ink mill base is obtained by dispersing the kneaded meat with a dispersing machine such as the above.
  • a photopolymerization initiator is added to the mill base for the ink, and if desired, other materials can be added to obtain an oil-based / UV combined ink.
  • the oil-based ink vehicle is obtained by dissolving the components described above as a vehicle suitable for oil-based inks, and the UV ink vehicle is prepared by dissolving the components described above as vehicles suitable for UV ink. Is. Further, a colorant may be added to the oil-based / UV combined ink.
  • Suitable vehicles for solvent-containing inks include at least a solvent.
  • a suitable vehicle for water-based ink includes water.
  • the vehicle suitable for the water-based ink may contain an organic solvent, a resin, or the like alone or in combination.
  • vehicles suitable for organic solvent-containing inks contain organic solvents and are substantially free of water. Further, the vehicle suitable for the organic solvent-containing ink may contain a resin.
  • the resin contained in the solvent-containing ink a resin described as a vehicle suitable for the oil-based ink or the UV ink may be used.
  • the resin contained in the water-based ink is preferably in the form of a water-soluble resin, a colloidal dispersion resin, or an emulsion resin.
  • a solvent described as a vehicle suitable for the oil-based ink may be used.
  • the ink may contain known adjuvants used in printing.
  • auxiliary agents include extender pigments, waxes, antifoaming agents, dispersants, plasticizers, crosslinking agents, leveling agents, conductivity imparting agents, penetrating agents, pH adjusting agents, preservatives or fungicides, and oxygen scavengers. And other additives. These adjuvants will be described below.
  • Extender pigments are frequently used when the viscosity of the ink is high and it is difficult to wipe the ink from the intaglio plate.
  • the extender pigment for example, barium sulfate, calcium carbonate, calcium sulfate, kaolin, talc, silica, corn starch, titanium dioxide, or a mixture thereof can be used.
  • the wax is an additive for imparting properties such as friction resistance, anti-blocking property, slipperiness and anti-scratch properties to the ink, and examples thereof include polyethylene wax and fluorinated wax.
  • the defoaming agent is an auxiliary agent used to suppress the generation of bubbles in the ink or reduce the bubbles generated in the ink.
  • the antifoaming agent for example, silicone compounds, polysiloxanes, polyglycols, polyalkoxy compounds and the like can be used alone or in combination.
  • examples of the antifoaming agent include BYK (registered trademark) -019, BYK (registered trademark) -022, BYK (registered trademark) -024, and BYK (registered trademark) -065 manufactured by Byk-Chemie. , And BYK (registered trademark) -088.
  • the dispersant is an auxiliary agent for improving the leveling property, stability and dispersibility of the ink. Specifically, the dispersant improves the wetting of the antimony-doped tin oxide or colorant by the vehicle component, or adsorbs the antimony-doped tin oxide or colorant to the vehicle component and / or is dispersed in the ink. It can be used to prevent reagglomeration of the antimony doped tin oxide or colorant.
  • dispersant examples include a low molecular dispersant, a polymer dispersant, a pigment derivative, and a coupling agent.
  • low molecular weight dispersant examples include soap, ⁇ -sulfo fatty acid ester salt (MES), alkylbenzene sulfonate (ABS), linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), and alkyl ether sulfate.
  • MES ⁇ -sulfo fatty acid ester salt
  • ABS alkylbenzene sulfonate
  • LAS linear alkylbenzene sulfonate
  • AS alkyl sulfate
  • alkyl ether sulfate examples include soap, ⁇ -sulfo fatty acid ester salt (MES), alkylbenzene sulfonate (ABS), linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), and alkyl ether sulfate.
  • Anionic compounds such as salts (AES) and alkylsulfuric acid triethanolamine; cationic compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chloride and alkylpyridinium chloride; amphoteric compounds such as amino acids, alkylcarboxybetaines, sulfobetaines and lecithins; Nonionic compounds such as fatty acid diethanolamide, polyoxyethylene alkyl ether (AE), and polyoxyethylene alkyl phenyl ether (APE) are exemplified.
  • a polymer having a portion corresponding to an anchor group and a barrier group may be arbitrarily used.
  • a non-aqueous polymer dispersant such as a partial alkyl ester of polyacrylic acid or a polyalkylene polyamine for the organic solvent-containing ink.
  • Water-based inks include naphthalene sulfonate formalin condensates, polystyrene sulfonates, polyacrylates, copolymers of vinyl compounds and carboxylic acid-containing monomers, and water-based polymers such as carboxymethyl cellulose. It is preferred to use a dispersant.
  • the pigment derivative is obtained by introducing a polar group such as a carboxyl group, a sulfone group, or a tertiary amino group into the pigment skeleton.
  • a polar group such as a carboxyl group, a sulfone group, or a tertiary amino group.
  • the pigment skeleton portion of the pigment derivative is easily adsorbed with the corresponding pigment, while the introduced polar group is excellent in affinity with the vehicle or other dispersant.
  • the pigment derivative can be synthesized by a known method according to the skeleton of the pigment contained in the ink.
  • dialkylaminomethylene copper phthalocyanine, amine salt copper phthalocyanine, and the like are used to form flexographic printing inks that contain phthalocyanine as a colorant.
  • the coupling agent is a material that adsorbs to the surface of the antimony-doped tin oxide or the colorant or chemically bonds to improve the adhesion between the antimony-doped tin oxide or the colorant and the vehicle.
  • the coupling agent include a silane coupling agent and a titanate coupling agent.
  • the plasticizer is an auxiliary agent for adjusting the film formability of the ink or the flexibility of the ink coating film.
  • plasticizers include aliphatic hydrocarbon oils such as naphthene oil and paraffin oil; liquid polydienes such as liquid polybutadiene and liquid polyisoprene; polystyrene; poly- ⁇ -methylstyrene; ⁇ -methylstyrene-vinylstyrene copolymer Hydrogenated rosin pentaerythritol ester; polyterpene resin; ester resin and the like.
  • the crosslinking agent is an auxiliary agent necessary for chemically bonding a plurality of substances, and is also called a gelling agent or a curing agent.
  • the crosslinking agent include isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, polymethylene polyphenyl polyisocyanate; trimethylolpropane-tris- ⁇ -N-aziridini Aziridine compounds such as lupropionate and pentaerythritol propane-tris- ⁇ -N-aziridinylpropionate; epoxy compounds such as glycerol polyglycidyl ether and trimethylolpropane polyglycidyl ether; aluminum triisopropoxide, mono- sec-Butoxyaluminum diisopropoxide, Aluminum tri-sec-butoxide
  • a leveling agent is an additive that, when added to an ink, lowers the surface tension of the ink and improves the surface smoothness of the coating film.
  • the leveling agent include silicone polymers, polyacrylate polymers, and polyvinyl ether polymers.
  • leveling agent for example, “BYK-310”, “BYK-323”, “BYK-320”, “BYK-377”, “BYK-UV3510”, “BYK-Silclean 3700”, “BYK” -UV3500 "and” BYK-UV3570 “” (both manufactured by Big Chemie Japan).
  • the conductivity imparting agent is an additive that imparts conductivity to the ink.
  • the conductivity imparting agent is preferably used in continuous ink jet printing.
  • Examples of the conductivity imparting agent include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as magnesium and calcium; and simple ammonium salts or quaternary ammonium salts. These salts are halogenated compounds (eg chloride, bromide, iodide, fluoride, etc.), perchlorate, nitrate, thiocyanate, formate, acetate, sulfate, sulfonate, propionate , Trifluoroacetate, triflate (trifluoro-methanesulfonate), hexafluorophosphate (eg potassium hexafluorophosphate), hexafluoro-antimonate, tetrafluoroborate, picrate and It may be a carboxylate or the like.
  • alkali metal salts such as lithium, sodium and potassium
  • alkaline earth metal salts such as magnesium and calcium
  • the penetrating agent is an additive for penetrating and fixing the ink to the printing medium.
  • the penetrant include potassium hydroxide, ethanol, isopropanol and the like.
  • the pH adjuster is an additive for controlling the pH of the ink within a predetermined range.
  • the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as acetic acid and benzoic acid; hydroxides such as sodium hydroxide and potassium hydroxide; halides such as ammonium chloride; sodium sulfate and the like. Sulfate such as potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, etc .; phosphates such as sodium hydrogen phosphate and sodium dihydrogen phosphate; organic acid salts such as ammonium acetate and sodium benzoate; tributylamine, And organic amines such as triethanolamine.
  • Preservatives or fungicides are additives for suppressing the generation or growth of microorganisms in the ink.
  • the antiseptic or fungicide include sodium benzoate, potassium sorbitanate, thiabendazole, benzimidazole, siabendazole, thiazosulfamide, pyridinethiol oxide, and the like. Further, it is preferable to contain a preservative or a fungicide in the water-based ink.
  • the oxygen scavenger is an additive used to remove dissolved oxygen in the ink.
  • the oxygen scavenger include organic oxygen scavengers such as ascorbic acid, catechol, erythorbic acid, pyrogallol, hydroquinone, reducing sugars, and tannic acid; and organic acid salts such as sodium ascorbate.
  • a polymerization inhibitor such as phenothiazine and t-butylhydroxytoluene; a sensitizer; a thermal stabilizer; an ultraviolet absorber; a light stabilizer; a light absorber; Anti-skinning agent; Antistatic agent; Conductive agent; Flame retardant; Transferability improver; Liquid repellent; Dry retarder; Antioxidant; Anti-set-off agent; or Nonionic surfactant An activator or the like may be included.
  • the adjuvants listed above can be used alone or in combination of two or more.
  • the colorant is a component that adds color to the ink.
  • the ink used in the present invention may contain a known colorant used for printing.
  • Examples of the colorant include inorganic pigments, organic pigments, dyes, organic pigments for toners, and the like.
  • inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, alumina white, calcium carbonate, ultramarine, graphite, aluminum powder, bengara, barium ferrite, copper and zinc alloy. Examples thereof include powder, glass powder, and carbon black.
  • organic pigments examples include soluble azo pigments such as ⁇ -naphthol pigments, ⁇ -oxynaphthoic acid pigments, ⁇ -oxynaphthoic acid anilide pigments, acetoacetate anilide pigments, and pyrazolone pigments; ⁇ -naphthol pigments Insoluble azo pigments such as pigments, ⁇ -oxynaphthoic acid anilide pigments, acetoacetanilide monoazos, acetoacetanilide disazos, pyrazolone pigments; copper phthalocyanine blue, halogenated (eg chlorine or brominated) copper phthalocyanine blue, Phthalocyanine pigments such as sulfonated copper phthalocyanine blue and metal-free phthalocyanine; quinacridone pigments, dioxazine pigments, selenium pigments (pyrantron, anthrone, indanthrone, anthrapyrimidine
  • the dye examples include azo dyes, complex salts of azo dyes and chromium, anthraquinone dyes, indigo dyes, phthalocyanine dyes, xanthene dyes, thiazine dyes, and the like.
  • the organic pigment includes a lake pigment.
  • a lake pigment is obtained by dyeing a dye on an inorganic pigment or extender, and the lake pigment also has water insolubility according to the water insolubility of the inorganic pigment or extender.
  • lake pigments include the fanal (FANAL (registered trademark)) color series available from BASF.
  • the organic dye for toner is an organic dye that can be contained in the toner, and has charging properties in addition to the general characteristics of the colorant.
  • a dye or an organic pigment may be used, but a dye is preferred from the viewpoint of transparency and coloring power.
  • the colorant can be used to adjust the color tone of the printing layer (A) and the printing layer (B).
  • a color matching dye examples include "Microlith (registered trademark) red” manufactured by Sakuramiya Chemical Co., Ltd., "Microlith (registered trademark) blue” manufactured by Sakuramiya Chemical Co., Ltd., and "Microlith (registered trademark) yellow” manufactured by Sakuramiya Chemical Co., Ltd. Etc.
  • the functional material may be inorganic or organic, and may be an additive that imparts functionality to the ink.
  • chromic materials examples include chromic materials, magnetic pigments, ultraviolet absorbers, optically variable materials, pearl pigments, and the like.
  • a chromic material is a material that develops a color in response to energy such as light, heat, electricity, and fades when the energy is blocked or lost.
  • the chromic material include fluorescent pigments, excited luminescent pigments, temperature-sensitive color changing materials, photochromic materials, and stress luminescent materials.
  • the colorants listed above can be used alone or in combination of two or more.
  • the blending ratio of each component contained in the ink is preferably about 0 to 20% by weight of the colorant when the viscosity of the ink is adjusted to about 50 to 1000 poise.
  • the vehicle is preferably about 10 to 90% by weight
  • the adjuvant is preferably 0 to about 10% by weight
  • the antimony-doped tin oxide is preferably about 1 to 50% by weight. .
  • the blending ratio of each component contained in the ink is about 1 to 50% by weight of the colorant when the viscosity of the ink is adjusted to about 50 to 1000 poise.
  • the vehicle is about 10-90% by weight and the adjuvant is preferably 0-about 10% by weight.
  • the viscosity of the ink can be arbitrarily adjusted as long as it is within the viscosity range suitable for the printing method used.
  • Infrared absorbing inks are obtained by dispersing antimony-doped tin oxide and / or colorants in a vehicle, optionally with auxiliary colorants.
  • a mixer such as a single-screw mixer or a twin-screw mixer; a two-roller mill, a three-roller mill, a bead mill, a ball mill, a sand grinder, an attritor, or the like, an antimony-doped tin oxide and The colorant can be dispersed in the vehicle.
  • the average particle diameter of the antimony-doped tin oxide in the ink is 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 60 ⁇ m or less, 40 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, It may be 5 ⁇ m or less, 2.5 ⁇ m or less, 1 ⁇ m or less, 0.5 ⁇ m or less, 0.1 ⁇ m or less, 0.05 ⁇ m or less, or 0.025 ⁇ m or less, and the average particle diameter is 0.001 ⁇ m or more, 0 It may be 0.01 ⁇ m or more, or 0.015 ⁇ m or more.
  • the average particle diameter refers to the median diameter of the laser diffraction / scattering method.
  • Means for adjusting the average particle size of the antimony-doped tin oxide in the ink to a range of 0.001 ⁇ m to 200 ⁇ m is not limited, but means for pulverizing the antimony-doped tin oxide during the production of the antimony-doped tin oxide; It is considered to be a combination with means for dispersing antimony-doped tin oxide in the vehicle during the production of the ink.
  • the antimony-doped tin oxide is sufficiently pulverized by the step S118 or S124.
  • the antimony-doped tin oxide is sufficiently dispersed in the vehicle by a mixer or a meat grinder.
  • the printed matter of the present invention is formed by printing ink on a substrate by a known printing method to form a printing layer (A) and a printing layer (B), and the printing layer (A) is at least partially formed from the printing layer (B). Can be obtained by overlapping.
  • the printing layer (A) and the printing layer (B) can be formed on the substrate by the same or different printing methods. Furthermore, when performing printing, it is preferable to form the printing layer (B) before or after the formation of the printing layer (A) so that the printing layer (A) and the printing layer (B) overlap.
  • the printing method may be plate printing or non-plate printing.
  • plate printing for example, relief printing such as flexographic printing and letterpress printing; lithographic printing such as offset printing; gravure printing; intaglio printing such as direct printing plate printing and etching printing; stencil printing such as screen printing; Is mentioned.
  • flexographic printing is a printing method in which ink is adhered to a roll having a concave portion, the ink in the concave portion is transferred to the convex portion of the relief cylinder, and then the ink on the convex portion is transferred to the printing medium.
  • Typographical printing is a printing method that prints using letterpress.
  • the letterpress is a plate obtained by forming or assembling line drawing parts such as type letters, ruled lines, patterns, and photographs as convex parts.
  • Offset printing is a printing method in which the ink attached to the plate is transferred to a transfer body, and then the ink attached to the transfer body is transferred to a substrate. Further, a rubber blanket is generally used as the transfer body.
  • Gravure printing is a printing method in which cells with recesses are formed in a plate cylinder, ink is put into the cells, and excess ink on the surface of the plate cylinder is scraped off with a doctor blade while the ink in the cells is transferred to the substrate. It is.
  • Intaglio printing forms depressions on the plate surface by line printing or etching, deposits ink on the entire plate, wipes ink adhering to the plate surface other than the depressions, and In this printing method, the printing medium is pressed against the printing medium, and the ink in the recesses is transferred to the printing medium.
  • the plate may be not only a flat plate but also a body plate.
  • the recesses formed on the printing plate correspond to the line drawing part, and the line drawing part is composed of a line drawing recessed from the surroundings. Further, a portion other than the concave portion on the printing plate is called a non-line drawing portion. Therefore, the cells used for gravure printing are not formed on the intaglio plate surface.
  • Screen printing is a printing method in which ink is put on a screen plate and ink is pushed out from the screen plate by sliding of a squeezee.
  • the screen plate is formed by applying a screen to the frame and providing an image area and a non-image area on the image by a resist method.
  • the non-image area is closed with a resin or the like by a resist method.
  • plateless printing examples include inkjet printing; other plateless printing such as electrophotography, thermal printing, and thermal transfer printing.
  • Inkjet printing is a printing method in which ink is ejected as ink droplets from a nozzle and deposited on a substrate. Inkjet printing does not use a plate, does not apply pressure to the substrate, and the nozzle and the substrate do not contact each other, so printing is faster without damaging the substrate compared to printing methods that use plates. It can be performed.
  • the method of ejecting ink from a nozzle is roughly divided into a continuous method and an on-demand method.
  • the continuous method is a method for electrically controlling the flight trajectory of the ink liquid by continuously discharging the ink liquid.
  • the on-demand method is a method for ejecting a necessary amount of ink during printing.
  • the on-demand method is roughly classified into a piezo method, a thermal method, and an electrostatic induction method, depending on a method of pressurizing and discharging ink.
  • the printed matter of the present invention can be obtained by using a single or a combination of the printing methods described above.
  • the printing layer (A) and / or the printing layer (B) contains the antimony-doped tin oxide
  • the printing layer (A) and / or the printing layer (B) is an infrared absorption printing layer. . Therefore, when one of the printing layer (A) and the printing layer (B) is an infrared absorbing printing layer and the other is an infrared non-absorbing printing layer, the printed matter is observed with an infrared detector, and the infrared absorbing printing layer A pattern is seen.
  • the printed matter (1) laminated in the order of infrared non-absorbing printing layer (4) / infrared absorbing printing layer (3) / substrate (2) is non-infrared absorbing. It can be observed from the printed layer (4) side.
  • the pattern of the infrared non-absorbing print layer (4) hides the pattern of the infrared absorbing print layer (3).
  • a pattern of the infrared non-absorbing print layer (4) is seen as shown in FIG.
  • both the printing layer (A) and the printing layer (B) are infrared absorption printing layers
  • the printing layer (A) and the density difference of the infrared absorption pattern can be detected between the overlapping portion and the non-overlapping portion of the printing layer (B).
  • the authenticity of the printed matter can be determined using the presence or absence of the infrared absorption pattern or the density gradient of the infrared absorption pattern.
  • determination methods may be combined with the determination method based on the infrared absorption print pattern and / or the infrared non-absorption print pattern.
  • Other determination methods include, for example, other functional materials such as chromic materials, magnetic pigments, ultraviolet absorbers, optical variable materials, and pearl pigments described above in the infrared non-absorbing print layer and / or infrared absorbing print layer. The method of making it contain and utilizing the functionality of a functional material is mentioned.
  • the used firing furnace is a shuttle-type firing furnace with a cooling device (manufactured by Tsuji Electric Furnace).
  • Steps 100-124 were performed as described in FIG. 1 using 118.8 g of metastannic acid and 1 g of antimony trioxide.
  • the aerated firing step (S114) was performed for about 8 hours with the temperature in the aerated furnace set to about 1100 ° C.
  • the aeration cooling step (S116) was performed at a cooling rate of about 200 [° C./hour] or more.
  • Examples 2 to 7 and Comparative Examples 1 and 2 were performed as described in Table 1 below.
  • the content of antimony oxide in the obtained antimony-doped tin oxide was changed by changing the weight of metastannic acid and antimony trioxide and / or the time of the aeration firing step (S114). I let you.
  • Comparative Example 1 a commercially available antimony-doped tin oxide raw material was prepared.
  • Example 5 and 6 the commercial item of the comparative example 1 was used for the ventilation baking process (S114) and the ventilation cooling process (S116).
  • the cooling rate in the ventilation cooling step (S116) was 200 [° C./h] or more in Example 5, and less than 200 [° C./h] in Example 6.
  • Example 7 a simple mixture of metastannic acid and antimony trioxide was subjected to an aeration firing step (S114) and an aeration cooling step (S116).
  • the content of antimony oxide in the product is measured by an order analysis method using a fluorescent X-ray analyzer RIX-1000 (manufactured by Rigaku Corporation). Moreover, as measurement conditions, the measurement is performed using antimony-doped tin oxide as a powder. The powder is measured under the condition that the particle diameter (median diameter by laser diffraction scattering method) is 120 nm.
  • FIGS. 2 to 5 are diagrams showing the results of X-ray diffraction by the antimony-doped tin oxide of the example
  • FIG. 6 is a diagram showing the results of X-ray diffraction of the comparative example.
  • the vertical axis indicates “intensity (CPS)” of reflected light when X-rays are irradiated
  • the horizontal axis indicates “2 ⁇ (deg)”.
  • CPS Counterbalance Per Second
  • “2 ⁇ ” indicates an irradiation angle when the measurement object is irradiated with X-rays.
  • the reason for “2 ⁇ ” is that if the angle (incident angle) for irradiating X-rays is ⁇ , the reflection angle is also ⁇ , and the sum of the incident angle and the reflection angle is 2 ⁇ . It is.
  • the graph of FIG. 2 (B) is a graph showing the result of X-ray diffraction by antimony-doped tin oxide of Example 2.
  • points where the intensity of reflected light greatly increases are generated at a plurality of locations.
  • the crystallinity is calculated using the measured values of 2 ⁇ (deg) and intensity (CPS) at the point where the intensity of the reflected light is the highest among the points where the intensity of the reflected light increases.
  • FIG. 7 is a conceptual diagram schematically showing a method for calculating the crystallinity.
  • the crystallinity can be calculated from the measurement result of X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • CPS Since CPS is the intensity (level) of reflected light, it has a waveform height in the illustrated example.
  • ⁇ 2 ⁇ is the width of the half width corresponding to a half value of the maximum value (peak value) of CPS obtained by the X-ray diffraction measurement (in FIG. 7, the length A1 is the same as the length A2. Length).
  • Example 2A is a graph showing the result of X-ray diffraction by the antimony-doped tin oxide of Example 1.
  • the maximum value of CPS is about 15000, and the waveform appearing at the point where the intensity of the reflected light is the highest is sharp and the width of the skirt portion is narrow. It has a sharp waveform.
  • the graph of FIG. 6 (A) is a graph showing the result of X-ray diffraction by the commercially available product of Comparative Example 1.
  • ⁇ 2 ⁇ the width of the bottom part of the waveform at which the CPS value reaches its peak is wider than those of the above-described Examples 1 to 7. This is considered to be caused by a large amount of impurities because it is antimony-doped tin oxide produced without using a vaporization purification method.
  • the graph of FIG. 6 (B) is a graph showing the result of X-ray diffraction by the product of Comparative Example 2.
  • the width of the bottom part of the waveform at which the CPS value reaches its peak is wider than those of the above-described Examples 1 to 7. This is considered to be caused by a large amount of impurities because it is antimony-doped tin oxide manufactured without using the above-described vaporization purification method.
  • This can also be seen from the fact that the crystallinity of Comparative Example 2 is lower than that of Example 2 even though Comparative Example 2 has the same antimony oxide content as Example 2.
  • the infrared absorption effect was measured by measuring the light reflectance using a spectrophotometer.
  • the equipment used, the measurement conditions, and the measurement method are as follows.
  • the infrared absorption pigment of an Example and a comparative example all are measuring by making a particle size (median diameter in a laser diffraction scattering method) into 120 nm. Further, the reflectance of the standard white plate was set as a standard value of about 100%. In addition, the said measuring method is based on "How to obtain
  • the acrylic / silicone varnish described in the above (2) includes a solid content such as a resin and a solvent that volatilizes and disappears when dried.
  • the acrylic / silicone varnish solids weight ratio is 40% by weight, the acrylic / silicone varnish solids content is 38 parts, the infrared absorbing pigment is 5 parts, and the infrared absorbing pigment solids weight ratio is 11.6. % By weight. The remaining 88.4% by weight is resin and / or other additives.
  • FIG. 8 shows that antimony-doped tin oxide in which antimony oxide is dissolved in the crystal lattice of tin oxide has an infrared absorption effect.
  • the infrared absorption effect is high, and the solid content of the antimony-doped tin oxide pigment, which is a particularly general printing condition, is desirable.
  • the weight ratio is 11.6% by weight and the reflectance is 30% or less, when a printed matter is observed with an authenticity determination device such as an infrared camera, a printed part containing antimony-doped tin oxide and other parts The difference is large and 10 out of 10 people can be distinguished, so it is easy to use for authenticity determination and is preferred.
  • Examples 2 to 4 having an antimony oxide content of 2.8% by weight or more maintain a reflectance of 30% or less in that region.
  • the comparative example 2 that has not undergone the aeration firing process is compared with the examples 2, 5 and 6 that have undergone the aeration firing process. It is clear that the infrared absorption effect is low. That is, the aeration firing process can improve the crystallinity of the antimony-doped tin oxide, thereby improving the infrared absorption effect. This is supported by comparing the crystallinity of Examples 2, 5, and 6 and Comparative Example 2 in Table 1 below.
  • Example 5 performed at a cooling rate of 200 [° C./hour] or higher was more than Example 6 performed at a cooling rate of less than 200 [° C./hour].
  • the half width ( ⁇ 2 ⁇ ) is narrow and the degree of crystallinity is high.
  • adjusting the cooling rate to 200 [° C./hour] or more in the ventilation cooling step contributes to the improvement in crystallinity of the antimony-doped tin oxide.
  • Examples 1 to 6 have an average reflectance in the visible light wavelength range (380 nm to 780 nm) and an infrared wavelength range (780 to 1100 nm) than Example 7. )
  • the average reflectance difference is large. Therefore, it can be seen that the antimony-doped tin oxides of Examples 1 to 6 can be used in a wide range of applications without being restricted by the color exhibited by antimony-doped tin oxide as compared with the antimony-doped tin oxide of Example 7. .
  • the crystallinity can be improved with the minimum content of antimony oxide, and antimony-doped tin oxide having a sufficient infrared absorption effect is produced. can do.
  • the obtained antimony-doped tin oxide has an antimony oxide content of 9.3 wt% or less and an antimony oxide tin oxide having a content of 9.9 wt% is substantially equal to or higher than that. Infrared absorption effect is obtained.
  • Infrared absorbing offset printing ink was obtained by mixing 80 parts by weight of the vehicle with 20 parts by weight of the infrared absorbing pigment of Example 2 and kneading with a three roller mill.
  • methyl ethyl ketone and toluene were mixed at a weight ratio of 1: 1 to obtain a solvent mixture.
  • the above composition was dispersed until the viscosity when measured with Zahn cup # 3 was about 18 seconds to obtain an infrared absorbing gravure printing ink.
  • a commercially available binder for flexographic printing ink (UV VECTA coat varnish Zaan cup # 4 45 seconds manufactured by T & K TOKA) was prepared.
  • the infrared absorbing pigment of Example 2 was pulverized until the average particle size became 280 nm using a pulverizer (“NanoJet Mizer” manufactured by Aisin Nano Technorose Co., Ltd.). In a mixer (Pony Mixer, Inoue Seisakusho Co., Ltd.), 30 parts by weight of the pulverized infrared absorbing pigment, 20 parts by weight of the binder resin, and 10 parts by weight of water were mixed to obtain a mixture.
  • the mixture was kneaded in a bead mill (Buhler Co., Ltd. K8 type lab bead mill), 30 parts by weight of the binder resin and 10 parts by weight of water were further added, and kneaded to obtain an infrared-absorbing flexographic printing ink.
  • a bead mill Buhler Co., Ltd. K8 type lab bead mill
  • Example 2 After mixing 5 parts by weight of the infrared absorbing pigment of Example 2 with 95 parts by weight of the UV curable varnish, the mixture was stirred with a mixer (Pony Mixer manufactured by Inoue Seisakusho Co., Ltd.) to prepare an infrared absorbing screen printing ink.
  • a mixer Pulmony Mixer manufactured by Inoue Seisakusho Co., Ltd.
  • infrared absorbing effect of infrared absorbing printing layer According to the following conditions (I) to (V), infrared absorbing ink was printed on high-quality paper (Shiraoi high-quality paper made by Nippon Paper Industries Co., Ltd.) and dried to form an infrared-absorbing printing layer to obtain five types of printed matter. .
  • Print sample preparation conditions Offset printing machine RI tester Ink volume: 0.125cc Ink film thickness: about 1 ⁇ m
  • the light reflectance of three types of printed samples was measured according to the following measurement conditions: (Measurement condition) Measuring device: UV-visible spectrophotometer U-4000 (manufactured by Hitachi, Ltd.) Measurement item: Reflectance (%) Measurement wavelength: 350-2500 nm
  • FIG. 12 shows the reflectance in the wavelength range of 350 to 1500 nm for the indigo (C), red (M), and yellow (Y) process inks.
  • FIG. 12 is a graph showing the reflectance of a printed matter obtained by offset printing of CMY process inks.
  • the reflectance of the printed matter obtained by gravure printing, flexographic printing, screen printing, or inkjet printing is the same as the reflectance of the printed matter obtained by offset printing. it is conceivable that. Therefore, by combining the reflectance graph of the CMY process ink shown in FIG. 12 and the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11, various infrared absorbing printing layers are formed in the printed matter of the present invention. The relationship between color tone and infrared absorptivity when formed by a printing method can be expected.
  • the red and yellow process inks do not absorb light in the infrared wavelength region (780 to 1100 nm).
  • the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11 since the average reflectance in the infrared wavelength region is lower than the average reflectance in the visible light wavelength region (380 nm to 780 nm), it is higher than that of visible light. Infrared light is also considered to be absorbed. Therefore, if the antimony-doped tin oxide used in the present invention is contained in red or yellow ink, or if the infrared absorbing ink used in the present invention is used as red or yellow ink, the color tone of red or yellow is affected. It can be seen that the ink can be provided with infrared absorptivity.
  • the indigo process ink slightly absorbs light in the infrared wavelength region (780 to 1100 nm).
  • the ratio of the indigo process ink to absorb infrared light is so low that it does not need to be considered.
  • the infrared absorbing ink containing antimony-doped tin oxide obtained in Examples 1 to 7 and containing no colorant does not correspond to black, indigo, red or yellow ink.
  • the infrared-absorbing ink containing antimony-doped tin oxide obtained in Examples 1 to 7 and containing no colorant has high brightness and a light white color. The effect on the color tone of yellow ink is considered to be small. Therefore, the infrared absorbing ink containing antimony-doped tin oxide obtained in Examples 1 to 7 and containing no colorant can be grasped as a special color ink or functional ink suitable for various printing methods. In that case, the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11 can be regarded as graphs representing the light reflection characteristics of the special color ink used in the present invention.
  • the obtained printed matter was observed using an infrared camera (Dino-Lite Pro manufactured by ANMO), and the infrared absorption effect was evaluated as follows. +: The infrared absorption effect of the layer formed with the infrared absorbing ink can be confirmed. -: The infrared absorption effect of the layer formed with the infrared absorbing ink cannot be confirmed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Printing Methods (AREA)

Abstract

L'invention concerne un article imprimé dans lequel une couche imprimée (A) et une couche imprimée (B) sont disposées sur un matériau de base. La couche imprimée (A) chevauche au moins partiellement la couche imprimée (B). La couche imprimée (A) et/ou la couche imprimée (B) incluent de l'oxyde d'étain dopé à l'antimoine. L'oxyde d'étain dopé à l'antimoine inclut de l'oxyde d'étain et de l'oxyde d'antimoine et satisfait (a) et/ou (b) : (a) la largeur de demi-valeur (∆2θ) d'une crête au voisinage de 2θ=27˚ obtenue à partir d'une mesure de diffraction des rayons X n'est pas supérieure à 0.30 ; et/ou (b) la teneur en oxyde d'antimoine est de 0.5 à 10.0 % en poids en utilisant le poids de l'oxyde d'étain dopé à l'antimoine comme référence, et le degré de cristallisation, c'est-à-dire une valeur obtenue en divisant, par la largeur de demi-valeur (∆2θ), la valeur de crête de la crête au voisinage de 2θ=27˚ obtenue à partir de la mesure de diffraction des rayons X, est d'au moins 58427.
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
GB2535884A (en) * 2015-02-25 2016-08-31 Inovink Ltd Improvements in relation to security printing
JP2019112504A (ja) * 2017-12-21 2019-07-11 サカタインクス株式会社 ラミネート用水性プライマーと水性白色インクジェット用インク組成物セット
US20220348034A1 (en) * 2019-09-13 2022-11-03 Kyodo Printing Co., Ltd. Printed object
WO2024110769A1 (fr) * 2022-11-24 2024-05-30 Any Biztonsági Nyomda Nyrt. Document de sécurité pourvu d'éléments de sécurité actifs dans la lumière infrarouge
JP7503637B2 (ja) 2020-01-10 2024-06-20 花王株式会社 水性エネルギー硬化型インクジェットインク

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JP2013119204A (ja) * 2011-12-07 2013-06-17 National Printing Bureau 透過潜像画像を有する印刷媒体
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WO2013146937A1 (fr) * 2012-03-28 2013-10-03 共同印刷株式会社 Support d'impression filigrané pour prévention des contrefaçons
WO2013168812A1 (fr) * 2012-05-11 2013-11-14 共同印刷株式会社 Oxyde d'étain dopé à l'antimoine, pigment apte à absorber le rayonnement infrarouge, encre apte à absorber le rayonnement infrarouge, matière imprimée et procédé de fabrication d'un oxyde d'étain dopé à l'antimoine

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JPH08337500A (ja) * 1995-04-10 1996-12-24 Sumitomo Chem Co Ltd 酸化スズウィスカおよびその製造方法
JPH10316425A (ja) * 1997-05-12 1998-12-02 Tokuyama Corp 球状複合酸化錫粉末の製造方法
JP2003176132A (ja) * 2001-09-28 2003-06-24 Sumitomo Metal Mining Co Ltd 日射遮蔽用アンチモン錫酸化物粒子および日射遮蔽膜形成用塗布液ならびに日射遮蔽膜
JP2009137088A (ja) * 2007-12-05 2009-06-25 Kyodo Printing Co Ltd 印刷物及び赤外線吸収インキを用いた印刷方法
JP2013119204A (ja) * 2011-12-07 2013-06-17 National Printing Bureau 透過潜像画像を有する印刷媒体
WO2013146937A1 (fr) * 2012-03-28 2013-10-03 共同印刷株式会社 Support d'impression filigrané pour prévention des contrefaçons
WO2013147033A1 (fr) * 2012-03-29 2013-10-03 三菱マテリアル株式会社 Matière de coupure du rayonnement infrarouge
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WO2013168812A1 (fr) * 2012-05-11 2013-11-14 共同印刷株式会社 Oxyde d'étain dopé à l'antimoine, pigment apte à absorber le rayonnement infrarouge, encre apte à absorber le rayonnement infrarouge, matière imprimée et procédé de fabrication d'un oxyde d'étain dopé à l'antimoine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2535884A (en) * 2015-02-25 2016-08-31 Inovink Ltd Improvements in relation to security printing
GB2535884B (en) * 2015-02-25 2018-05-09 Inovink Ltd Improvements in relation to security printing
US10259255B2 (en) 2015-02-25 2019-04-16 Inovink Limited Security printing
JP2019112504A (ja) * 2017-12-21 2019-07-11 サカタインクス株式会社 ラミネート用水性プライマーと水性白色インクジェット用インク組成物セット
US11401435B2 (en) 2017-12-21 2022-08-02 Sakata Inx Corporation Aqueous primer and aqueous white inkjet ink composition set for lamination
JP7170391B2 (ja) 2017-12-21 2022-11-14 サカタインクス株式会社 ラミネート用水性プライマーと水性白色インクジェット用インク組成物セット
US20220348034A1 (en) * 2019-09-13 2022-11-03 Kyodo Printing Co., Ltd. Printed object
JP7503637B2 (ja) 2020-01-10 2024-06-20 花王株式会社 水性エネルギー硬化型インクジェットインク
WO2024110769A1 (fr) * 2022-11-24 2024-05-30 Any Biztonsági Nyomda Nyrt. Document de sécurité pourvu d'éléments de sécurité actifs dans la lumière infrarouge

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